A hydrophilic coating solution and medical devices

Abstract

A hydrophilic coating solution and a medical device are disclosed, belonging to the field of medical device technology. By weight percentage, the hydrophilic coating solution comprises: 4.5 wt% to 15 wt% of a curable hydrophilic polymer, 1.5 wt% to 20 wt% of a crosslinking agent, 0.02 wt% to 3 wt% of an initiator, and 0.02 wt% to 5 wt% of a surfactant, with the balance being a solvent; wherein the crosslinking agent comprises at least two substances having crosslinkable functional groups, and the crosslinking agent includes monomers and / or polymers. The hydrophilic coating formed by applying the above hydrophilic coating solution to the surface of a substrate of a medical device exhibits good adhesion stability and lubrication stability, meeting the requirements for use of the medical device and improving its safety.

Description

Technical Field

[0001] This application relates to the field of medical device technology, and more specifically, to a hydrophilic coating solution and a medical device. Background Technology

[0002] Medical devices such as guidewires, guides, urinary catheters, and intermittent catheters need to be inserted into or subsequently removed from the body through winding pathways to achieve their function without causing discomfort or irritation to the patient's soft tissues. For this reason, such devices require lubricated surfaces.

[0003] The lubricating surface properties not only facilitate manipulation of the patient's vascular system and minimize soft tissue damage, but also aid in the drainage of bodily fluids. Therefore, such medical devices typically incorporate a hydrophilic surface layer or coating that becomes smooth and achieves low-friction properties upon wetting and absorbing water. In addition to biocompatibility and low friction in wet conditions, the relevant properties of hydrophilic coatings used in medical devices include low extractable content, good surface adhesion, and high durability or abrasion resistance to prevent the release of particulate materials during use.

[0004] Therefore, it is necessary to provide a hydrophilic coating solution to form a stable, well-lubricated hydrophilic coating on the surface of a substrate. Summary of the Invention

[0005] In view of the above-mentioned shortcomings, this application provides a hydrophilic coating solution and a medical device to improve the problems of poor adhesion stability and lubrication stability of hydrophilic coatings in related technologies.

[0006] This application is implemented as follows:

[0007] In a first aspect, an example of this application provides a hydrophilic coating solution comprising, by weight percentage: 4.5 wt% to 15 wt% of a curable hydrophilic polymer, 1.5 wt% to 20 wt% of a crosslinking agent, 0.02 wt% to 3 wt% of an initiator, 0.02 wt% to 5 wt% of a surfactant, and the balance being a solvent; wherein the curable hydrophilic polymer comprises at least two polymers having curable functional groups, the crosslinking agent comprises at least two substances having crosslinkable functional groups, and the crosslinking agent comprises monomers and / or polymers.

[0008] In the above-mentioned process, at least two curable hydrophilic polymers at 4.5 wt% to 15 wt% and at least two crosslinking agents at 1.5 wt% to 20 wt% are combined in the hydrophilic coating solution, and a surfactant is added to improve the adhesion and lubricity of the hydrophilic coating formed after the hydrophilic coating solution is cured on the substrate surface. The hydrophilic coating can still maintain good adhesion and lubricity after aging, and the hydrophilic coating has good adhesion stability and lubrication stability.

[0009] In conjunction with the first aspect, in optional embodiments of this application, the product comprises, by weight percentage: 4.5 wt% to 10 wt% of a curable hydrophilic polymer, 6 to 12 wt% of a crosslinking agent, 0.02 wt% to 3 wt% of an initiator, 0.5 wt% to 1 wt% of a surfactant, and the balance being a solvent.

[0010] In the above process, the hydrophilic coating solution contains 4.5 wt% to 10 wt% of two curable hydrophilic polymers and 6 to 12 wt% of two crosslinking agents, which can further improve the lubrication stability and adhesion stability of the hydrophilic coating formed by curing the hydrophilic coating solution.

[0011] In conjunction with the first aspect, in optional embodiments of this application, the curable hydrophilic polymer may be selected from at least two of the following groups: polyethylene glycol, polypropylene glycol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyacryl alcohol, polyvinyl alcohol, polyamide, polyetherimide, polypeptide amine, polyvinylpyrrolidone, polyethylene oxide, or polyurethane.

[0012] In the above-mentioned process, the hydrophilic coating solution contains at least two different curable hydrophilic polymers. The combined use of different types of curable hydrophilic polymers can also reduce the surface energy of the coating surface, obtain good hydrophilicity, and further improve the lubricity of the hydrophilic coating.

[0013] In conjunction with the first aspect, in optional embodiments of this application, the curable hydrophilic polymer is selected from at least two of polyvinylpyrrolidone, polyethylene glycol, and polyether.

[0014] Optionally, polyvinylpyrrolidone is selected from at least one of PVP-K30, PVP-K90 or PVP-K120.

[0015] In the above process, the lubricity of the hydrophilic coating can be further improved by using the combination of polyvinylpyrrolidone, polyethylene glycol or polyether.

[0016] In conjunction with the first aspect, in optional embodiments of this application, the crosslinkable functional group is selected from at least one of acrylate, acrylamide, or methyl methacrylate.

[0017] Optionally, the crosslinking agent is selected from polyester and / or polyether substances.

[0018] Optionally, the crosslinking agent is selected from one or more of the following groups: trimethylolpropane triacrylate, hydroxypropyl acrylate, isobornyl acrylate, butyl methacrylate, bisphenol A dimethacrylate, bisphenol A glycerol dimethacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, isobutyl methacrylate, tetrahydroxybutyl acrylate, bisphenol A ethoxymethyl dimethacrylate, propoxylated trimethylolpropane triacrylate. Trimethylolpropane ethoxylate triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane)tetraacrylate, poly(propylene glycol) dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, poly(ethylene glycol) methacrylate, polymethyl methacrylate, polypropylene glycol methacrylate, polypropylene glycol diacrylate, poly(ethylene glycol) diacrylate, polyethylene glycol methyl ether methacrylate, methoxy polyethylene glycol acrylate, poly(propylene glycol) methacrylate.

[0019] In conjunction with the first aspect, in optional embodiments of this application, the crosslinking agent includes at least three substances having crosslinkable functional groups.

[0020] In the above process, at least three different monomers or polymers with crosslinkable functional groups are added to the hydrophilic coating solution, and the amount of crosslinking agent added is relatively high, which can realize inter-chain branching and form a hydrophilic coating with an interpenetrating crosslinked network structure. The prepared coating fully expands in water to form a hydrogel, achieving a hydrophilic lubrication effect and ensuring that it has sufficient adhesion to the substrate, avoiding the entire hydrophilic layer from falling off, thereby improving the adhesion stability of the hydrophilic coating.

[0021] In conjunction with the first aspect, in optional embodiments of this application, the initiator is selected from photosensitizing initiators and / or thermosensitive initiators.

[0022] Optionally, the initiator is selected from one or more of 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, benzoin, benzophenone, methyl benzoate or 1-hydroxycyclohexylphenyl ketone.

[0023] In the above process, photoinitiators and thermoinitiators are used in combination with at least one of the other components in the solution to form a hydrophilic coating with good lubricity and adhesion stability after the hydrophilic coating solution is cured.

[0024] In conjunction with the first aspect, in optional embodiments of this application, the surfactant is selected from ionic surfactants and / or nonionic surfactants.

[0025] Optionally, the surfactant is selected from one or more of alkoxyethylene hydroxyethanol, sodium dodecyl sulfate, sodium cholate, sodium di(2-ethylhexyl)sulfosuccinate, hexadecyltrimethylammonium bromide, dodecyl dimethylamine oxide, sodium N-lauroyl sarcosinate and sodium deoxycholate or polyoxyethylene-polyoxypropylene copolymer.

[0026] Optionally, the surfactant is selected from one or more of Triton™ BG-10, Triton™ CG110, Triton™ X207, Triton™ N-57, Triton™ CA, Triton™ X-100, Tergitol™ TMN6, Tergitol™ L, Tergitol™ XD, Tergitol™ TXH, Tergitol™ T15, Tergitol™ TXJ, Tergitol™ 15-S-7, Tergitol™ 15-S-30, Tergitol™ 15-S-40, Tween 80, or Tween 20.

[0027] In the above-mentioned process, adding the above-mentioned hydrophilic surfactant to the hydrophilic coating solution and using it in combination with other components in the hydrophilic coating solution can improve the stability of the hydrophilic coating solution, improve the surface quality of the substrate, form a uniform adhesion coating on the substrate surface, facilitate the formation of more cross-linked structures in the hydrophilic coating, increase the firmness of the connection between the hydrophilic coating and the substrate, and improve the adhesion stability of the hydrophilic coating.

[0028] In conjunction with the first aspect, in optional embodiments of this application, the solvent is selected from water and / or organic solvents.

[0029] Optionally, the organic solvent is selected from one or more components of the following group: ethyl acetate, acetone, butanone, dichloromethane, chloroform, methanol, anhydrous ethanol, n-propanol, isopropanol, or n-butanol.

[0030] In a second aspect, an example of this application provides a medical device including a substrate and a hydrophilic coating attached to the surface of the substrate; the hydrophilic coating is formed by curing a hydrophilic coating solution provided in the first aspect.

[0031] Optionally, the substrate is selected from the guide;

[0032] Optionally, the substrate may be selected from catheters or guidewires;

[0033] Optionally, the substrate may be selected from urinary catheters.

[0034] In the above implementation process, the hydrophilic coating solution provided in the embodiments of this application is coated on the surface of the substrate and cured to form a hydrophilic coating. The hydrophilic coating solution contains a high content of various polymers with curable functional groups, which can cooperate with various crosslinking agents and surfactants to reduce the surface energy of the hydrophilic coating surface, form inter-chain grafts, improve the surface quality of the substrate, improve hydrophilicity and the firmness of bonding with the substrate, so that the hydrophilic coating has good lubrication stability and adhesion stability. Attached Figure Description

[0035] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below.

[0036] Figure 1 The friction force-displacement curve of the hydrophilic coating at zero moment of friction test provided in Example 1 of this application;

[0037] Figure 2 This is a friction force-displacement curve of the hydrophilic coating provided in Example 1 of this application after 2 years of aging.

[0038] Figure 3 This is a friction force-displacement curve of the hydrophilic coating at zero-moment friction test provided in Example 2 of this application;

[0039] Figure 4 This is a friction force-displacement curve of the hydrophilic coating provided in Example 2 of this application after 2 years of aging.

[0040] Figure 5 This is a friction force-displacement curve of the hydrophilic coating at zero-moment friction test provided in Example 3 of this application;

[0041] Figure 6 This is a friction force-displacement curve of the hydrophilic coating provided in Example 3 of this application after 2 years of aging.

[0042] Figure 7 This is a friction force-displacement curve of the hydrophilic coating at zero-moment friction test provided in Example 4 of this application;

[0043] Figure 8 This is a friction force-displacement curve of the hydrophilic coating provided in Example 4 of this application after 2 years of aging.

[0044] Figure 9 Friction force-displacement curve of the hydrophilic coating provided in Comparative Example 1 of this application after 2 years of aging;

[0045] Figure 10 Friction force-displacement curve of the hydrophilic coating provided in Comparative Example 2 of this application after 2 years of aging;

[0046] Figure 11 The friction force-displacement curve is shown in the friction test results of the hydrophilic coating provided in Comparative Example 3 of this application after 2 years of aging. Detailed Implementation

[0047] The embodiments of this application will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of this application. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.

[0048] Medical devices such as urinary catheters typically require lubricated surfaces to reduce soft tissue damage and facilitate the drainage of fluids from the body.

[0049] To improve the lubricity of the catheter surface, a hydrophilic lubricating coating is usually applied to the surface of the catheter substrate.

[0050] Many medical devices, such as guidewires and urinary catheters, are currently made of metal or flexible plastic materials, such as polyolefins, polyvinyl chloride, polyamide 12 or polyamide block copolymers, and polyurethane. Typically, hydrophilic polymers have low adhesion to the surface of such substrates.

[0051] However, in addition to biocompatibility and low friction in wet conditions, the relevant properties of hydrophilic coatings used in medical devices also include low extractable content, good surface adhesion, and high durability or abrasion resistance to prevent the release of particulate materials during use. If the hydrophilic polymer has low adhesion to the substrate surface, it is prone to peeling off during use.

[0052] Currently, most hydrophilic coatings are based on water-soluble polymers, which readily absorb water upon contact with a water source, forming a hydrogel layer that easily detaches from the substrate surface. Furthermore, many medical devices, such as guidewires and catheters, are made of metals or flexible plastic materials, such as polyolefins, polyvinyl chloride, polyamides or polyamide block copolymers, and polyurethanes. Current hydrophilic coatings exhibit low adhesion to the substrate surface, and their lubricity decreases with use, making them prone to detachment.

[0053] Therefore, in order to improve the bonding stability between the hydrophilic coating and the substrate surface and reduce the degree of lubricity degradation, the inventors attempted to pretreat the substrate before forming the hydrophilic coating, such as using plasma treatment to chemically modify the substrate surface, or applying a primer or base coating to the substrate surface first, in order to improve the adhesion level between the substrate and the hydrophilic coating.

[0054] However, pretreatment of the substrate will prolong the preparation time, and the shelf life of the base coating composition or primer is limited. It may still exhibit drawbacks such as excessively high leaching or extractability and insufficient adhesion.

[0055] Therefore, this application provides a hydrophilic coating solution that can improve the adhesion stability and lubrication stability of hydrophilic coatings.

[0056] The hydrophilic coating solution provided in this application, by weight percentage, comprises: 4.5 wt% to 15 wt% of a curable hydrophilic polymer, 1.5 wt% to 20 wt% of a crosslinking agent, 0.02 wt% to 3 wt% of an initiator, 0.02 wt% to 5 wt% of a surfactant, and the balance being a solvent; wherein the curable hydrophilic polymer comprises at least two polymers having curable functional groups, the crosslinking agent comprises at least two substances having crosslinkable functional groups, and the crosslinking agent comprises monomers and / or polymers.

[0057] Curable hydrophilic polymers include at least two polymers having curable functional groups, meaning that they can be two different types of polymers, both of which have the same curable functional groups; or they can be two different types of polymers, the curable functional groups of which are not the same.

[0058] Curable hydrophilic polymers refer to polymers whose curable functional groups can cure themselves.

[0059] Adding at least two different curable hydrophilic polymers to the hydrophilic coating solution can reduce the surface energy of the hydrophilic coating formed after the hydrophilic coating solution is cured, thereby improving hydrophilicity, lubricity, and stability of the hydrophilic coating.

[0060] This application does not limit the specific types of curable hydrophilic polymers. In some possible embodiments, the curable hydrophilic polymer may be selected from one or more of the following groups: polyethers, polyvinylpyrrolidone (PVP), polyesters, polyvinyl alcohol, polysaccharides and their copolymers.

[0061] Furthermore, the curable hydrophilic polymer may be selected from at least two of the following groups: polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene oxide, polyacrylic acid, polyacrylamide, polyacrylamide, polyvinyl alcohol, polyvinyl alcohol, polyamide, polyetherimide, polypeptide amine, polyvinylpyrrolidone (PVP), polyethylene oxide, or polyurethane.

[0062] In some possible embodiments, to further improve the lubrication effect, the curable hydrophilic polymer may be selected from at least two of polyvinylpyrrolidone, polyethylene glycol, and polyether.

[0063] For example, the curable hydrophilic polymer can be selected from polyvinylpyrrolidone and polyether.

[0064] For example, the curable hydrophilic polymer can be selected from polyvinylpyrrolidone and polyethylene glycol. Blending polyvinylpyrrolidone with polyethylene glycol can further improve lubricity.

[0065] Furthermore, polyvinylpyrrolidone is selected from at least one of PVP-K30, PVP-K90, or PVP-K120.

[0066] For example, the curable hydrophilic polymer may be selected from PVP-K30, PVP-K90 and polyether.

[0067] For example, the curable hydrophilic polymer may be selected from PVP-K120 and polyether.

[0068] For example, the curable hydrophilic polymer may be selected from PVP-K30, PVP-K120, polyethylene glycol and polyether.

[0069] For example, the curable hydrophilic polymer may be selected from PVP-K90, PVP-K120, polyethylene glycol and polyether.

[0070] Furthermore, in some possible embodiments, the number-average molecular weight of the curable hydrophilic polymer is between 400 and 200,000 Daltons.

[0071] Furthermore, this application does not limit the specific weight content of the curable hydrophilic polymer in the hydrophilic coating solution. For example, the weight percentage of the curable hydrophilic polymer can be one of 4.5wt%, 5wt%, 5.5wt%, 6wt%, 6.5wt%, 7wt%, 7.5wt%, 8wt%, 8.5wt%, 9wt%, 9.5wt%, 10wt%, 10.5wt%, 11wt%, 11.5wt%, 12wt%, 12.5wt%, 13wt%, 13.5wt%, 14wt%, 14.5wt%, or 15wt%, or any combination thereof.

[0072] For example, the weight percentage of the curable hydrophilic polymer can be 4.5 wt% to 6 wt%. Alternatively, the weight percentage of the curable hydrophilic polymer can be 4.5 wt% to 10 wt%; or, the weight percentage of the curable hydrophilic polymer can be 5.5 wt% to 10 wt%.

[0073] A crosslinking agent includes at least two substances having crosslinkable functional groups. A crosslinking agent includes monomers and / or polymers, meaning that the crosslinking agent can be at least two different types of monomeric substances, or at least two different types of polymers, or at least one monomeric substance and at least one polymer. Whether it is a monomeric substance or a polymer, it has crosslinkable functional groups.

[0074] For example, the crosslinkable functional group may be selected from acrylates, acrylamides, or methyl methacrylates.

[0075] For example, the crosslinking agent may be selected from one or more of the following group: trimethylolpropane triacrylate, hydroxypropyl acrylate, isobornyl acrylate, butyl methacrylate, bisphenol A dimethacrylate, bisphenol A glycerol dimethacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, isobutyl methacrylate, tetrahydroxybutyl acrylate, bisphenol A ethoxymethyl dimethacrylate, propoxylated trimethylolpropane triacrylate. Trimethylolpropane ethoxylate triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane)tetraacrylate, poly(propylene glycol) dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, poly(ethylene glycol) methacrylate, polymethyl methacrylate, polypropylene glycol methacrylate, polypropylene glycol diacrylate, poly(ethylene glycol) diacrylate, polyethylene glycol methyl ether methacrylate, methoxy polyethylene glycol acrylate, poly(propylene glycol) methacrylate.

[0076] In one possible embodiment, the crosslinking agent comprises a monomer and a polymer having the same crosslinkable functional groups.

[0077] In one possible embodiment, the crosslinking agent may include a monomeric substance with different crosslinkable functional groups and a polymer.

[0078] In one possible embodiment, the crosslinking agent may include three substances having crosslinkable functional groups.

[0079] For example, the crosslinking agent may be a mixture of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.

[0080] For example, the crosslinking agent may be a mixture of polyethylene glycol diacrylate, triethylene glycol diacrylate and pentaerythritol triacrylate.

[0081] For example, the crosslinking agent may be a mixture of polyethylene glycol diacrylate, bis(trimethylolpropane)tetraacrylate and pentaerythritol triacrylate.

[0082] For example, the crosslinking agent may be a mixture of polyethylene glycol diacrylate, ethylene glycol dimethacrylate and pentaerythritol triacrylate.

[0083] Furthermore, the weight content of the crosslinking agent can be one of or between any two of the following: 1.5 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%.

[0084] For example, the weight content of the crosslinking agent can be 12 wt%. Alternatively, the weight content of the crosslinking agent can be 12 wt% to 20 wt%; or, the weight content of the crosslinking agent can be 12 wt% to 15 wt%; or, the weight content of the crosslinking agent can be 6 wt% to 15 wt%.

[0085] By combining and compounding multiple crosslinking agents, and increasing the proportion of crosslinking agents, it is possible to cooperate with a variety of curable hydrophilic polymers to achieve inter-chain branching and form a hydrophilic coating with an interpenetrating crosslinked network structure. The prepared coating fully expands in water to form a hydrogel, which can achieve a hydrophilic and super-slippery effect and ensure sufficient adhesion to the substrate, thus preventing the entire hydrophilic coating from falling off.

[0086] In some possible embodiments, the initiator may be selected from at least one of photoinitiators and thermoinitiators.

[0087] For example, the initiator may be selected from one or more of 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, benzoin, benzophenone, methyl benzoate or 1-hydroxycyclohexylphenyl ketone.

[0088] For example, the initiator may be selected from 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone.

[0089] In some possible embodiments, the weight content of the initiator can be one or a range between any two of 0.02wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, or 3wt%.

[0090] For example, the weight content of the initiator can be 0.44 wt% to 3 wt%. Alternatively, the weight content of the initiator can be 0.44 wt% to 2.5 wt%; or the weight content of the initiator can be 0.44 wt% to 1 wt%; or the weight content of the initiator can be 0.1 wt% to 0.44 wt%.

[0091] In some possible embodiments, the surfactant may be selected from at least one of ionic surfactants and nonionic surfactants.

[0092] For example, the surfactant is selected from one or more of sodium dodecyl sulfate, sodium cholate, sodium di(2-ethylhexyl)sulfosuccinate, hexadecyltrimethylammonium bromide, dodecyl dimethylamine oxide, sodium N-lauroyl sarcosinate and sodium deoxycholate or polyoxyethylene-polyoxypropylene copolymer.

[0093] For example, the surfactant is selected from one or more of Triton™ BG-10, Triton™ CG110, Triton™ X207, Triton™ N-57, Triton™ CA, Triton™ X-100, Tergitol™ TMN6, Tergitol™ L, Tergitol™ XD, Tergitol™ TXH, Tergitol™ T15, Tergitol™ TXJ, Tergitol™ 15-S-7, Tergitol™ 15-S-30, Tergitol™ 15-S-40, Tween 80, or Tween 20.

[0094] For example, the surfactant may be selected from alkoxy polyethylene hydroxyethanol.

[0095] Surfactants in hydrophilic coating solutions can cooperate with various curable hydrophilic polymers and crosslinking agents in the hydrophilic coating solution to improve the stability of the hydrophilic coating solution and improve the surface quality of the substrate. This allows a uniform and firmly adhered hydrophilic coating to be formed on the substrate surface, which is conducive to the formation of more crosslinked structures in the hydrophilic coating and increases the strength of the bond between the hydrophilic coating and the substrate surface.

[0096] In some possible embodiments, the surfactant content by weight may be one or a range between any two of 0.02wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, or 5wt%.

[0097] For example, the weight content of the surfactant may be 0.5wt% to 1wt%; or, the weight content of the surfactant may be 0.05wt% to 2wt%; or, the weight content of the surfactant may be 0.05wt% to 3wt%; or, the weight content of the surfactant may be 0.1wt% to 4wt%.

[0098] In some possible embodiments, the solvent may be selected from at least one of water and organic solvents.

[0099] For example, the organic solvent is selected from one or more components of the following group: ethyl acetate, acetone, butanone, dichloromethane, chloroform, methanol, anhydrous ethanol, n-propanol, isopropanol, or n-butanol.

[0100] For example, the solvent may be selected from ethanol; or, the solvent may be selected from ethanol and water.

[0101] For further details, please refer to Figure 1 This application also provides a method for preparing a hydrophilic coating solution, comprising:

[0102] S1, according to weight percentage, weigh 4.5wt% to 15wt% of a curable hydrophilic polymer, 1.5wt% to 20wt% of a crosslinking agent, 0.02wt% to 3wt% of an initiator, 0.02wt% to 5wt% of a surfactant, and the balance is a solvent; wherein, the curable hydrophilic polymer includes at least two polymers having curable functional groups.

[0103] S2. Add crosslinking agent and solvent to the curable hydrophilic polymer in sequence, and stir in the dark for 1-3 hours. After the solution is clear, add surfactant and initiator, and stir in the dark for 1-3 hours to obtain hydrophilic coating solution.

[0104] The hydrophilic coating solution provided in this application is applied to the surface of a substrate, and after photocuring, a lubricating coating can be formed on the surface of the substrate. For example, the substrate can be a conduit.

[0105] The hydrophilic coating provided in this application example has good initial lubricity and adhesion stability. Over time and with increased use, the hydrophilic coating can still maintain good lubricity and adhesion stability, and it is not easy to fall off during use.

[0106] The hydrophilic coating solution of this application will be further described in detail below with reference to the embodiments.

[0107] Example 1

[0108] Example 1 provides a hydrophilic coating solution, prepared as follows:

[0109] Weigh 12 wt% crosslinking agent, 5 wt% curable hydrophilic polymer, 1 wt% surfactant, 0.44 wt% initiator and 81.56 wt% solvent by weight, place them in a brown bottle, stir magnetically for 2 hours, and filter through a 500-mesh nylon screen to obtain a hydrophilic coating solution.

[0110] The crosslinking agent includes 6 wt% polyethylene glycol diacrylate and 6 wt% ethylene glycol dimethacrylate; the curable hydrophilic polymer includes 2 wt% PVP-K30, 2 wt% PVP-K90 and 1 wt% polyether; the surfactant is selected from alkoxylated polyethylene glycol hydroxyethanol; the initiator is selected from 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone; and the solvent is selected from ethanol solution. See Table 1 for some components.

[0111] Example 2

[0112] Example 2 provides a hydrophilic coating solution, the preparation method of which is as follows:

[0113] Weigh 12 wt% crosslinking agent, 4.5 wt% curable hydrophilic polymer, 1 wt% surfactant, 0.44 wt% initiator and 82.06 wt% solvent by weight, place them in a brown bottle, stir magnetically for 2 hours, and filter through a 500-mesh nylon screen to obtain a hydrophilic coating solution.

[0114] The crosslinking agent includes 4 wt% polyethylene glycol diacrylate, 4 wt% triethylene glycol diacrylate, and 4 wt% pentaerythritol triacrylate; the curable hydrophilic polymer includes 3 wt% PVP-K120 and 1.5 wt% polyether; the surfactant is selected from alkoxylated polyethylene glycol hydroxyethanol; the initiator is selected from 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone; and the solvent is selected from ethanol solution. See Table 1 for some components.

[0115] Example 3

[0116] Example 3 provides a hydrophilic coating solution, the preparation method of which is as follows:

[0117] Weigh 12 wt% crosslinking agent, 6 wt% curable hydrophilic polymer, 0.5 wt% surfactant, 0.44 wt% initiator and 81.06 wt% solvent by weight, place them in a brown bottle, stir magnetically for 2 hours, and filter through a 500-mesh nylon mesh to obtain a hydrophilic coating solution.

[0118] The crosslinking agent comprises a mixture of 4 wt% polyethylene glycol diacrylate, 4 wt% bis(trimethylolpropane)tetraacrylate, and 4 wt% pentaerythritol triacrylate; the curable hydrophilic polymer comprises 3 wt% PVP-K30, 1 wt% PVP-K120, 0.5 wt% polyethylene glycol (PEG), and 1.5 wt% polyether; the surfactant is selected from alkoxylated polyethylene glycol hydroxyethanol; the initiator is selected from 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone; and the solvent is selected from ethanol solution. See Table 1 for some components.

[0119] Example 4

[0120] Example 4 provides a hydrophilic coating solution, the preparation method of which is as follows:

[0121] Weigh 12 wt% crosslinking agent, 5.5 wt% curable hydrophilic polymer, 0.5 wt% surfactant, 0.44 wt% initiator and 81.56 wt% solvent by weight, place them in a brown bottle, stir magnetically for 2 hours, and filter through a 500-mesh nylon mesh to obtain a hydrophilic coating solution.

[0122] The crosslinking agent comprises a mixture of 4 wt% polyethylene glycol diacrylate, 4 wt% ethylene glycol dimethacrylate, and 4 wt% pentaerythritol triacrylate; the curable hydrophilic polymer comprises 2 wt% PVP-K90, 1 wt% PVP-K120, 1 wt% polyethylene glycol (PEG), and 1.5 wt% polyether; the surfactant is selected from alkoxylated polyethylene glycol hydroxyethanol; the initiator is selected from 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone; and the solvent is selected from an ethanol solution. See Table 1 for some components.

[0123] Comparative Example 1

[0124] Comparative Example 1 provides a hydrophilic coating solution, prepared as follows:

[0125] Weigh 0.5 wt% crosslinking agent, 2 wt% curable hydrophilic polymer, 0.05 wt% surfactant, 0.05 wt% initiator and 97.4 wt% solvent by weight, place them in a brown bottle, stir magnetically for 2 hours, and filter through a 500-mesh nylon mesh to obtain a hydrophilic coating solution.

[0126] The crosslinking agent includes 0.25 wt% ethylene glycol diacrylate and 0.25 wt% polyethylene glycol diacrylate; the curable hydrophilic polymer includes 2 wt% PVP; the surfactant is selected from end-group polyether modified polysiloxane; the initiator is selected from 1-hydroxycyclohexylphenyl ketone; and the solvent is selected from ethanol solution. See Table 1 for some components.

[0127] Comparative Example 2

[0128] Comparative Example 2 provides a hydrophilic coating solution, prepared as follows:

[0129] Weigh 0.9 wt% crosslinking agent, 3 wt% curable hydrophilic polymer, 0.1 wt% surfactant, 0.08 wt% initiator and 95.92 wt% solvent by weight, place them in a brown bottle, stir magnetically for 2 hours, and filter through a 500-mesh nylon mesh to obtain a hydrophilic coating solution.

[0130] The crosslinking agent includes 0.3 wt% propoxylated glycerol triacrylate, 0.3 wt% ethylene glycol diacrylate, and 0.3 wt% polyethylene glycol diacrylate; the curable hydrophilic polymer includes 3 wt% PVP; the surfactant is selected from polydimethylsiloxane; the initiator is selected from 0.04 wt% 1-hydroxycyclohexylphenyl ketone and 0.04 wt% 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone; the solvent includes 80 wt% isopropanol and 15.92 wt% deionized water. See Table 1 for some components.

[0131] Comparative Example 3

[0132] Comparative Example 3 provides a hydrophilic coating solution, prepared as follows:

[0133] Weigh 0.8 wt% crosslinking agent, 3 wt% curable hydrophilic polymer, 0.1 wt% surfactant, 0.08 wt% initiator and 95.92 wt% solvent by weight, place them in a brown bottle, stir magnetically for 2 hours, and filter through a 500-mesh nylon mesh to obtain a hydrophilic coating solution.

[0134] The crosslinking agent includes 0.4 wt% propoxylated glycerol triacrylate and 0.4 wt% polyethylene glycol diacrylate; the curable hydrophilic polymer includes 1.5 wt% polyvinylpyrrolidone with a molecular weight of 1 million Daltons and 1.5 wt% polyethylene oxide with a molecular weight of 300,000 Daltons; the surfactant is selected from fluorinated alkyd copolymers; the initiator is selected from 0.04 wt% 1-hydroxycyclohexylphenyl ketone and 0.04 wt% 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone; the solvent includes 85 wt% anhydrous ethanol and 11.02 wt% deionized water. See Table 1 for some components.

[0135] Table 1

[0136]

[0137]

[0138] Test case

[0139] Friction tests and stability tests before and after aging were conducted on the hydrophilic coatings formed after curing the hydrophilic coating solutions provided in Examples 1-4 and Comparative Examples 1-3.

[0140] Sample preparation for aging: The core theory of accelerated aging testing is that the chemical reactions during material degradation follow the Arrhenius reaction rate function; for every 10°C increase or decrease in temperature during a homogeneous process, the rate of the chemical reaction doubles or halves. Based on this theory, the accelerated aging factor can be estimated using the following formula:

[0141]

[0142] In the formula, AAF refers to the aging acceleration factor, TAA refers to the aging acceleration temperature, and TRT refers to the ambient temperature. Q 10 This refers to the aging factor, which is generally determined by testing materials at various temperatures. Typically, Q is taken as... 10 The value of 2 is a common and conservative method for calculating the aging-accelerating factor.

[0143] After obtaining the AAF estimate, the accelerated aging time can be determined using the following formula:

[0144] AAT=D(RT) / AAF

[0145] Among them, AAT refers to Accelerated Aging Time, RT refers to the expected or required actual time, and AAF refers to Accelerated Aging Factor.

[0146] After curing, the catheter samples are packaged and sterilized. After sterilization and analysis, the samples are sent to an aging oven at a temperature of 55°C for two years of accelerated aging.

[0147] Friction test: The cured conduit sample was immersed in an aqueous solution at 25±3℃ for 2 minutes. A friction tester was used with a holding force of 500g and a tensile speed of 200mm / min for 15 repeated lifting cycles.

[0148] Stability test: If the catheter sample remains lubricated after 15 repeated pull-ups, the coating is considered stable. If the coating curve changes significantly during the 15 pull-ups, the coating is considered unstable and at risk of detachment during friction.

[0149] The friction-displacement curves of the hydrophilic coating formed after curing the hydrophilic coating solution provided in Example 1 at time zero and after two years of aging are shown in the following figures. Figure 1 and Figure 2 The friction-displacement curves of the hydrophilic coating formed after curing the hydrophilic coating solution provided in Example 2 at time zero and after two years of aging are shown in the following figures. Figure 3 and Figure 4The friction-displacement curves of the hydrophilic coating formed after curing the hydrophilic coating solution provided in Example 3 at time zero and after two years of aging are shown in the following figures. Figure 5 and Figure 6 The friction-displacement curves of the hydrophilic coating formed after curing the hydrophilic coating solution provided in Example 4 at time zero and after two years of aging are shown in the following figures. Figure 7 and Figure 8 The friction-displacement curves of the hydrophilic coating formed after curing the hydrophilic coating solution provided in Comparative Example 1 after two years of aging are shown in the following figures. Figure 9 The friction-displacement curves of the hydrophilic coating formed after curing the hydrophilic coating solution provided in Comparative Example 2 after two years of aging are shown in the following figures. Figure 10 The friction-displacement curves of the hydrophilic coating formed after curing the hydrophilic coating solution provided in Comparative Example 3 after two years of aging are shown in the following figures. Figure 11 The test results are shown in Table 2.

[0150] Table 2

[0151]

[0152] Results analysis:

[0153] The change in friction value of the hydrophilic coating before and after 2 years of aging is related to its lubrication stability and coating adhesion stability. A greater change in friction value before and after 2 years of aging indicates instability of the hydrophilic coating, making it prone to detachment, leading to increased friction and decreased lubrication. Table 1 shows that the hydrophilic coatings formed by curing the hydrophilic coating solutions provided in Examples 1-4 of this application did not show a significant increase in friction after 2 years of aging compared to the friction at zero time; in fact, they even decreased. However, in Comparative Examples 1-3, the friction increased significantly after 2 years of aging compared to the friction at zero time. This demonstrates that the hydrophilic coating solution provided in the examples of this application, comprising 4.5wt%–15wt% curable hydrophilic polymer, 1.5wt%–20wt% crosslinking agent, 0.02wt%–3wt% initiator, and 0.02wt%–5wt% surfactant, and with the crosslinking agent including at least two substances having crosslinkable functional groups, can produce a hydrophilic coating with good lubrication effect and strong lubrication stability.

[0154] Furthermore, the hydrophilic coatings formed by curing the hydrophilic coating solutions provided in Examples 1-4 of this application maintain good adhesion stability at both the initial time and after 2 years of aging, and the hydrophilic coatings can adhere uniformly and stably to the surface of the conduit. In contrast, the hydrophilic coatings provided in Comparative Examples 1-3, although exhibiting good adhesion stability at the initial time, all showed signs of peeling after 2 years of aging, indicating poor stability. This demonstrates that the hydrophilic coating solutions provided in the embodiments of this application, comprising 4.5wt%–15wt% curable hydrophilic polymer, 1.5wt%–20wt% crosslinking agent, 0.02wt%–3wt% initiator, and 0.02wt%–5wt% surfactant, wherein the crosslinking agent includes at least two substances with crosslinkable functional groups, can produce hydrophilic coatings with high adhesion stability.

[0155] Furthermore, as can be seen from Examples 3 and 4, the use of multiple PVP and PEG in combination in the hydrophilic coating solution can further reduce the friction of the hydrophilic coating at zero time and after 2 years of aging, and can further improve the lubricity of the hydrophilic coating.

[0156] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A hydrophilic coating solution characterized in that, The product comprises, by weight percentage: 4.5 wt% to 15 wt% of a curable hydrophilic polymer, 1.5 wt% to 20 wt% of a crosslinking agent, 0.02 wt% to 3 wt% of an initiator, 0.02 wt% to 5 wt% of a surfactant, and the balance being a solvent; wherein the curable hydrophilic polymer comprises at least two polymers having curable functional groups, the crosslinking agent comprises at least two substances having crosslinkable functional groups, and the crosslinking agent comprises monomers and / or polymers.

2. The hydrophilic coating solution of claim 1, wherein, The product comprises, by weight percentage: 4.5 wt% to 10 wt% of curable hydrophilic polymer, 6 to 12 wt% of crosslinking agent, 0.02 wt% to 3 wt% of initiator, 0.5 wt% to 1 wt% of surfactant, and the balance being solvent.

3. The hydrophilic coating solution of claim 1, wherein, The curable hydrophilic polymer may be selected from at least two of the following groups: polyethylene glycol, polypropylene glycol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyacrylamide, polyvinyl alcohol, polyamide, polyetherimide, polypeptide amine, polyvinylpyrrolidone, polyethylene oxide, or polyurethane.

4. The hydrophilic coating solution according to claim 3, characterized in that, The curable hydrophilic polymer is selected from at least two of the polyvinylpyrrolidone, the polyethylene glycol, and the polyether; Optionally, the polyvinylpyrrolidone is selected from at least one of PVP-K30, PVP-K90, or PVP-K120.

5. The hydrophilic coating solution according to claim 1, characterized in that, The crosslinkable functional group is selected from at least one of acrylate, acrylamide, or methyl methacrylate; Optionally, the crosslinking agent is selected from polyesters and / or polyethers; Optionally, the crosslinking agent is selected from one or more of the following groups: trimethylolpropane triacrylate, hydroxypropyl acrylate, isobornyl acrylate, butyl methacrylate, bisphenol A dimethacrylate, bisphenol A glycerol dimethacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, isobutyl methacrylate, tetrahydroxybutyl acrylate, bisphenol A ethoxymethyl dimethacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane ethoxy acrylate triacrylate, pentaerythritol tetraacrylate, di(trimethylolpropane)tetraacrylate, polypropylene glycol dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol methyl ether acrylate, polyethylene glycol methacrylate, polymethyl methacrylate, polypropylene glycol methacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol methyl ether methacrylate, methoxy polyethylene glycol acrylate, and polypropylene glycol methacrylate.

6. The hydrophilic coating solution according to claim 5, characterized in that, The crosslinking agent includes at least three substances having the crosslinkable functional groups.

7. The hydrophilic coating solution according to claim 1, characterized in that, The initiator is selected from photoinitiators and / or thermoinitiators; Optionally, the initiator is selected from one or more of 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, benzoin, benzophenone, methyl benzoate, or 1-hydroxycyclohexylphenyl ketone.

8. The hydrophilic coating solution according to claim 1, characterized in that, The surfactant is selected from ionic surfactants and / or nonionic surfactants; Optionally, the surfactant is selected from one or more of alkoxyethylene hydrooxyethanol, sodium dodecyl sulfate, sodium cholate, sodium di(2-ethylhexyl)sulfosuccinate, hexadecyltrimethylammonium bromide, dodecyl dimethylamine oxide, N-lauroyl sarcosinate sodium salt and sodium deoxycholate or polyoxyethylene-polyoxypropylene copolymer. Optionally, the surfactant is selected from one or more of Triton™ BG-10, Triton™ CG-110, Triton™ X-207, Triton™ N-57, Triton™ CA, Triton™ X-100, Tergitol™ TMN-6, Tergitol™ L, Tergitol™ XD, Tergitol™ TXH, Tergitol™ TT-15, Tergitol™ TXJ, Tergitol™ 15-S-7, Tergitol™ 15-S-30, Tergitol™ 15-S-40, Tween 80, or Tween 20.

9. The hydrophilic coating solution according to claim 1, characterized in that, The solvent is selected from water and / or organic solvents; Optionally, the organic solvent is selected from one or more components of the group consisting of ethyl acetate, acetone, butanone, dichloromethane, chloroform, methanol, anhydrous ethanol, n-propanol, isopropanol, or n-butanol.

10. A medical device, characterized in that, It includes a substrate and a hydrophilic coating attached to the surface of the substrate; the hydrophilic coating is formed by curing the hydrophilic coating solution according to any one of claims 1-9; Optionally, the substrate is selected from the guide; Optionally, the substrate is selected from catheters or guidewires; Optionally, the substrate is selected from urinary catheters.

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