Coating compositions, methods for producing hydrophilic coatings on substrates, and medical devices containing such coatings

Abstract

The present disclosure provides a polymerizable compound of formula [1], wherein G is a residue of a hydrophobic hydroxy-functional oligomer, n is 1 to 10, and each R is independently a C to C 20 a residue of an aliphatic, cycloaliphatic, or aromatic hydrocarbon compound, and Z is a moiety having a polymerizable group; [Formula 1] TIFF2023525674000013.tif22147 The present disclosure relates to a coating composition comprising a hydrophilic polymer; a photoinitiator; optionally one or more additional components; and a solvent. The polymerizable compound of formula [1] is typically present in an amount of 2.0 to 30% by weight, based on the total dry weight of the composition. Such a coating composition allows for the production of a single-layer hydrophilic coating that adheres well to the surface of a polymer substrate without the need for a primer layer or chemically modifying the substrate surface. When wet, the coating exhibits excellent lubricity and durability. In a further aspect, the present disclosure provides a method for applying a hydrophilic and optionally lubricious coating to an article; and an article, such as a medical device, such as a catheter, guidewire, or implantable delivery device, having a single-layer hydrophilic and optionally lubricious coating on at least a portion of its surface.

Description

Detailed Description of the Invention

[0001] [Field] The disclosed invention relates to a photocurable coating composition for producing a hydrophilic coating on a substrate that becomes lubricious when wetted with a wetting agent. The invention also relates to a method for producing a hydrophilic or lubricious coating on a substrate, such as the surface of a medical device or part thereof, and to the coated part or medical device, such as a catheter for intravascular or urinary applications.

[0002] [background] Medical devices, such as intravascular devices like guidewires, introducers, catheters, and intermittent catheters, are inserted into and subsequently removed from tortuous pathways within the body to perform their functions without causing discomfort to the patient or irritating or damaging the patient's soft tissues. For this reason, the surfaces of such devices must be lubricious, or smooth. Lubricious surface properties not only facilitate manipulation within the patient's vascular system and minimize soft tissue damage, but can also facilitate the evacuation of fluids from the body. Therefore, such medical devices often contain a hydrophilic surface layer or coating. This coating becomes lubricious and acquires low-friction properties upon wetting and imbibing, for example, by applying an aqueous wetting fluid for a period of time before inserting the device into the patient's body, or by contact with bodily fluids during insertion.

[0003] Relevant properties of such (lubricious) hydrophilic coatings for use on medical devices include low extractables to prevent particulate release during use, good adhesion to surfaces, and high durability or wear resistance, in addition to biocompatibility and low friction properties in wet conditions.

[0004] Most hydrophilic coatings are based on crosslinked, water-soluble polymers, which have a relatively low crosslink density and readily absorb water upon exposure to the source, sometimes swelling to several times their dry thickness to form a hydrogel-like layer. Many medical devices, such as guidewires and catheters, are made from metals or flexible plastic materials, such as polyolefins, PVC, polyamide 12 or polyamide block copolymers, and polyurethanes. Generally, the adhesion of hydrophilic polymers to the surface of such substrates is insufficient to meet the requirements for use as coatings on medical devices. Therefore, depending on the substrate, pretreatment, such as chemical modification of the surface using plasma or corona treatment, and / or application of a primer or basecoat layer, may be required to improve the adhesion level between the substrate and the hydrophilic coating.

[0005] WO 2007 / 065720A2 describes a two-layer hydrophilic coating for urinary catheters, which comprises a primer layer and a topcoat layer produced by applying a non-aqueous primer composition containing a polyether having a polymerizable group and a photoinitiator, followed by an aqueous topcoat composition containing a nonionic and an ionic hydrophilic polymer and a photoinitiator, respectively, followed by UV curing.

[0006] WO 2008 / 031596 A1 discloses a photocurable hydrophilic coating composition comprising an acrylamide-functional polymerizable compound, a nonionic hydrophilic polymer and optionally an ionic hydrophilic polymer, and a photoinitiator. This composition is used to form a two-layer hydrophilic coating on the polymer surface of a medical device, for example, by applying a primer layer using the composition described in WO 2006 / 056482 A1 or WO 2007 / 065720 A2.

[0007] EP 0 591 091 A1 proposes a coating composition that will provide a durable, single-layer lubricious coating on a substrate: the composition is an aqueous solution of a hydrophilic polymer and, optionally, an osmolality-increasing compound, in which a water-insoluble polymeric binder compound is present in a dispersed state to improve adhesion.

[0008] The hydrophilic coating solution described in EP 2173397 A2 contains a multifunctional acrylic network former, a hydrophilic polymer, two photoinitiators, and an acid-functionalized acrylate as an adhesion promoter, this last compound co-reacting with the network former and will bond to the polymeric surface of a substrate such as a catheter.

[0009] Disadvantages of known coating compositions and systems may include long curing times, which result in compositions, two-layer systems with limited shelf life, and / or relatively high manufacturing costs. Additionally, the cured coatings may exhibit very high levels of leachables or extractables and poor mechanical robustness, especially after wetting and swelling with water. While various improvements have been proposed and described in the literature, a need still appears to exist for coating compositions that can be efficiently processed and applied on a variety of substrates, preferably as hydrophilic coatings that exhibit a level of adhesion such that the use of chemical surface pretreatments or primer coatings can be omitted, and in which the cured coatings become lubricious upon contact with wetting agents and exhibit a balanced combination of adhesion and durability.

[0010] [overview] It is an object of the present disclosure to provide coating compositions that overcome at least some of the above problems, i.e., coating compositions that are stable on storage, can be efficiently applied as a single layer hydrophilic coating on a substrate, and / or result in coatings that exhibit strong lubricity when wet.

[0011] According to the aspects and embodiments as described herein below and characterized in the claims, there is provided a photocurable coating composition suitable for producing a hydrophilic coating on a substrate, which coating becomes lubricious upon contact with a wetting agent, and which composition can be efficiently applied and cured to form a single layer hydrophilic coating on a variety of substrates while exhibiting good adhesion, lubricity, and durability in use. Accordingly, one aspect of the present invention is a claimed coating composition, more particularly a photocurable coating composition suitable for producing a hydrophilic coating that becomes lubricious when wet, comprising: (a) a polymerizable compound of formula [1], wherein G is a residue of a hydrophobic hydroxy-functional oligomer; n is 1 to 10; and each R is independently a C to C 20 a residue of an aliphatic, cycloaliphatic, or aromatic hydrocarbon compound, and Z is a moiety having a polymerizable group; [ka] (b) a hydrophilic polymer; (c) a photoinitiator; (d) optionally one or more additional ingredients; (e) a solvent for components (a) to (c); and The composition contains the polymerizable compound of formula [1] in an amount of 2.0 to 30% by mass based on the total dry mass of the composition.

[0012] It has been surprisingly found that such coating compositions can be used to produce well-adhering, single-layer hydrophilic coatings on the surfaces of a variety of polymer substrates, such as aliphatic polyamides, polyamide block copolymers, polyurethanes, and polyvinyl chloride, typically without the need for an adhesion-promoting primer layer or chemically modifying the substrate surface. The coating compositions are stable, can be stored for several years before use, and can be efficiently applied to substrates using conventional coating equipment with relatively short cycle times. When wetted, such as with an aqueous wetting agent, the coatings exhibit excellent lubricity and durability.

[0013] EP 0 591 091 A1 discloses a coating composition for producing a single-layer hydrophilic coating on a substrate, but also teaches that it is possible to obtain a coating with sufficient adhesion only if the hydrophobic polymeric binder compound is dispersed and not dissolved in an aqueous solution of other components. A disadvantage of such a composition may be its limited stability and shelf life.

[0014] U.S. Patent Application Publication No. 2018 / 0312697A1 describes a radiation-curable coating composition containing an acrylic polymer having a polymerizable group, a compound having multiple polymerizable groups, a urethane (meth)acrylate having 2 to 4 polymerizable groups, and a photopolymerization initiator. This composition can be cured to produce a highly crosslinked coating layer, which exhibits excellent appearance and repairability from surface damage such as scratches. Such coatings lack the ability to absorb significant amounts of water, which is necessary to form a hydrogel exhibiting lubricity. The applied urethane (meth)acrylate compound does not contain residues of hydrophobic hydroxy-functional oligomers.

[0015] In another aspect, the present invention relates to a hydrophilic coating obtainable by curing a layer of a coating composition according to the present invention.

[0016] A further aspect of the present invention is applying a coating composition according to the present invention to at least a portion of the surface of an article; at least partially removing the solvent from the applied coating composition; curing the applied coating composition by exposure to UV light during or after solvent removal to form a hydrophilic coating; Optionally, contacting the hydrophilic coating with a wetting fluid to form a lubricious coating. The present invention relates to a method for applying a hydrophilic and optionally lubricious coating to an article, comprising:

[0017] Another aspect of the present invention relates to articles, such as medical devices, obtainable by the methods of the present invention, having a single-layer hydrophilic coating and optionally a lubricious coating on at least a portion of their surface. Examples of articles that can benefit from having such a coating include intravascular devices, such as cardiovascular and neurovascular devices; urological devices for the treatment of the urinary tract or urinary system; and devices for ophthalmic use, such as catheters, guidewires, and delivery devices for, for example, prosthetic heart valves or intraocular lenses.

[0018] Although this specification generally relates to and illustrates polyether diol-based polymerizable compounds, other hydrophobic, oligomeric, or polymeric compounds having terminal groups capable of reacting with isocyanate groups can also be used to prepare polymerizable compounds that are suitable for use in coating compositions.

[0019] Detailed Description of the Embodiments Coatings or surface layers that are capable of becoming lubricious or slippery upon contact with a wetting agent, such as an aqueous composition, are described herein as hydrophilic coatings, and the resulting coatings, which after wetting are typically hydrogels, are described as lubricious coatings.

[0020] In the context of this disclosure, hydrophobicity refers to the physical property of a molecule or surface that is seemingly repelled by water, as opposed to hydrophilicity, which refers to attracting water. Hydrophobic compounds tend to be non-polar and have an affinity for other neutral molecules and non-polar solvents. Because water molecules are polar, most hydrophobic compounds have limited or no solubility in water. Depending on their structure, hydrophobic molecules can cluster in water to form droplets, or in the presence of surfactants, form micelles or other semi-ordered structures.

[0021] A single-layer coating refers to a coating layer applied onto a substrate in one or, optionally, multiple coating steps from one coating composition, as opposed to a two-layer coating applied from two different coating compositions, such as a primer and a topcoat composition. A primer refers to a coating composition or undercoat that is applied to a substrate surface to enhance the adhesion of a subsequent topcoat that provides a specific function but exhibits poor adhesion when applied directly to the substrate surface.

[0022] According to one aspect, the present invention provides a method for manufacturing a semiconductor device comprising: (a) a polymerizable compound of formula [1] wherein G is the residue of a hydrophobic hydroxy-functional oligomer; n is 1 to 10; and each R is independently a C to C 20 a residue of an aliphatic, cycloaliphatic, or aromatic hydrocarbon compound, and Z is a moiety having a polymerizable group; [ka] (b) a hydrophilic polymer; (c) a photoinitiator; (d) optionally one or more additional ingredients; (e) a solvent for components (a) to (c); Includes; The present invention provides a photocurable coating composition suitable for producing hydrophilic coatings, wherein the polymerizable compound of formula [1] is present in an amount of 2.0 to 30% by weight, based on the total dry weight of the composition.

[0023] The coating compositions of the present invention are photocurable, meaning that they can be reacted or crosslinked by exposure to electromagnetic radiation to form a water-insoluble but water-swellable hydrophilic polymer network. The intensity and wavelength of the radiation can be selected depending on the type and amount of photoinitiator and polymerizable or reactive component present, as well as the desired crosslink density. In particular, appropriate wavelengths in the UV, visible, or IR portions of the spectrum can be used; typically, a UV light source is used to initiate curing. High-energy radiation, such as E-beam and gamma rays, can also be applied to cure the coating. Those skilled in the art will be able to select appropriate radiation sources and conditions based on their own knowledge, this disclosure, and optionally some experimentation.

[0024] [Polymerizable compound of formula [1]] A coating composition for producing a hydrophilic coating comprises at least one polymerizable compound of formula [1], also referred to as component (a). While the composition may contain a single such polymerizable compound, it may also contain a mixture of two or more chemically distinct polymerizable compounds of formula [1], e.g., differing in one or more of G, Z, or R1. Furthermore, the polymerizable compound may be a mixture of chemically similar compounds, e.g., compounds having different numbers of polymerizable groups, such as from 1 to 10. For a single compound or molecule, n will be an integer; for a mixture of compounds, the number n represents the average number of polymerizable groups per molecule (which can be calculated based on the type and amount of starting materials used in the synthesis of the compound or can be analytically determined). In embodiments, the composition comprises a polymerizable compound of formula [1] with a functionality n greater than 1, e.g., at least 1.1, to provide a specific degree of crosslinking in the cured coating. In embodiments, the polymerizable compound is multifunctional, having a functionality n of at least 1.2, 1.4, 1.6, 1.8, 1.9, or 2.0. In embodiments, n is up to 8, 6, 4, 3, or 2.5. In other embodiments, n is about 1.8 to 3, or preferably about 1.8 to 2.2.

[0025] The polymerizable compound contains a group G, which is the residue of a hydrophobic, hydroxy-functional oligomer. While not wishing to be bound by any theory, the inventors hypothesize that the hydrophobicity of G and the polymerizable compound, possibly in conjunction with the presence of urethane (and / or urea) linkages, plays an important role in the interaction and adhesion of the cured coating with the surface of the substrate. The oligomer typically has a (number-average) molar mass Mn of about 200 to 8000 g / mol. In embodiments, the oligomer has a molar mass Mn of at least 300, 500, or 700 g / mol. In other embodiments, the molar mass Mn is at most 7000, 6000, 5000, or 4000 g / mol. This molar mass range can affect the hydrophobicity of the compound of formula [1], providing a balance between solubility in the coating composition, affinity for the surface of the substrate, and the degree of crosslinking of the composition upon curing. The molar mass of an oligomer can be determined using known methods, such as GPC using polystyrene standards and THF as solvent, or can be calculated from its functionality n and the number of hydroxy end groups per mass unit, which can be determined by chemical analysis, such as titration.

[0026] The polymerizable compound contains a group G that is the residue of a hydroxy-functional hydrophobic oligomer, which may be selected from the group consisting of polyethers, polyesters, polycarbonates, polyurethanes, polyepoxides, polyamides, poly(meth)acrylamides, poly(meth)acrylates, polyolefins, or any combination thereof. In embodiments, the hydroxy-functional oligomer is a polyether, preferably a water-insoluble polyether. Examples of suitable polyethers include polytetrahydrofuran (also called poly(tetramethylene ether)), poly(tetramethylene oxide), or poly(1,4-butanediol) (typically abbreviated as PTHF); or copolymers thereof, such as a copolymer based on 1,4-butanediol and 2-methyl-1,4-butanediol (also called copolymer of tetrahydrofuran and methyltetrahydrofuran, typically abbreviated as PTGL). In an embodiment, the hydroxy-functional oligomer may be partially present in the compound in the form of a dimer or trimer, for example, due to chain extension resulting from the reaction of an oligomer having two hydroxyl groups with a diisocyanate compound during the synthesis of the polymerizable compound of formula [1].

[0027] In embodiments, component (a) further comprises a polymerizable compound containing a group G that is the residue of a hydrophobic, amine-functional oligomer. The hydrophobic oligomer has functionality and can be selected from the same group of oligomers as described above for the hydroxy-functional oligomers. That is, such polymerizable compounds contain urea linkages and can be represented by formula [1a], where each R and Z can independently be the same as described herein for compounds of formula [1]. In further embodiments, component (a) comprises or consists of a mixture of compounds of formula [1] and [1a], the amount of the latter compound being at most 80, 60, 40, 20, 10, or 5% by weight, based on the total amount of component (a). In another embodiment, component (a) consists (essentially) of compounds of formula [1a]. [ka]

[0028] In the polymerizable compound of formula [1], each R1 is independently a C6 to C 20 R1 is a residue of an aliphatic, cycloaliphatic, or aromatic hydrocarbon compound. R1 is typically generated by synthesizing a polymerizable compound from a hydroxy-functional oligomer, a diisocyanate compound, and a (hydroxy-functional) compound having a polymerizable group. In an embodiment, each R1 is such a residue derived from a diisocyanate compound selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate (TDI), 1,4-phenylene diisocyanate, hexamethylene diisocyanate (HDI), tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), or isophorone diisocyanate (IPDI). In other embodiments, each R1 is independently a residue of 2,4-toluene, 2,6-toluene, hexane, butane, cyclohexane, or isophorone. In other embodiments, each R1 is a residue of TDI, HDI, or IPDI.

[0029] In the polymerizable compound of formula [1], Z is a moiety having a polymerizable group. The polymerizable group may be any group known to those skilled in the art that reacts with other similar groups under the influence of radiation and in the presence of a photoinitiator to form oligomers or polymers, for example, via a radical-induced addition reaction. A suitable polymerizable group activated by a photoinitiator can co-react with a hydrophilic polymer present in the coating composition to form a graft on the polymer and / or crosslink the polymer. Those skilled in the art will be able to select an appropriate group based on general knowledge. In embodiments, the polymerizable group is an unsaturated group and may be selected from an olefinic group, a styrenic group, or a (meth)acrylic group. The polymerizable compound of formula [1] may also have different Z moieties, i.e., a mixture of compounds having different polymerizable groups. The Z moiety forming part of the polymerizable compound of formula [1] may be, for example, the result of reacting at least one hydroxy-functional compound having a polymerizable group with the isocyanate group of R1.

[0030] In an embodiment, Z of the polymerizable compound of formula [1] is a moiety having a (meth)acrylic group. In a further embodiment, Z is a (meth)acrylic compound of formula [2], and each R2 is independently C1 to C 10 alkyl, and each R3 is independently hydrogen or methyl. [ka]

[0031] In further embodiments, Z is a moiety of formula [2] and each R3 is hydrogen; i.e., Z comprises an acrylate group. In other embodiments, each R2 is independently C2-C4 alkyl. In embodiments, each R2 is ethyl or propyl. In other embodiments, each R2 is ethyl.

[0032] In embodiments, the polymerizable compound of formula [1] generally has a number-average molar mass (Mn) of at least 500 g / mol, or at least 750 g / mol, or 1000 g / mol. Typically, the polymerizable compound has an Mn of at most 100,000 g / mol, or at most 50,000, 25,000, 10,000, 6,000, or at most 4,000 g / mol. Polymerizable compounds with molar masses within such ranges can provide cured coatings with favorable crosslink density, i.e., an appropriate balance of water swellability (to provide lubricity) and mechanical robustness (abrasion resistance and adhesion).

[0033] In embodiments, the polymerizable compound of formula [1] is soluble in relatively polar solvents but is insoluble or has only very limited solubility in water. In the context of the present disclosure, this means that at least 1 g, preferably at least 2, 3, 4, or 5 g, of the polymerizable compound of formula [1] can be dissolved in 100 g of the solvent of the coating composition at 25° C.

[0034] In embodiments, the polymerizable compound of formula [1] can be prepared by reacting a hydroxy-functional oligomer with a diisocyanate and a hydroxy-functional compound having a polymerizable group. Such reactions are known in the art, and one skilled in the art would be able to select appropriate procedures and conditions to carry out such synthesis. For example, the hydroxy-functional oligomer can be first reacted with a diisocyanate having a molar ratio of isocyanate to hydroxy groups of 2, followed by reaction of the remaining isocyanate groups with a hydroxy-functional compound having a polymerizable group. If statistical chain extension of the oligomer is not desired, the reaction can be carried out with a molar excess of diisocyanate, which can be removed, for example, by distillation, before reaction with the compound having the polymerizable group. In an exemplary embodiment, the polymerizable compound according to formula [1] is the reaction product of a tetrahydrofuran-based or tetrahydrofuran and methyltetrahydrofuran-based copolyether diol, toluene diisocyanate, and hydroxyethyl acrylate.

[0035] Photocurable coating compositions suitable for producing hydrophilic coatings capable of becoming lubricious when wet include a polymerizable compound of formula [1], which may be present in an amount of about 2.0 to 30 wt. % based on the total dry weight of the composition; i.e., based on the sum of the weights of components a), b), c), and d), excluding solvent component e). The amount based on the total dry weight of the coating composition can alternatively be reported as based on the weight of the dried and cured coating obtained from the composition, which is substantially the same.

[0036] In other embodiments, component (a) may be present in the composition in a relatively low amount of at least 0.5 wt. %, but in that case, the cure time and / or amount of photoinitiator may need to be increased to obtain satisfactory performance of the coating on the substrate. Thus, in such embodiments, the coating composition comprises the multifunctional polymerizable compound of formula [1] in an amount of at least 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.4, 1.5, or 1.8 wt. %, based on the total dry weight of the composition.

[0037] In further embodiments, the coating composition comprises the multifunctional polymerizable compound of Formula [1] in an amount of at least 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, or 6.0 wt. % based on the total dry weight of the composition. In other embodiments, the coating composition comprises the multifunctional polymerizable compound of Formula [1] in an amount of at most 25, 20, 15, 12, or 10 wt. % based on the total dry weight of the composition.

[0038] [Hydrophilic polymer] The coating composition for producing a hydrophilic coating comprises at least one hydrophilic polymer as component (b). Herein, a hydrophilic polymer is understood to be a high molar mass, linear or branched polymer that exhibits an affinity for water and other polar liquids and may be soluble in water. Such hydrophilic polymers attract and / or absorb water even when present in a cured coating on a surface. The hydrophilic polymer capable of imparting hydrophilic properties to the coating may be a natural, synthetic, or biological polymer, a copolymer, or a mixture of two or more such (co)polymers. The hydrophilic polymer is soluble in the (generally polar organic) solvent of the coating composition and is typically a non-ionic polymer. The hydrophilic polymer may be at least one polymer selected from the group consisting of poly(lactams) such as polyvinylpyrrolidone, polyurethanes, copolymers of (meth)acrylates and (meth)acrylic acid, polyvinyl alcohols, polyvinyl ethers, polyethyleneimines, polyethylene oxides, polyamides, polyanhydrides, polyphosphazenes, cellulosics such as carboxymethylcellulose, hydroxymethylcellulose, and hydroxypropylcellulose, heparin, dextran, polysaccharides such as chitosan, hyaluronic acid, alginates, gelatin, and chitin, polyesters such as polylactides, polyglycolides, and polycaprolactones, polypeptides such as collagen, albumin, oligopeptides, polypeptides, short-chain peptides, proteins, and oligonucleotides. Typically, the hydrophilic polymer does not contain polymerizable groups such as unsaturated groups, but the polymer may co-react with species formed from or by a photoinitiator and / or a polymerizable compound of formula [1]. In embodiments, the hydrophilic polymer is susceptible to reaction with radicals, for example, generated by exposing the coating composition to radiation, resulting in a specific degree of crosslinking. This cross-linking will still allow the hydrophilic polymer to absorb water, but will reduce or prevent extraction of the polymer from the coating when present, for example, on the surface of a medical device that is exposed to aqueous media during use.Typically, the hydrophilic polymer has a molar mass Mn in the range of about 8 to 5000 kg / mol. In embodiments, the molar mass is about 20 to 3000, or 200 to 2000 kg / mol. The molar mass (Mn) can be determined using common techniques such as GPC or light scattering.

[0039] In an embodiment, the hydrophilic polymer in the coating composition is polyvinylpyrrolidone (PVP) or polyethylene oxide. In a further embodiment, the hydrophilic polymer is PVP or a copolymer thereof. For PVP and polymers of the same class, the K value is typically used as an indication of their molar mass. The K value can be determined by the Viscotek Y501 automatic relative viscometer, method W1307, revision 5 / 2001; the manual can be found at www.ispcorp.com / products / hairscin / index_3.html. In an embodiment, the PVP has a molar mass equivalent to at least K15, or preferably at least K30 or K80. In a further embodiment, at least K90 and at most K120 PVP is applied in the coating composition.

[0040] In an alternative embodiment, the coating composition may optionally contain, in addition to the nonionic hydrophilic polymer, at least one ionic or ionizable hydrophilic polymer, also referred to as a polyelectrolyte. Herein, a polyelectrolyte is understood to be a high-molar mass, linear or branched polymer in which 5 to 100% of its monomer units contain ionizable groups or groups that become ionized when the polyelectrolyte is in an aqueous medium of appropriate pH. Herein, ionizable is understood to mean that it is not (completely) ionized in a neutral aqueous solution, i.e., a solution having a pH between 6 and 8, but can be ionized by changing conditions such as pH. The presence of a polyelectrolyte in the coating composition can improve the lubricity and dry-out time of a wetted hydrophilic coating. Herein, dry-out time is defined as the period during which a hydrophilic coating maintains its lubricity in open air after a device containing the hydrophilic coating is removed from the wetting liquid in which it was stored and / or wetted. Hydrophilic coatings with improved or longer dry-out times are less likely to lose water and dry out before insertion into a patient's body or upon contact with, for example, a mucous membrane or vein within the body. This tendency to lose water and dry out can lead to complications and / or tissue damage during device manipulation within the body. Considerations for selecting an appropriate polyelectrolyte include, for example, its biocompatibility, as well as its solubility and viscosity in aqueous media relative to the solvent used in the coating composition. Polyelectrolytes with relatively high molar masses are preferred for increasing dry-out times and will also exhibit reduced tendency to migrate from the coating. Therefore, for ease of handling and solubility, the molar mass (Mn) is preferably at least 20, 50, or 100 kg / mol and less than 1000, 500, or 300 kg / mol.

[0041] Examples of ionizable (or ionized) groups that may be present in polyelectrolytes are ammonium, phosphonium, sulfonium, carboxylate, sulfate, sulfinic, sulfonic, phosphate, and phosphonic groups. Such groups are very effective at binding water. Polyelectrolytes also contain Na + , Li + Or K + Alkali metal ions such as Ca 2+ and Mg 2+ Anions may also be present, particularly when the polyelectrolyte contains a quaternary amine salt, e.g., a quaternary ammonium group. Such anions may include, for example, Cl. - , Br - , I - and F - and the like, as well as sulfates, nitrates, carbonates and phosphates.

[0042] Suitable polyelectrolytes are, for example, salts of homo- and copolymers of acrylic acid, salts of homo- and copolymers of methacrylic acid, salts of homo- and copolymers of maleic acid, salts of homo- and copolymers of fumaric acid, salts of homo- and copolymers of monomers containing sulfonic acid groups, homo- and copolymers of monomers containing quaternary ammonium salts, and mixtures and / or derivatives thereof. Examples of suitable polyelectrolytes are poly(acrylamide-co-acrylic acid) salts, for example, poly(acrylamide-co-acrylic acid) sodium salt, poly(acrylamide-co-methacrylic acid) salts, for example, poly(acrylamide-co-methacrylic acid) sodium salt, poly(methacrylamide-co-acrylic acid) salts, for example, poly(methacrylamide-co-acrylic acid) sodium salt, poly(methacrylamide-co-methacrylic acid) salts, for example, poly(methacrylamide-co-methacrylic acid) sodium salt, poly(acrylic acid) salts, for example, poly(acrylic acid) sodium salt, poly(methacrylic acid) salts, for example, poly(methacrylic acid) sodium salt, poly(acrylic acid-co-maleic acid) salts, for example, poly(acrylic acid-co-maleic acid) sodium salt, poly(methacrylic acid-co-maleic acid) salts, for example, poly(methacrylic acid-co-maleic acid) sodium salt, poly(acrylamide-co -maleic acid) salts such as poly(acrylamide-co-maleic acid) sodium salt, poly(methacrylamide-co-maleic acid) salts such as poly(methacrylamide-co-maleic acid) sodium salt, poly(acrylamido-2-methyl-1-propanesulfonic acid) salts, poly(4-styrenesulfonic acid) salts, poly(acrylamide-co-dialkylammonium chloride), quaternized poly[bis-(2-chloroethyl)ether-alt-1,3-bis[3-(dimethylamino)propyl[urea]], polyallylammonium phosphate, poly(diallyldimethylammonium chloride), poly(sodium trimethyleneoxyethylenesulfonic acid), poly(dimethyldodecyl(2-acrylamidoethyl)ammonium bromide), poly(2-N-methylpyridinium ethylene iodide), polyvinylsulfonic acid, and salts of poly(vinyl)pyridine, polyethyleneimine, and polylysine.

[0043] Particularly suitable polyelectrolytes for use in the present (non-aqueous) compositions are copolymer polyelectrolytes, which can be random or block copolymers. The copolymer polyelectrolytes are copolymers containing at least two different monomer units, at least one of which contains an ionizable or ionized group and at least one of which does not contain an ionizable or ionized group. An example of such a copolymer polyelectrolyte is poly(acrylamide-co-acrylic acid) salt.

[0044] It should be noted that ionic or ionizable polymers can also function as osmolality-increasing components, as can low molar mass ionic or ionizable compounds such as sodium chloride.

[0045] When the coating composition includes a polyelectrolyte, its concentration is relatively low, at least lower than the concentration of the hydrophilic polymer. In embodiments, the coating composition includes a polyelectrolyte, and the weight ratio of the nonionic hydrophilic polymer to the polyelectrolyte is 99:1 to 60:40, or 95:5 to 75:25.

[0046] The amount of hydrophilic polymer in the coating composition can vary widely, depending on the other ingredients, and generally is at least 10, 20, 30, 40, 50, 60, 70, or 80 weight percent, and up to 97, 95, 93, 92, 91, or 90 weight percent, based on the dry weight of the composition.

[0047] [Photopolymerization initiator] The coating composition for producing the hydrophilic coating of the present invention comprises at least one photoinitiator as component (c). Norrish type I and / or Norrish type II initiators may be applied in the coating composition. Both types are free radical-generating photoinitiators, but are distinguished by the process by which the initiating radicals are formed. Compounds that generate radicals by cleavage of a monomolecular bond upon irradiation are called Norrish type I or homolic photoinitiators. Norrish type II photoinitiators generate radicals indirectly by hydrogen abstraction from a suitable synergist, which may be a low molar mass compound or a polymer.

[0048] Examples of suitable Norrish Type I or free radical photoinitiators are benzoin derivatives, methylolbenzoin and 4-benzoyl-1,3-dioxolane derivatives, benzil ketals, α,α-dialkoxyacetophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, bisacylphosphine oxides, acylphosphine sulfides, halogenated acetophenone derivatives, and the like.Commercially available examples of suitable Norrish Type I photoinitiators include Irgacure 2959 (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone), Irgacure 651 (benzil dimethyl ketal or 2,2-dimethoxy-1,2-diphenylethane, Ciba-Geigy), Irgacure 184 (1-hydroxy-cyclohexyl-phenyl ketone as the active ingredient, Ciba-Geigy), Darocur 1173 (2-hydroxy-2-methyl-1-phenylpropan-1-one as the active ingredient, Ciba-Geigy), Irgacure 907 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, Ciba-Geigy), Irgacure 1173 ... 369 (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one as the active ingredient, Ciba-Geigy), Esacure KIP 150 (poly{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one}, Fratelli Lamberti), Esacure KIP 100F (a blend of poly{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one} and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Fratelli Lamberti), Esacure KTO 46 (a blend of poly{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one}, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and a methylbenzophenone derivative, Fratelli Lamberti), acylphosphine oxides such as Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide, BASF), Irgacure 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, Ciba-Geigy), Irgacure 1700 (a 25:75% blend of bis(2,6-dimethoxybenzoyl)2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Ciba-Geigy). Mixtures of Type I photoinitiators can also be used.

[0049] Examples of Norrish Type II photoinitiators that can be used in the coating compositions of the present invention include benzophenone, xanthone, derivatives of benzophenone (e.g., chlorobenzophenone), substituted benzophenone blends of benzophenone and benzophenone derivatives (e.g., Photocure 81, a 50 / 50 blend of 4-methylbenzophenone and benzophenone), Michler's ketone, ethyl Michler's ketone, thioxanthone and other xanthone derivatives such as Quantacure ITX (isopropylthioxanthone), benzil, anthraquinone (e.g., 2-ethylanthraquinone), coumarin, or chemical derivatives or combinations of these photoinitiators. Further examples include 2-benzoylbenzoic acid, 3-benzoylbenzoic acid, 4-benzoylbenzoic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 4-benzoyl-N,N,N-trimethylbenzene-methaminium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propanaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthate). and salts of derivatives thereof such as sodium, potassium, calcium, magnesium, iron, copper, and zinc salts.

[0050] In embodiments, the coating composition includes a Norrish type II photoinitiator. The presence of such an initiator can be advantageous because such compounds can induce crosslinking of polymers such as PVP in addition to initiating polymerization of the polymerizable compound of formula [I].

[0051] In a further embodiment, the coating composition comprises a mixture of Norrish Type I and Norrish Type II photoinitiators. When a mixture is applied, the weight ratio of Norrish Type I photoinitiator to Norrish Type II photoinitiator is typically 10:1 to 1:10. In an embodiment, the weight ratio is 7:1 to 1:7, or 5:1 to 1:5, preferably 2:1 to 1:2.

[0052] In embodiments, the amount of photoinitiator in the coating composition can be 0.2 to 5 weight percent based on the dry weight of the composition, hi other embodiments, the amount of photoinitiator in the coating composition is at least 0.3, 0.4, or 0.5 weight percent, and at most 4.5, 4.0, 3.5, or 3.0 weight percent, based on the dry weight of the composition.

[0053] [Additional Ingredients] In addition to the above-described components (a) to (c), the coating composition for producing a hydrophilic coating may optionally contain at least one additional component (or additive) as component (d). Examples of additional components include a hydrophilic polymerizable compound (hence different from component (a)); a low-molar mass osmolality-increasing component, such as urea, glycerol, or an ionic or ionizable compound such as sodium chloride. Other examples include one or more conventional additives, such as surfactants; antioxidants; radical stabilizers; UV absorbers; light stabilizers; thermal polymerization inhibitors; (silane) coupling agents; coating surface modifiers; leveling agents; colorants, such as pigments or dyes; preservatives; plasticizers; lubricants; fillers; wetting improvers; or chain transfer agents. Most such additive compounds are typically applied at relatively low concentrations, such as 0.01 to 3% by weight, based on the total dry weight of the coating composition.

[0054] In an embodiment, the coating composition includes a surfactant as component (d). The surfactant can, for example, improve the spreading of the coating composition on the surface of the substrate and / or the surface properties of the applied and cured coating. Generally, surfactants are surface-active agents composed of a hydrophobic moiety, usually a long-chain alkyl, attached to a hydrophilic or water-solubility-enhancing functional group. Depending on the charge present in the hydrophilic portion of the molecule (after dissociation in an aqueous medium), surfactants can be classified into ionic surfactants, such as anionic or cationic surfactants, and nonionic surfactants. Examples of ionic surfactants include sodium dodecyl sulfate (SDS), sodium cholate, bis(2-ethylhexyl) sulfosuccinate sodium salt, cetyltrimethylammonium bromide (CTAB), lauryldimethylamine oxide (LDAO), N-lauryl sarcosine sodium salt, and sodium deoxycholate (DOC). Examples of nonionic surfactants include alkyl polyglucosides such as Triton® BG-10 Surfactant and Triton CG-110 Surfactant, branched secondary alcohol ethoxylates such as the Tergitol® TMN series, ethylene oxide / propylene oxide copolymers such as the Tergitol L series and Tergitol XD, XH, and XJ Surfactants, nonylphenol ethoxylates such as the Tergitol NP series, octylphenol ethoxylates such as the Triton X series, secondary alcohol ethoxylates such as the Tergitol 15-S series, and specialty alkoxylates such as Triton CA Surfactant, Triton N-57 Surfactant, Triton X-207 Surfactant, Tween 80 (polyethylene glycol sorbitan monooleate, having about 80 ethylene oxide units), and Tween 20 (polyethylene glycol sorbitan monolaurate; having about 20 ethylene oxide units). When used, surfactants are typically applied at relatively low concentrations, e.g., 0.1 to 2% by weight based on the total weight of the dry coating.

[0055] In embodiments, the coating composition also includes, as component (d), one or more additional polymerizable compounds, such as polymerizable compounds having more hydrophilic properties different from the polymerizable compound of formula [1]. These compounds may have a low molar mass or may be oligomeric, and may have an average of one or more polymerizable groups, such as olefinic, styrenic, or (meth)acrylic unsaturated groups. Suitable examples include polyfunctional compounds having two or more polymerizable groups, often referred to as crosslinking monomers. Such compounds are well known to those skilled in the art and can be added to increase and / or control the crosslink density of the cured coating. Examples include various commercially available crosslinkers, such as dimethacrylates, diacrylates, or diacrylamides. Other examples include oligomeric compounds, such as poly(ethylene oxide) diacrylate (PEG-DA) or poly(ethylene oxide) diacrylamide (PEG-DAA). When such compounds are present in the coating composition, their concentration can be at least 0.1, 1, 2, or 3 wt. % and up to 30, 25, 20, 15, 10, or 5 wt. %. In other embodiments, the concentration of such hydrophilic polymerizable compounds is lower than the concentration of the hydrophobic polymerizable compound of Formula [1], for example, up to 80, 60, 40, 20, or 10 wt. % relative to the weight of the hydrophobic polymerizable compound.

[0056] In an embodiment, component (d) is soluble in a solvent and dissolved in the coating composition. Those skilled in the art will understand that, depending on the type of component (d), such a component can also be dispersed in the composition as long as it does not adversely affect the formation and curing of a coating layer from the coating composition.

[0057] [solvent] The coating composition for producing a hydrophilic coating comprises at least one solvent as component (e), in which components (a)-c, and optionally (d)) can be homogeneously dissolved. Examples of suitable solvents are generally relatively polar organic liquids. In embodiments, the solvent is miscible with water, at least to some extent. Examples of suitable solvents include C1-C6 alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, and t-butanol; acetone; methyl ethyl ketone; tetrahydrofuran; and mixtures thereof. The solvent may contain water, provided that such a mixed solvent is capable of dissolving at least components (a)-(c), preferably all components (a)-(d), of the composition. In a further embodiment, the solvent is at least one selected from methanol, ethanol, and isopropanol, including mixtures thereof or mixtures containing some water, such as 96% ethanol (containing about 4% water). In embodiments, the solvent or mixture of solvents has a relatively high volatility or a relatively low boiling point, for example up to 150, 130, 120, 110, or 100° C., so that the solvent can evaporate quickly from the layer of coating composition applied to the substrate; thereby allowing for relatively fast solidification of the liquid composition and fast curing of the coating, allowing for short cycle times and an efficient and economical coating process.

[0058] The coating composition can include widely varying amounts of solvent, allowing for the creation of solutions with tunable viscosities for use in various coating techniques. In other embodiments, the coating composition includes an amount of solvent such that the solution has a relatively low viscosity, allowing for the application of thin coating layers onto elongated articles such as catheters and guidewires, for example, via a dip-coating process.

[0059] In embodiments, the coating composition comprises 40 to 99.5 wt.% solvent, based on the total weight of the composition, hi other embodiments, the coating composition comprises at least 50, 60, 70, 80, 85, 90 wt.% solvent, and up to 99.0, 98.5, 98, 97.5, 97.0, 96.5, 96.0, 95.5, or 95.0 wt.% solvent.

[0060] In an exemplary embodiment, the photocurable coating composition comprises, based on the total dry weight of the composition: · 2.0 to 30 mass% of component (a); · 97.8 to 30% by mass of component (b); 0.2 to 5% by mass of component (c); and 0 to 35% by mass of component (d) and the sum of (a) to (d) is 100%.

[0061] In another exemplary embodiment, the photocurable coating composition comprises, based on the total dry weight of the composition: 3.5 to 30% by mass of component (a); · 96.3 to 30 mass% of component (b); 0.2 to 5% by mass of component (c); and 0 to 35% by mass of component (d) and the sum of (a) to (d) is 100%.

[0062] In another embodiment, the photocurable coating composition comprises, based on the total dry weight of the composition, 4 to 25 weight percent of component (a); 95.2 to 46 weight percent of component (b); 0.3 to 4 weight percent of component (c); and 0.5 to 25 weight percent of component (d); and the sum of (a) through (d) is 100%.

[0063] In a further embodiment, the photocurable coating composition comprises, based on the total dry weight of the composition, 5 to 20 weight percent of component (a); 93.6 to 46 weight percent of component (b); 0.4 to 3.5 weight percent of component (c); and 1 to 20 weight percent of component (d); and the sum of (a) through (d) is 100%.

[0064] In another embodiment, the photocurable coating composition comprises, based on the total dry weight of the composition, 6 to 12 weight percent of component (a); 91.5 to 75 weight percent of component (b); 0.5 to 3 weight percent of component (c); and 2 to 10 weight percent of component (d); and the sum of (a) through (d) is 100%.

[0065] In an exemplary embodiment, the photocurable coating composition has a viscosity of about 5 to 200 mm, as determined using an Ubbelohde viscometer at 25° C. as shown in the Experimental Section. 2 / s (or cSt; centistokes). The viscosity of the coating composition is one of the variables that can be varied to affect the thickness of the coating layer applied to the substrate surface. For vascular applications such as catheters, a relatively thin hydrophilic coating layer may be preferred. Thus, in embodiments, the coating composition has a kinematic viscosity of about 5-50 mm 2 / s; preferably at least 6, 8 or 10, and at most 40, 35, 30 or 25 mm 2 If a somewhat thicker hydrophilic coating layer is desired, such as in the case of an intermittent catheter or a Foley catheter, the coating composition may have a kinematic viscosity of 50 to 200 mm / s. 2 / s; preferably at least 60, 70, 80, 90 or 100 mm 2 / s, maximum 450, 400, 350, 300 or 250 mm 2 The coating composition is typically prepared by methods known in the art, such as by dissolving all of the ingredients in a selected solvent under mild conditions.

[0066] In another aspect, the present invention relates to a hydrophilic coating obtained by drying and curing a layer of a coating composition according to the present invention.

[0067] In a further aspect, the present invention relates to a lubricious hydrophilic coating obtainable by drying and curing a layer of a coating composition according to the present invention and thereafter contacting the coating with a wetting agent.

[0068] A wetting agent is typically defined as a liquid composition containing water, which is used to wet a hydrophilic coating, for example, by contacting the surface of the coating on a substrate so that the coating absorbs a specific amount of one or more components of the wetting agent and increases the lubricity of the coating. Both oil-based and water-based wetting agents have been described in the art. In embodiments, a water-based or aqueous wetting agent is applied to wet the hydrophilic coating of the present invention. Typically, such aqueous wetting agents contain, in addition to water, one or more other components known in the art; compounds that reduce surface tension and facilitate spreading of the wetting agent on the coating surface, such as surfactants or other water-soluble organic compounds such as higher alcohols or glycerol esters; compounds that stabilize the wetted coating, such as antioxidants like vitamin E; compounds that help better retain water in the wetted hydrophilic coating, such as salts or urea; compounds that control pH, such as organic or inorganic buffers; and / or antibiotic or antibacterial compounds. Depending on the situation, those skilled in the art will be able to select a wetting agent with the appropriate composition based on general knowledge and, optionally, some routine experimentation.

[0069] A further aspect of the present invention is applying to at least a portion of the surface of the article a coating composition according to the present invention as described herein above; at least partially removing the solvent from the applied coating composition; curing the applied coating composition by exposure to UV light during or after solvent removal to form a hydrophilic coating; Optionally, contacting the hydrophilic coating with a wetting agent to form a lubricious coating. The present invention relates to a method for applying a hydrophilic and optionally lubricious coating to an article, comprising:

[0070] In this method, the coating composition can be applied to the surface using techniques known in the art, such as dip coating, spray coating, wash coating, vapor deposition, or by using a brush or roller, depending on the type of article. For elongated, relatively thin articles such as guidewires and catheters, dip coating may be the preferred application technique. The articles can have a variety of shapes, including films, sheets, rods, tubes, molded parts of regular or irregular shapes, fibers, and fabrics; and can be made from different materials and have surfaces with different textures, such as porous, non-porous, smooth, rough, uniform, or uneven surfaces. An advantage of the coating composition of the present invention is that it can be applied directly to the surface, preferably cleaned, without the need for chemical pretreatment with a primer coating. Therefore, the process typically does not include a step of chemically pretreating the surface to be coated or applying a primer composition before applying the coating composition of the present invention.

[0071] The thickness of the applied coating composition layer, and the thickness of the hydrophilic coating after drying and curing, can be controlled by varying the coating parameters, such as immersion time, withdrawal speed, or viscosity of the hydrophilic coating formulation, and the number of coating steps. Typically, the thickness of the dried hydrophilic coating on the surface of the article ranges from 0.1 to 300 μm, preferably at least 0.2, 0.3, 0.4, 0.5 μm, and more preferably at most 200, 100, 50, 40, 30, 20, or 15 μm.

[0072] In this method, the photocuring step involves exposing the article to a suitable radiation source, such as a UV lamp, for a time sufficient to substantially react the polymerizable compounds in the coating. Those skilled in the art will be able to select appropriate conditions, such as the intensity and wavelength of the radiation, as well as the exposure time, depending on the type of photoinitiator and based on general knowledge and some experimentation. Generally, the exposure or curing time is from about 5, 10, or 20 seconds to about 50, 100, 250, or 500 seconds, depending on the type and energy of the radiation source used.

[0073] In the optional step of contacting the hydrophilic coating with a wetting agent to form the lubricious coating, the wetting agent may be any composition known in the art for such purpose, hi embodiments, the wetting agent is an aqueous wetting agent as described herein above.

[0074] Another aspect of the invention relates to articles obtainable by the methods of the invention, such as medical devices, having a single layer, hydrophilic, optionally lubricious coating on at least a portion of its surface.

[0075] In embodiments, the medical device has a single layer hydrophilic coating that, after wetting, exhibits a lubricity of up to 15 g, determined as average friction by the method described in the Experimental Section using a Harland Friction Tester FTS 6000. In other embodiments, the medical device has a single layer hydrophilic coating that, after wetting, exhibits a lubricity of up to 14, 13, 12, 11, 10, 9, 8, or 7 g.

[0076] Examples of articles that can benefit from having such a coating according to the present invention include substrates used in the study of living cells and biological systems, including diagnostics, therapeutics, and experimental human medicine, veterinary medicine, and agriculture. Other articles include medical devices for diagnostic and / or therapeutic purposes; cardiovascular devices, neurovascular devices, peripheral vascular devices, devices for use in the urinary tract, and devices for use in ophthalmology, orthopedics, and surgery. Examples include catheters, guidewires, stents, delivery devices for, e.g., prosthetic heart valves, or intraocular lenses, contact lenses, implantable devices, extracorporeal devices, and tools and instruments. Articles that particularly benefit from applying the hydrophilic and optionally lubricious coating of the present invention to at least a portion of their surface include medical devices or components such as intermittent catheters, balloon catheters, PTCA catheters, stent delivery catheters, introducer sheaths, guidewires, stents, syringes, metal and plastic implants, contact lenses, and medical tubing.

[0077] The terms "a," "an," "the," and similar uses in connection with the description of the present invention (particularly in connection with the claims below) are to be construed as including both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The words "comprising," "having," "including," and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to"), unless otherwise expressly stated. The recitation of ranges of values ​​herein is merely intended to serve as a shorthand method of individually referring to each separate value falling within the range, and each separate value is incorporated into the specification as if it were individually set forth herein. Unless otherwise claimed, the use of any and all examples or exemplary language (e.g., "such as" or "like") provided herein is intended merely to better describe the invention and does not pose a limitation on the scope of the invention. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0078] Preferred embodiments of the present invention, including the best mode known to the inventors for carrying out the invention, are described herein. Variations of these preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect that skilled artisans will take advantage of such variations, and the inventors intend that the invention may be practiced otherwise than as specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. While specific optional features are described as embodiments of the invention, the description is meant to include and specifically disclose all combinations of these embodiments unless specifically indicated otherwise or physically impossible.

[0079] The various aspects, embodiments and methods of implementation of the present invention as described above are further summarized below by a series of exemplary embodiments.

[0080] [1] A photocurable coating composition suitable for the preparation of a hydrophilic coating, comprising: (a) a polymerizable compound of formula [1] wherein G is the residue of a hydrophobic hydroxy-functional oligomer; n is 1 to 10; and each R is independently a C to C 20 a residue of an aliphatic, cycloaliphatic, or aromatic hydrocarbon compound, and Z is a moiety having a polymerizable group; [ka] (b) a hydrophilic polymer; (c) a photoinitiator; (d) optionally one or more additional ingredients; (e) a solvent for components (a) to (c); A composition comprising the components of:

[0081] [2] The composition of embodiment 1, wherein component (a) is present in an amount of 0.5 to 30% by weight, based on the total dry weight of the composition.

[0082] [3] The composition of embodiment 2, wherein component (a) is present in an amount of at least 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.4, 1.5, or 1.8 wt. %, based on the total dry weight of the composition.

[0083] [4] The composition of embodiment 1, wherein component (a) is present in an amount of 2.0 to 30% by weight, based on the total dry weight of the composition.

[0084] [5] The composition of any one of embodiments 1 to 4, wherein the composition comprises one polymerizable compound of formula [1].

[0085] [6] The composition of any one of embodiments 1-4, wherein the composition comprises a mixture of two or more chemically distinct polymerizable compounds of formula [1], e.g., where one or more of G, Z, or R1 differ.

[0086] [7] The composition of any one of embodiments 1-4, wherein the composition comprises a mixture of chemically similar compounds of formula [1] that differ in the number of polymerizable groups, preferably n having an average value of 1 to 10.

[0087] [8] The composition of any one of embodiments 1 to 7, wherein component (a) further comprises a polymerizable compound containing a group G that is the residue of a hydrophobic amine-functional oligomer.

[0088] [9] The composition of any one of embodiments 1 to 8, wherein the composition comprises a polymerizable compound of formula [1] having a functionality n greater than 1, preferably at least 1.1, 1.2, 1.4, 1.6, 1.8, 1.9, or 2.0 and at most 8, 6, 4, 3, or 2.5.

[0089]

[10] The composition of embodiment [5], wherein functionality n is about 1.8 to 3, or about 1.8 to 2.2.

[0090]

[11] The composition of any one of embodiments 1 to 10, wherein the group G is the residue of at least one hydrophobic oligomer having a (number average) molar mass Mn of about 200 to 8000 g / mol, preferably the oligomer has a molar mass Mn of at least 300, 500 or 700 g / mol and at most 7000, 6000, 5000 or 4000 g / mol.

[0091]

[12] The composition of any one of embodiments 1-11, wherein the group G is a residue of at least one hydrophobic oligomer selected from the group consisting of polyethers, polyesters, polycarbonates, polyurethanes, polyepoxides, polyamides, poly(meth)acrylamides, poly(meth)acrylates, and polyolefins.

[0092]

[13] The composition of any one of embodiments 1-12, wherein the group G is a residue of a polyether oligomer, preferably a polyether oligomer that is insoluble in water, such as polytetrahydrofuran or a copolymer thereof, e.g., a copolymer based on 1,4-butanediol and 2-methyl-1,4-butanediol.

[0093]

[14] The composition of any one of embodiments 1-13, wherein the group G is a residue of a hydrophobic oligomer that exists at least partially in the form of a dimer or trimer, for example resulting from the reaction of an oligomer having two hydroxyl groups with a diisocyanate.

[0094]

[15] Each R1 is independently C6 to C 20 15. The composition of any one of embodiments 1-14, wherein the residue is an aliphatic, cycloaliphatic, or aromatic hydrocarbon compound.

[0095]

[16] The composition of any one of embodiments 1 to 15, wherein R1 is produced by synthesizing a polymerizable compound of formula [1] from a hydroxy-functional oligomer, a hydroxy-functional compound having a polymerizable group, and a diisocyanate compound OCN-R1-NCO.

[0096]

[17] The composition of embodiment 16, wherein the diisocyanate compound is at least one selected from the group consisting of 4,4'-diphenylmethane diisocyanate (MDI), 2,4-toluene diisocyanate, 2,6-toluene diisocyanate (TDI), 1,4-phenylene diisocyanate, hexamethylene diisocyanate (HDI), tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate (HMDI), and isophorone diisocyanate (IPDI).

[0097]

[18] The composition of any one of embodiments 1-17, wherein each R1 is independently at least one residue selected from the group consisting of 2,4-toluene, 2,6-toluene, hexane, butane, cyclohexane, and isophorone.

[0098]

[19] The composition of any one of embodiments 1-18, wherein each R1 is a residue of TDI, HDI, or IPDI.

[0099]

[20] The composition of any one of embodiments 1-19, wherein Z has a polymerizable group that reacts with other similar groups under the influence of radiation and in the presence of a photoinitiator to form an oligomer or polymer, preferably via a radical-induced addition reaction.

[0100]

[21] The composition of any one of embodiments 1-20, wherein Z has a polymerizable group that, when activated by a photoinitiator, co-reacts with a hydrophilic polymer present in the coating composition to form grafts on the polymer and / or crosslink the polymer.

[0101]

[22] The composition of any one of embodiments 1 to 21, wherein Z has an unsaturated polymerizable group, preferably selected from the group consisting of an olefinic group, a styrenic group, and a (meth)acrylic group.

[0102]

[23] The composition of any one of embodiments 1-22, wherein Z has a (meth)acrylic group.

[0103]

[24] The composition of any one of embodiments 1-23, wherein Z is obtained from reacting a hydroxy-functional compound having a polymerizable group with an isocyanate group of R1.

[0104]

[25] Z is a (meth)acrylic moiety of formula [2], and each R2 is independently C1 to C 10 25. The composition of any one of embodiments 1-24, wherein R is alkyl and each R3 is independently hydrogen or methyl.

[0105]

[26] The composition of embodiment 25, wherein Z is a moiety of formula [2] and each R3 is hydrogen.

[0106]

[27] The composition of embodiment 25 or 26, wherein Z is a moiety of formula [2] and each R2 is independently C2-C4 alkyl, preferably each R2 is ethyl or propyl, or each R2 is ethyl.

[0107]

[28] The composition of any one of embodiments 1 to 27, wherein the polymerizable compound of formula [1] has a number average molar mass (Mn) of 500 to 100,000 g / mol, preferably at least 750 or 1,000 g / mol, and at most 50,000, 25,000, 10,000, 6,000, or 4,000 g / mol.

[0108]

[29] The composition of any one of embodiments 1 to 28, wherein the polymerizable compound of formula [1] is soluble in relatively polar solvents but insoluble or poorly soluble in water.

[0109]

[30] The composition of any one of embodiments 1-29, wherein the polymerizable compound of formula [1] is prepared by reacting a hydroxy-functional oligomer with a diisocyanate and a hydroxy-functional compound having a polymerizable group.

[0110]

[31] The composition of any one of embodiments 1-30, wherein the polymerizable compound of formula [1] is prepared by first reacting a hydroxy-functional oligomer with a diisocyanate in a molar ratio of isocyanate to hydroxy groups of 2, and subsequently reacting the remaining isocyanate groups with a hydroxy-functional compound having a polymerizable group.

[0111]

[32] The composition of any one of embodiments 1-30, wherein the polymerizable compound of formula [1] is made by first reacting a hydroxy-functional oligomer with a molar excess of a diisocyanate, followed by removal of unreacted diisocyanate, and then reacting the remaining isocyanate groups with a hydroxy-functional compound having a polymerizable group.

[0112]

[33] The composition of any one of embodiments 1-32, wherein the polymerizable compound according to formula [1] is a reaction product of a tetrahydrofuran-based or tetrahydrofuran and methyltetrahydrofuran-based copolyether diol, toluene diisocyanate, and hydroxyethyl acrylate.

[0113]

[34] The composition of any one of embodiments 1-33, wherein the polymerizable compound of formula [1] is present in an amount of at least 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, or 6.0 wt. %, based on the total dry weight of the composition.

[0114]

[35] The composition of any one of embodiments 1-34, wherein the polymerizable compound of formula [1] is present in an amount of up to 30, 25, 20, 15, 12, or 10 wt. %, based on the total dry weight of the composition.

[0115]

[36] The composition of any one of embodiments 1-35, wherein the coating composition comprises as component (b) at least one hydrophilic polymer, which is a linear or branched polymer; a homopolymer or a copolymer; a natural, bio-derived, or synthetic polymer; or a blend thereof.

[0116]

[37] The composition of any one of embodiments 1-36, wherein the hydrophilic polymer is a non-ionic polymer that is soluble in the (organic) solvent of the coating composition.

[0117]

[38] The composition of any one of embodiments 1-37, wherein the hydrophilic polymer is at least one polymer selected from the group consisting of polylactams, polyurethanes, copolymers of (meth)acrylates and (meth)acrylic acid, polyvinyl alcohols, polyvinyl ethers, polyethyleneimines, polyethylene oxides, polyamides, polyesters, polyanhydrides, polyphosphazenes, cellulosics, heparins, dextran, polysaccharides, alginates, gelatins, polypeptides, proteins, and oligonucleotides.

[0118]

[39] The composition of any one of embodiments 1 to 38, wherein the hydrophilic polymer has a molar mass Mn of about 8 to 5000 kg / mol, preferably a molar mass of about 20 to 3000 or 200 to 2000 kg / mol.

[0119]

[40] The composition of any one of embodiments 1-39, wherein the hydrophilic polymer is polyvinylpyrrolidone (PVP) or polyethylene oxide.

[0120]

[41] The composition of any one of embodiments 1-40, wherein the hydrophilic polymer is PVP or a copolymer thereof, preferably the PVP having a molar mass corresponding to at least K15, or at least K30 or K80.

[0121]

[42] The composition of any one of embodiments 1-41, wherein the hydrophilic polymer is PVP or a copolymer thereof and has a molar mass corresponding to at least K90 and at most K120.

[0122]

[43] The composition of any one of embodiments 1-42, wherein the coating composition further comprises a polyelectrolyte that is soluble in the (organic) solvent of the coating composition.

[0123]

[44] The composition of embodiment 43, wherein the polyelectrolyte has a molar mass Mn of at least 20, 50, or 100 kg / mol and less than 1000, 500, or 300 kg / mol.

[0124]

[45] The composition of any one of embodiments 43-44, wherein the polyelectrolyte has ionizable or ionized groups that may be selected from ammonium groups, phosphonium groups, sulfonium groups, carboxylate groups, sulfate groups, sulfinic groups, sulfonic groups, phosphate groups, and phosphonic groups.

[0125]

[46] The composition of any one of embodiments 43-45, wherein the polyelectrolyte comprises a metal ion, such as an alkali metal ion or an alkaline earth metal ion.

[0126]

[47] The composition of any one of embodiments 43-46, wherein the polyelectrolyte comprises anions such as halides, sulfates, nitrates, carbonates, and phosphates.

[0127]

[48] ​​The composition of any one of embodiments 43-47, wherein the polyelectrolyte is a homo- and copolymer of acrylic acid, a homo- and copolymer of methacrylic acid, a homo- and copolymer of maleic acid, a homo- and copolymer of fumaric acid, a homo- and copolymer of a monomer comprising a sulfonic acid group, a homo- and copolymer of a monomer comprising a quaternary ammonium salt, or a mixture and / or salt of a derivative thereof.

[0128]

[49] The polymer electrolytes include poly(acrylamide-co-acrylic acid) salts, poly(acrylamide-co-methacrylic acid) salts, poly(methacrylamide-co-acrylic acid) salts, poly(methacrylamide-co-methacrylic acid) salts, poly(acrylic acid) salts, poly(methacrylic acid) salts, poly(acrylic acid-co-maleic acid) salts, poly(methacrylic acid-co-maleic acid) salts, poly(acrylamide-co-maleic acid) salts, poly(methacrylamide-co-maleic acid) salts, poly(acrylamido-2-methyl-1-propanesulfonic acid) salts, poly(4-styrenesulfonic acid) salts, poly(acrylamide- 49. The composition of any one of embodiments 43-48, wherein the compound is a salt of poly(vinyl)pyridine, a salt of polyethyleneimine, or a salt of polylysine.

[0129]

[50] The composition of any one of embodiments 43-49, wherein the polyelectrolyte is a copolymer, such as a random or block copolymer, comprising at least two different types of monomer units.

[0130]

[51] The composition of any one of embodiments 43-50, wherein the polyelectrolyte is a copolymer comprising a monomer having an ionizable or ionized group, such as a poly(acrylamide-co-acrylic acid) salt, and a monomer having no ionizable or ionized group.

[0131]

[52] The composition of any one of embodiments 43-51, wherein the polyelectrolyte is present at a concentration lower than the concentration of the hydrophilic polymer.

[0132]

[53] The composition of any one of embodiments 43-52, wherein the mass ratio of nonionic hydrophilic polymer to polyelectrolyte is from 99:1 to 60:40, or from 95:5 to 75:25.

[0133]

[54] The composition of any one of embodiments 1-53, wherein the hydrophilic polymer is present in an amount of at least 10, 20, 30, 40, 50, 60, 70, or 80% by weight, and at most 97, 95, 93, 92, 91, or 90% by weight, based on the dry weight of the composition.

[0134]

[55] The composition of any one of embodiments 1-54, wherein component (c) is at least one Norrish Type I photoinitiator and / or at least one Norrish Type II photoinitiator.

[0135]

[56] The composition of any one of embodiments 1-55, wherein the photoinitiator is at least one Norrish Type I photoinitiator selected from the group consisting of benzoin derivatives, methylolbenzoin and 4-benzoyl-1,3-dioxolane derivatives, benzil ketals, α,α-dialkoxyacetophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, bisacylphosphine oxides, acylphosphine sulfides, and halogenated acetophenone derivatives.

[0136]

[57] The composition of any one of embodiments 1-56, wherein the photoinitiator is at least one Norrish Type II photoinitiator selected from the group consisting of aromatic ketones, for example, benzophenone, xanthone, derivatives of benzophenone (e.g., chlorobenzophenone), substituted benzophenone, benzophenone, blends of benzophenone derivatives (e.g., Photocure 81, a 50 / 50 blend of 4-methylbenzophenone and benzophenone), Michler's Ketone, Ethyl Michler's Ketone, thioxanthone, xanthone derivatives such as Quantacure ITX (isopropylthioxanthone), benzil, anthraquinone (e.g., 2-ethylanthraquinone), coumarin, and chemical derivatives of these photoinitiators.

[0137]

[58] The photoinitiator is 2-benzoylbenzoic acid, 3-benzoylbenzoic acid, 4-benzoylbenzoic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 4-benzoyl-N,N,N,-trimethylbenzene-methaminium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-1-propananeaminium chloride, 2-hydroxy-3-(3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl) 58. The composition of any one of embodiments 1-57, wherein the at least one Norrish Type II photoinitiator is selected from the group consisting of (oxy)-N,N,N-trimethyl-1-propanaminium chloride, thioxanthone-3-carboxylic acid, thioxanthone-4-carboxylic acid, anthraquinone-2-sulfonic acid, 9,10-anthraquinone-2,6-disulfonic acid, anthraquinone-2-sulfonic acid, anthraquinone-2-carboxylic acid, and salts of derivatives thereof.

[0138]

[59] The composition of any one of embodiments 1-58, wherein the coating composition comprises at least a Norrish Type II photoinitiator.

[0139]

[60] The composition of any one of embodiments 1-59, wherein the coating composition contains a mixture of a Norrish Type II photoinitiator and a Norrish Type I photoinitiator, preferably in a weight ratio of Norrish Type II photoinitiator to Norrish Type I photoinitiator of 10:1 to 1:10; 7:1 to 1:7; 5:1 to 1:5; or 2:1 to 1:2.

[0140]

[61] The composition of any one of embodiments 1-60, wherein the amount of photoinitiator in the coating composition is 0.2 to 5 wt.%, preferably the amount is at least 0.3, 0.4, or 0.5 wt.%, and at most 4.5, 4.0, 3.5, or 3.0 wt.% (based on the dry weight of the composition).

[0141]

[62] The composition of any one of embodiments 1 to 61, wherein the composition comprises as component (d) one or more additional components which may include: a low molar mass osmolality increasing component such as an ionic or ionizable compound such as urea, glycerol, or sodium chloride; a surfactant; an antioxidant; a radical stabilizer; a UV absorber; a light stabilizer; a thermal polymerization inhibitor; a coupling agent such as a silane compound; a coating surface modifier; a leveling agent; a colorant such as a pigment or dye; a preservative; a plasticizer; a lubricant; a filler; a wetting improver; or a chain transfer agent.

[0142]

[63] The composition of embodiment 62, wherein each additional component may be present in an amount of 0.01 to 3 wt.%, based on the total dry weight of the composition.

[0143]

[64] The composition of any one of embodiments 1-63, wherein the coating composition further comprises a surfactant as component (d).

[0144]

[65] The composition of embodiment 64, wherein the surfactant is an anionic or cationic surfactant.

[0145]

[66] The composition of embodiment 65, wherein the ionic surfactant is a compound selected from the group consisting of sodium dodecyl sulfate (SDS), sodium cholate, bis(2-ethylhexyl)sulfosuccinic acid sodium salt, cetyltrimethylammonium bromide (CTAB), lauryldimethylamine-oxide (LDAO), N-laurylsarcosine sodium salt, and sodium deoxycholate (DOC).

[0146]

[67] The composition of embodiment 64, wherein the surfactant is a nonionic surfactant.

[0147]

[68] The composition of embodiment 67, wherein the surfactant is a compound selected from the group consisting of alkyl polyglucosides such as Triton™ BG-10 and Triton™ CG-110; branched secondary alcohol ethoxylates such as Tergitol™ TMN; ethylene oxide / propylene oxide copolymers such as Tergitol L and Tergitol XD, XH, and XJ; nonylphenol ethoxylates such as Tergitol NP; octylphenol ethoxylates such as Triton X; secondary alcohol ethoxylates such as Tergitol 15-S; specialty alkoxylates such as Triton CA, Triton N-57, and Triton X-207; Tween 80 (sorbitan monooleate polyethylene glycol having about 80 ethylene oxide units); and Tween 20 (monolaurate polyethylene glycol having about 20 ethylene oxide units).

[0148]

[69] The composition of any one of embodiments 64-68, wherein the surfactant is present in an amount of 0.1 to 2 wt. %, based on the total weight of the dry coating.

[0149]

[70] The composition of any one of embodiments 1-69, wherein the coating composition comprises, as component (d), one or more additional polymerizable compounds different from the polymerizable compound of formula [1].

[0150]

[71] The composition of embodiment 70, wherein the further polymerizable compound has more hydrophilic characteristics than the polymerizable compound of formula [1].

[0151]

[72] The composition of embodiment 70 or 71, wherein the additional polymerizable compound is an oligomer and has an average of one or more polymerizable groups, such as olefinic, styrenic, or (meth)acrylic unsaturated groups.

[0152]

[73] The composition of any one of embodiments 70-72, wherein the additional polymerizable compound has two or more polymerizable groups.

[0153]

[74] The composition of any one of embodiments 70-73, wherein the additional polymerizable compound is a dimethacrylate, diacrylate, or diacrylamide.

[0154]

[75] The composition of any one of embodiments 70-74, wherein the additional polymerizable compound is poly(ethylene oxide) diacrylate (PEG-DA) or poly(ethylene oxide) diacrylamide (PEG-DAA).

[0155]

[76] The composition of any one of embodiments 70-75, wherein the additional polymerizable compound is present in an amount of at least 0.1, 1, 2, or 3 wt. %, and at most 25, 20, 15, 10, 5, 4, 3, 2, or 1 wt. %, based on the total dry weight of the composition.

[0156]

[77] The composition of any one of embodiments 70-76, wherein the additional polymerizable compound is present in a lower amount than the polymerizable compound of Formula [1]; preferably in an amount of up to 80, 60, 40, 20, or 10% by weight of the polymerizable compound of Formula [1].

[0157]

[78] The composition of any one of embodiments 1-77, wherein the coating composition comprises, as component (e), at least one solvent capable of dissolving the other components (a)-(c) and optionally (d), and which is at least partially miscible with water.

[0158]

[79] The composition of any one of embodiments 1-78, wherein the solvent is a relatively polar organic liquid selected from a C1-C6 alcohol, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol; acetone; methyl ethyl ketone; tetrahydrofuran; or a mixture thereof.

[0159]

[80] The composition of any one of embodiments 1-79, wherein the solvent comprises water.

[0160]

[81] The composition of any one of embodiments 1-80, wherein the solvent is at least one selected from methanol, ethanol, and isopropanol; including mixtures thereof or mixtures containing some water, such as 96% ethanol.

[0161]

[82] The composition of any one of embodiments 1-81, wherein the coating composition contains 40-99.5 wt. % solvent.

[0162]

[83] The composition of any one of embodiments 1-82, wherein the coating composition contains at least 50, 60, 70, 80, 85, 90, or 95 wt. % solvent, and at most 99.0, 98.5, 98, 97.5, or 97.0 wt. % solvent.

[0163]

[84] The composition of any one of embodiments 1-83, wherein the coating composition contains an amount of solvent such that the solution has a relatively low viscosity and allows for the application of thin coating layers to elongated articles such as catheters and guidewires, for example, via a dip-coating process.

[0164]

[85] The coating composition has a viscosity of about 5 to 200 mm as determined using an Ubbelohde viscometer at 25°C. 2 / s, preferably the kinematic viscosity is at least 6, 8 or 10 and at most 450, 400, 350, 300 or 250 mm 2 The composition of any one of embodiments 1-84, wherein

[0165]

[86] The coating composition is about 5 to 50 mm 2 / s; preferably at least 6, 8 or 10 and at most 40, 35, 30 or 25 mm 2 86. The composition of any one of embodiments 1-85, having a kinematic viscosity of 1 / s.

[0166]

[87] The coating composition is about 50 to 200 mm 2 / s; preferably at least 60, 70, 80, 90 or 100 mm 2 / s, and up to 450, 400, 350, 300 or 250 mm 2 86. The composition of any one of embodiments 1-85, having a kinematic viscosity of 1 / s.

[0167]

[88] The composition of any one of embodiments 1-87, wherein the photocurable coating composition comprises, based on the total dry weight of the composition, 2.0-30 wt.% of component (a); 97.8-30 wt.% of component (b); 0.2-5 wt.% of component (c); and 0-35 wt.% of component (d); and the sum of (a)-(d) is 100%.

[0168]

[89] The composition of any one of embodiments 1-87, wherein the photocurable coating composition comprises, based on the total dry weight of the composition, 3.5-30 wt.% of component (a); 96.3-30 wt.% of component (b); 0.2-5 wt.% of component (c); and 0-35 wt.% of component (d); and the sum of (a)-(d) is 100%.

[0169]

[90] The composition of any one of embodiments 1-87, wherein the photocurable coating composition comprises, based on the total dry weight of the composition, 4-25 wt.% of component (a); 95.2-46 wt.% of component (b); 0.3-4 wt.% of component (c); and 0.5-25 wt.% of component (d); and the sum of (a)-(d) is 100%.

[0170]

[91] The composition of any one of embodiments 1-87, wherein the photocurable coating composition comprises, based on the total dry weight of the composition, 5-20 wt.% of component (a); 93.6-46 wt.% of component (b); 0.4-3.5 wt.% of component (c); and 1-20 wt.% of component (d); and the sum of (a)-(d) is 100%.

[0171]

[92] The composition of any one of embodiments 1-87, wherein the photocurable coating composition comprises, based on the total dry weight of the composition, 2-10 wt. % of component (a); 95.5-77 wt. % of component (b); 0.5-3 wt. % of component (c); and 2-10 wt. % of component (d); and the sum of (a)-(d) is 100%.

[0172]

[93] A method of making the composition of any one of embodiments 1-92 by dissolving all ingredients in a selected solvent under mild conditions.

[0173]

[94] A hydrophilic coating obtained by drying and curing a layer of the coating composition of any one of embodiments 1 to 923.

[0174]

[95] A lubricious hydrophilic coating obtained by drying and curing a layer of the coating composition of any one of embodiments 1-92, and then contacting the dried and cured layer with a wetting agent.

[0175]

[96] applying the coating composition of any one of embodiments 1-92 to at least a portion of a surface of an article; at least partially removing the solvent from the applied coating composition; photocuring the applied coating composition by exposure to a radiation source during or after solvent removal to form a hydrophilic coating; Optionally contacting the hydrophilic coating with a wetting agent to form a lubricious coating; 1. A method of applying a hydrophilic and optionally lubricious coating to an article, comprising:

[0176]

[97] The method of embodiment 96, wherein the coating composition is applied to at least a portion of the surface by dip coating, spray coating, wash coating, vapor deposition, brushing, or rolling.

[0177]

[98] The method of any one of embodiments 96-97, wherein the article is a film, sheet, rod, tube, molded article, fiber, or fabric.

[0178]

[99] The method of any one of embodiments 96-98, wherein the article has a surface that is porous, non-porous, smooth, rough, uniform, or uneven.

[0179]

[0100] The method of any one of embodiments 96-99, wherein the article is elongated and relatively thin, such as a guidewire or catheter, and the coating composition is applied using a dip-coating or spraying technique.

[0180]

[0101] The method of any one of embodiments 96 to 100, wherein the coating composition is applied after cleaning the surface but without chemically pretreating the surface to be coated or applying a primer composition.

[0181]

[0102] The method of any one of embodiments 96 to 101, wherein the radiation source is a UV lamp.

[0182]

[0103] The method of any one of embodiments 96 to 102, wherein the hydrophilic coating after drying and curing has a thickness of 0.1 to 300 μm, preferably a thickness of at least 0.2, 0.3, 0.4, 0.5 μm, and at most 200, 100, 50, 40, 30, 20, or 15 μm.

[0183]

[0104] The method of any one of embodiments 96-103 or the lubricious hydrophilic coating of embodiment 95, wherein the wetting agent is oil-based or water-based.

[0184]

[0105] The method of any one of embodiments 96-103 or the lubricious hydrophilic coating of embodiment 95, wherein the wetting agent is a water-based or aqueous wetting agent.

[0185]

[0106] The method of any one of embodiments 96 to 103 or the lubricious hydrophilic coating of embodiment 95, wherein the wetting agent is a water-based composition and further comprises at least one component selected from a compound that reduces surface tension and facilitates spreading of the wetting agent on the coating surface, for example, a surfactant or other organic compound soluble in water such as a higher alcohol or glycerol ester; a compound that stabilizes the wet coating, such as an antioxidant such as vitamin E; a compound that improves water retention in the wet hydrophilic coating, such as a salt or urea; a compound that controls pH, such as an organic or inorganic buffer; and an antibiotic or antibacterial compound.

[0186]

[0107] An article such as a medical device or component thereof having a single layer hydrophilic and optionally lubricious coating on at least a portion of its surface, obtained by the method of any one of embodiments 96-106.

[0187]

[0108] The article of embodiment 107, wherein the single layer hydrophilic coating exhibits a lubricity of up to 15 g after wetting, determined as average friction by the method described in the experimental section using a Harland Friction Tester FTS 6000.

[0188]

[0109] The article of embodiment 108, wherein the single layer hydrophilic coating exhibits a lubricity of up to 14, 13, 12, 11, 10, 9, 8, or 7 g after wetting.

[0189]

[0110] The article of any one of embodiments 107-109, which is a substrate for use in the study of living cells and biological systems, including diagnostics, therapeutics, and experimental human medicine, veterinary medicine, and agriculture.

[0190]

[0111] Any one of the articles of embodiments 107 to 109, which is a medical device for diagnostic and / or therapeutic use, such as a cardiovascular device, a neurovascular device, a peripheral vascular device, or a device for use in urology, ophthalmology, orthopedics, or general surgery.

[0191]

[0112] The article of embodiment 111, which is a catheter, a guidewire, a delivery device for an artificial valve, a delivery device for an intraocular lens, a contact lens, an implantable device, an extracorporeal device, or a medical implement or instrument.

[0192]

[0113] The article of any one of embodiments 111-112, which is an intermittent catheter, a balloon catheter, a PTCA catheter, a stent delivery catheter, a guidewire, a stent, a syringe, a metal or plastic implant, or a medical tubing. Further exemplary embodiments are as follows: items 1 to 15. [Item 1] 1. A photocurable hydrophilic coating composition comprising: (a) a polymerizable compound of formula [1] (wherein G is a residue of a hydrophobic hydroxy-functional oligomer; n is 1 to 10; and each R 1 independently, C 6 ~C 20 a residue of an aliphatic, cycloaliphatic, or aromatic hydrocarbon compound, and Z is a moiety having a polymerizable group; [ka] (b) a hydrophilic polymer; (c) a photoinitiator; (d) optionally one or more additional ingredients; (e) a solvent for components (a) to (c); and A composition in which the polymerizable compound of the formula [1] is present in an amount of 2.0 to 30% by mass based on the total dry mass of the composition. [Item 2] 2. The coating composition according to item 1, wherein n is 1.8 to 3, or preferably 1.8 to 2.2. [Item 3] 3. The coating composition of claim 1 or 2, wherein G is a residue of a hydroxy-functional hydrophobic oligomer selected from the group consisting of polyethers, polyesters, polycarbonates, polyurethanes, polyepoxides, polyamides, poly(meth)acrylamides, poly(meth)acrylates, and polyolefins, or any combination thereof. [Item 4] 4. The coating composition according to any one of items 1 to 3, wherein the hydroxy-functional oligomer is a polyether, preferably polytetrahydrofuran diol or poly(tetrahydrofuran-co-methyltetrahydrofuran) diol. [Item 5] R 1 is a residue of 2,4-toluene, 2,6-toluene, hexane, butane, cyclohexane, or isophorone. [Item 6] 5. The coating composition according to any one of items 1 to 4, wherein the polymerizable group is an unsaturated group such as an olefinic group, a styrenic group, or a (meth)acrylic group. [Item 7] Z is a (meth)acrylic moiety of formula [2] (wherein each R 2 independently, C 1 ~C 10 alkyl, and each R 3 and are independently hydrogen or methyl.

change

[0193] The following experiments and samples further elucidate embodiments of the present invention but, of course, should not be construed as in any way limiting the scope of the claims.

[0194] [experiment] [Composition] [Compounds used] ComfortCoat® 41002 / 43003 and 41001 / 43005 are commercial medical grade (primer / topcoat) hydrophilic coating products from DSM Biomedical (Sittard-Geleen, NL).

[0195] PEG-DAA, polyethylene glycol-diacrylamide, prepared from polyethylene oxide diamine (Mn 1500 g / mol; Aldrich) and acryloyl chloride as described in WO2008031596A1.

[0196] PTGL-TDI-HEA, a copolyether di(urethane acrylate), was prepared from poly(2-methyl-1,4-butanediol)-co-(1,4-butanediol)diol (PTGL, Mn 1000 g / mol; Hodogaya), toluene diisocyanate (TDI; Aldrich), and hydroxyethyl acrylate (HEA; Aldrich) as described in WO 2008031596 A1.

[0197] PTGL-IPDI-HEA, a copolyether di(urethane acrylate), was prepared from poly(1,4-butanediol)-co-(2-methyl-1,4-butanediol) diol (PTGL, Mn 1000 g / mol; Hodogaya), isophorone diisocyanate (IPDI; Aldrich), and hydroxyethyl acrylate (HEA; Aldrich) according to the following general procedure. The amount of the appropriate polyether diol was charged to a 250 ml reactor (equipped with a stirrer, air inlet, dropping funnel, and condenser). After charging, the reactor was heated to 45°C, and then dry, clean air was purged into the reactor. Next, the calculated amount of the appropriate diisocyanate (based on a 2 / 1 molar ratio of diisocyanate / diol) was charged to the reactor with stirring. After this step, 1.5 mol% BHT based on the diol was added to the reactor. After waiting 1 hour for the reaction to begin, the temperature was raised to 60°C and maintained for an additional 2 hours. The isocyanate (NCO) content of the mixture was then measured using a potentiometric titrator to confirm that it was within 10% of the theoretical isocyanate content. If the measured value was not within 10%, the reaction was continued for an additional 15 minutes and rechecked until the value was obtained. The calculated amount of hydroxyethyl acrylate was then added to the mixture along with 0.1 mol% DBTDL as a catalyst. The temperature was then raised to 85°C. The resulting mixture was allowed to react for an additional hour at 85°C, after which the NCO content was confirmed by potentiometric titration. When the isocyanate content was less than 0.1% based on the mass of the components, the reaction was either stopped or the mixture was heated for an additional 15 minutes at 85°C.

[0198] The following polymerizable compounds were prepared in the same manner as above. PTHF-IPDI-HEA, based on poly(tetrahydrofuran)diol (PTHF, Mn 1000 g / mol; Aldrich), isophorone diisocyanate (IPDI; Aldrich), and hydroxyethyl acrylate (HEA; Aldrich); PPG1000-IPDI-HEA, based on poly(propylene oxide) diol (PPG, Mn 1000 g / mol; Aldrich), IPDI (Aldrich), and (HEA; Aldrich); PPG2000-TDI-HEA, based on poly(propylene oxide) diol (PPG, Mn 2000 g / mol; Aldrich), IPDI (Aldrich), and (HEA; Aldrich); PPG8000-TDI-HEA, based on poly(propylene oxide) diol (PPG, Mn 8000 g / mol; Aldrich), IPDI (Aldrich), and (HEA; Aldrich); and PEG-IPDI-HEA, based on poly(ethylene oxide) diol (PPG, Mn 1000 g / mol; Aldrich), IPDI (Aldrich) and (HEA; Aldrich).

[0199] As polyvinylpyrrolidone, grade PVP K 90 (supplier BASF) was used unless otherwise indicated.

[0200] Benzophenone was obtained from Ciba Specialty Chemicals (trade name Darocure™).

[0201] 2-Hydroxy-1-[4-(hydroxyethoxy)phenyl]-2-methyl-1-propanone (Irgacure™ 2959) was obtained from Aldrich.

[0202] Tween 80 (polyoxyethylene (80) sorbitan monooleate) was obtained from Merck.

[0203] Ethanol (96%, ultrapure) was obtained from Merck.

[0204] [Coating composition] Tables 1-4 list the components of the coating compositions used in the following experiments, excluding the solvent ethanol. Therefore, the weight percentages indicated relate to the dry weight of the liquid coating solution (non-volatile materials therein), which will substantially correspond to the weight percentages (of the corresponding reacted components) in the dried and cured coating. The compositions were prepared by first dissolving a determined amount of urethane acrylate compound in ethanol (room temperature, in the dark), and then adding PVP and other ingredients with gentle shaking overnight. The ethanol content of the coating compositions varied between approximately 90-98% by weight, depending on the target solution viscosity. All coating compositions were typically prepared in 10-22 mm ethanol solutions unless otherwise indicated. 2 The viscosities were determined using an Ubbelohde viscometer at 25.0±0.3° C. in the range of 1 / s.

[0205] [Base material] The following substrates were used for the coating: polyamide 12 rod with an outer diameter of 1 mm and a length of 600 mm (Zeus, part number 192124); 14 Fr PVC tubing (Raumedic AG, DE); polyamide 12 natural tubing with an outer diameter of 4.7 mm and an inner diameter of 4.57 mm (Nordson, part number 115-2621); Pebax 63D blue tubing with an outer diameter of 2.24 mm and an inner diameter of 2.16 mm (Nordson, part number 115-1327); and Pebax 72D clear tubing with an outer diameter of 1.98 mm and an inner diameter of 1.22 mm (Nordson, part number 115-0678).

[0206] [method] [coating] Polymer rods or tubes approximately 40 cm long were dip-coated in a cleanroom using an Allmepp CCS-12.175 coater. UV lamp intensity was measured with an ILT-1400 meter equipped with an ILT SEL0052224 detector. Each polymer rod or tube (sealed at the bottom and fitted with a metal wire) was cleaned and secured in one of 12 positions on the coater. Approximately 30 cm long, the rod or tube was immersed in the coating formulation for 10 seconds, withdrawn at a speed of 0.5–10 cm / s, and exposed to UV light for 60–360 seconds while rotating at 4 rpm. For two-layer coating systems, the sample was first immersed in the primer, withdrawn at 1 cm / s, cured for 30 seconds, and then the topcoat was applied as described above. The coated samples were stored in sealed PE bags.

[0207] [Lubricity, durability and dry-out] Tests to determine the lubricity and durability of coated samples were performed using a Harland Friction Tester FTS 6000. Two friction pads were applied to the sample with a clamping force of 300 g, and the sample was immersed in demi-water at room temperature (approximately 20-22°C). For testing coatings on tubes, a wire (or mandrel) was inserted into the tube. For each cycle, the sample was moved upward 12 cm at 10 mm / s while measuring friction force, then the clamps were opened and the sample was returned to the starting position. This test was repeated for 25 cycles. The pads were cleaned after 10, 15, and 20 cycles. The lubricity of the coating was reported as the average friction force over 25 cycles (mean friction), and the durability (or wear resistance) of the coating was reported as the difference between the average friction force of the last three cycles and the average friction force of the first three cycles (change in friction). Reported values ​​are the average of 10 samples.

[0208] An average friction force of 15 g is considered the maximum for adequate lubrication performance; above such a level, unacceptable damage to the coating layer or loss of portions of the coating is typically observed.

[0209] The dry-out behavior of wetted hydrophilic coatings on urinary catheter tubing, i.e., the tendency of lubricity to change over time, was also investigated using a Harland friction tester. In this test, frictional force is measured on wetted coatings after 5 and 10 minutes of wetting in air at 20-22°C and 45-55% relative humidity. A maximum average frictional force of 10 g after 10 minutes is considered the maximum value for adequate lubrication of urinary catheters for practical use in humans.

[0210] [Shelf life evaluation] The shelf life of the coating formulations was evaluated by accelerated aging at 50° C. and 60° C., with samples taken after 1.5 and 3 months at 60° C. and after 6 months at 50° C. Viscosity, photoinitiator and polymerizable compound concentrations were measured.

[0211] The shelf life of the coated products was evaluated by applying the coating formulation to polyamide 12 rods at a withdrawal speed of 0.5 cm / s and a cure time of 120 seconds, and evaluating the initial lubricity and wear performance as described above. The samples were placed in pouches and sterilized by exposure to ethylene oxide (EtO; Synergy Health, Venlo, NL) for approximately 3 hours at 46°C and 0.37 bar. The samples were then stored in an oven. The shelf life of the sterilized coated polyamide 12 rods was evaluated by measuring the lubricity and wear performance after 6 months of storage at 50°C, and after 1.5 and 3 months of storage in an oven at 60°C.

[0212] [result] [Comparative Experiment A] As a reference for Examples 1-19, a commercially available two-layer hydrophilic coating system was used: ComfortCoat® 41002 (primer) and ComfortCoat® 43003 (hydrophilic topcoat).

[0213] The results in Table 1 show that this two-layer system can be applied to polyamide 12 (PA 12) substrate rods by dip coating and UV curing to obtain thin, well-adhered coatings. It exhibits excellent lubrication performance after wetting with water and high durability with little change in lubricity during test cycles (CE A). When only the topcoat was used without a primer, the PA 12 substrate was unable to form a stable, adherent coating, even under varying coating conditions.

[0214] [Examples 1 to 4 and Comparative Experiments B to D] In these experiments, coating compositions were prepared containing ethanol (96%) as a solvent, a hydrophilic polymer (PVP), two photoinitiators, and a surfactant, as well as two different polymerizable compounds based on polyether diol oligomers with polymerizable end groups, applied in different weight ratios: polyethylene oxide with acrylamide groups (PEG-DAA) and a copolyether of 1,4-butanediol and methylated 1,4-butanediol with urethane acrylate end groups (PTGL-TDI-HEA). The results, summarized in Table 1, clearly demonstrate that crosslinked coatings with good adhesion, high lubricity, and low wear are only obtained when the composition contains a certain amount of the water-insoluble PTGL-TDI-HEA compound. In the friction test, a friction force greater than 15 g is considered to indicate a coating with insufficient lubricity. Furthermore, the absence of visible damage, such as scratches, in the coating is visually determined by staining the tested coating with Congo Red, confirming the friction test performance.

[0215] [Examples 5 to 13] While some small amounts of PTGL-TDI-HEA may be necessary for adhesion, it appears that higher amounts may induce excessive crosslinking and reduce the lubricity of the coating. Therefore, a series of compositions were tested in which different amounts of PTGL-TDI-HEA were applied as the sole polymerizable polyether. The results in Table 1 indicate that amounts of approximately 4 to 25 wt.% provide excellent coating performance, even after only 60 seconds of UV curing. Furthermore, the presence of a Norrish Type I initiator is not essential, and omitting surfactants, which generally improve coating spreading on surfaces, does not appear to worsen friction test results.

[0216] [Examples 14 to 15 and Comparative Experiments E to I] In these experiments, several polyether urethane acrylates with different polarities or water solubility were evaluated as polymerizable compounds in the coating compositions.

[0217] Example 14 differs primarily from, e.g., Example 6 in that the polymerizable compound was made with an aliphatic diisocyanate instead of an aromatic compound (IPDI vs. TDI), and from Example 15 in that poly(tetrahydrofuran)diol (PTHF) additionally replaced the copolyether. Coating compositions containing these compounds yield hydrophilic coatings that exhibit good performance.

[0218] Comparative experiments E to I were carried out using polymerizable compounds based on poly(ethylene oxide) diol (PEG) and poly(propylene oxide) diol (PPG). The test results demonstrate that when the coating composition contains a polyether urethane acrylate as the more polar, at least partially water-soluble polymerizable compound, poor adhesion to the PA 12 substrate causes damage and loss of the coating during the friction test.

[0219] [Examples 16 to 19 and Comparative Experiments J to M] In these experiments, the performance of coatings made from compositions based on PTGL-IPDI-HEA as the polymerizable compound was evaluated on different substrates, materials typically used in vascular devices, and compared with a reference two-layer coating system. The results showed that similar excellent performance could be obtained on all substrates.

[0220] Shelf Life of Coating Compositions and Coated Articles Accelerated aging experiments were conducted using a coating composition according to Example 6 (containing about 97% by weight ethanol). Aging at 6 months / 50°C and 3 months / 60°C is expected to translate to a shelf life at ambient conditions of about 4 years.

[0221] During testing of the coating compositions, the concentrations of polymerizable components and initiator, as well as the kinematic viscosity of the solutions, were determined at the start and after 1.5, 3, and 6 months at 60°C and 50°C, respectively. All parameters were found to be stable within experimental error, except for a decrease in the concentration of the Irganox 2959 initiator component of approximately 20% (3 months at 60°C) and 10% (6 months at 50°C). The aged compositions were then applied to PA 12 substrates and subjected to friction tests using clamping forces of 300g and 800g. All test results indicated comparable coating performance and no degradation due to accelerated aging.

[0222] The aging of sterilized PA 12 substrates on which the coatings were applied and cured was also evaluated using a friction test. Sterilization and aging at 50°C and 60°C were found to not degrade lubricity or durability.

[0223] [Comparative Experiment N and Examples 20 to 24] As a reference for other experiments, a commercially available two-layer hydrophilic coating system was used: ComfortCoat® 41001 (primer) and ComfortCoat® 43005 (hydrophilic topcoat). This coating system was applied to PVC tubing in two steps by dip coating and UV curing, resulting in a well-adhered coating that exhibited excellent lubricity after wetting with water and good dryout behavior, i.e., minimal change in lubricity over time. This hydrophilic coating system is commonly applied to urinary catheters and has a layer thickness greater than that of the previous set of experiments. High lubricity and minimal dryout after approximately 10 minutes are important performance parameters for people who routinely need to empty their bladders with a drainage bag using such intermittent catheter systems.

[0224] It was observed that it was not possible to produce a stable, adherent coating on a PVC substrate when the use of a primer was omitted and only the topcoat composition was applied, nor was it possible by modifying the coating conditions.

[0225] The experimental results, summarized in Table 4, demonstrate that hydrophilic coating compositions based on ethanol as a solvent according to the present invention can also be applied as single-layer hydrophilic and lubricious coatings on urinary catheters, providing performance within the desired window (Examples 20-24), similar to the commercially available reference ComfortCoat® 41001 / 43005. Because the coating compositions of the present invention differ significantly from this two-layer system, e.g., in the crosslinker (PTGL-TDI-HEA) and solvent (ethanol), parameters such as crosslinker concentration and coating composition viscosity, combined with coating conditions such as withdrawal speed and cure time, require optimization. While the test results for the application of the composition of Example 20 were within the bounds of target performance under the test conditions, the data for Examples 21-24 demonstrate that further improvements are possible with such compositions by varying processing conditions (see Table 4).

[0226]

Table 1

[0227]

Table 2

[0228]

Table 3

[0229]

Table 4

Claims

1. 1. A photocurable hydrophilic coating composition comprising: (a) a polymerizable compound of formula [1], wherein G is a residue of a hydrophobic hydroxy-functional oligomer; n is 1 to 10, and each R １ are independently a residue of 2,4-toluene, 2,6-toluene, hexane, butane, cyclohexane, or isophorone, and Z is a moiety having an unsaturated polymerizable group; 【Chemical 1】 (b) a hydrophilic polymer; and (c) a photoinitiator; (d) optionally one or more additional ingredients; (e) a solvent capable of dissolving components (a) to (c); and A coating composition, wherein the polymerizable compound of formula [1] is present in an amount of 2.0 to 30% by weight, based on the total dry weight of the coating composition.

2. 2. The coating composition of claim 1, wherein n is 1.8 to 3.

3. The coating composition of claim 1, wherein n is 1.8 to 2.

2.

4. 4. The coating composition of claim 1, wherein G is a residue of a hydrophobic hydroxy-functional oligomer selected from the group consisting of polyethers, polyesters, polycarbonates, polyurethanes, polyepoxides, polyamides, poly(meth)acrylamides, poly(meth)acrylates, and polyolefins, or any combination thereof.

5. The coating composition of any one of claims 1 to 4, wherein the hydrophobic hydroxy-functional oligomer is a polyether.

6. The coating composition of claim 1, wherein the hydrophobic hydroxy-functional oligomer is polytetrahydrofuran diol or poly(tetrahydrofuran-co-methyltetrahydrofuran)diol.

7. The coating composition according to any one of claims 1 to 6, wherein the unsaturated polymerizable group is a (meth)acrylic group.

8. Z is a (meth)acrylic moiety of formula [2] (wherein each R ２ is independent, C １ ~C １０ alkyl, and each R ３ and are independently hydrogen or methyl. 【Chemistry 2】

9. The coating composition according to any one of claims 1 to 8, wherein the polymerizable compound of formula [1] is a reaction product of (i) a polyether diol based on tetrahydrofuran or containing tetrahydrofuran and methyltetrahydrofuran, (ii) toluene diisocyanate, and (iii) hydroxyethyl acrylate.

10. The coating composition of any one of claims 1 to 9, wherein the hydrophilic polymer comprises a non-ionic polymer.

11. A coating composition according to any one of claims 1 to 10, wherein the hydrophilic polymer is polyvinylpyrrolidone or polyethylene oxide.

12. The coating composition of any one of claims 1 to 11, wherein the photoinitiator comprises a Norrish Type II photoinitiator.

13. A coating composition according to any one of claims 1 to 12, wherein the coating composition comprises a mixture of a Norrish Type II photoinitiator and a Norrish Type I photoinitiator.

14. The coating composition according to any one of claims 1 to 13, further comprising a surfactant, an antioxidant, an osmolality-increasing compound, and / or a hydrophilic polymerizable compound.

15. 15. The coating composition of any one of claims 1 to 14, wherein the coating composition comprises 40 to 99.5 wt% solvent, the solvent being a polar organic liquid that is miscible with water.

16. The coating composition of claim 1, wherein the coating composition comprises 40 to 99.5% by mass of a solvent, and the solvent comprises methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, or tetrahydrofuran.

17. based on the total dry weight of the coating composition, 2.0 to 30% by weight of component (a); 97.8 to 30% by weight of component (b); 0.2 to 5% by weight of component (c); and 0 to 35% by mass of component (d) and the sum of (a) to (d) is 100%.

18. 1. A method for applying a hydrophilic and optionally lubricious coating to an article, comprising: - applying a coating composition according to any one of claims 1 to 17 to at least a portion of the surface of the article; At least partially removing solvent from the applied coating composition; - curing the applied coating composition by exposure to a radiation source during or after solvent removal to form a hydrophilic coating; Optionally contacting the hydrophilic coating with a wetting agent to form a lubricious coating; A method comprising:

19. 1. A medical device or component thereof having a single layer hydrophilic and optionally lubricious coating on at least a portion of its surface, A medical device or a component thereof, wherein the coating is a cured product of the coating composition according to any one of claims 1 to 17.

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