Coating compositions, methods for preparing lubricating coatings, and medical materials

Abstract

This application relates to a coating composition, a method for preparing a lubricating coating, and a medical material. The coating composition, by weight, comprises: 1-5 parts of a hydrophilic polymer, 2-8 parts of a terpolymer, 0.2-0.5 parts of a first crosslinking agent, and 0.2-1 parts of a second crosslinking agent; wherein the terpolymer comprises a first repeating unit, a second repeating unit, and a third repeating unit connected by covalent bonds, the first repeating unit having the structural formula [insert structural formula here], the second repeating unit having the structural formula [insert structural formula here], and the third repeating unit having the structural formula [insert structural formula here]; the first crosslinking agent is used to crosslink the hydrophilic polymer with the third repeating unit, and the second crosslinking agent is used to crosslink the first repeating unit and / or the second repeating unit. The coating composition is used to prepare a lubricating coating, which can improve the adhesion of the coating while ensuring lubricity.

Description

Technical Field

[0001] This application relates to the field of medical materials, and in particular to a coating composition, a method for preparing a lubricating coating, and medical materials. Background Technology

[0002] In clinical practice, when inserting catheters into body cavities, some catheters are coated with lubricants such as silicone oil to reduce friction. However, this lubrication is only temporary, and the silicone oil or similar substances easily detach from the catheter surface, causing discomfort to the patient within the body cavity. Other methods employ hydrophilic lubricating coatings, which become highly lubricating upon contact with bodily fluids or other moisture-containing environments, thus reducing friction during insertion. However, while traditional lubricating coatings offer good surface lubrication, their adhesion is weak, making them prone to detachment. Summary of the Invention

[0003] Based on this, some embodiments of this application provide a coating composition for preparing a lubricating coating, which can improve the adhesion of the coating while ensuring lubricity.

[0004] In addition, some other embodiments of this application also provide a method for preparing a lubricating coating and a medical material.

[0005] A coating composition for forming a coating on a substrate, comprising, by weight parts: 1 to 5 parts of a hydrophilic polymer, 2 to 8 parts of a terpolymer, 0.2 to 0.5 parts of a first crosslinking agent, and 0.2 to 1 part of a second crosslinking agent;

[0006] The terpolymer comprises a first repeating unit, a second repeating unit, and a third repeating unit connected by covalent bonds. The structural formula of the first repeating unit is as follows: The structural formula of the second repeating unit is The structural formula of the third repeating unit is as follows: R1 and R2 are each independently a C1-C3 alkyl group, and R3 is hydrogen or methyl;

[0007] The first crosslinking agent is used to crosslink the hydrophilic polymer with the third repeating unit, and the second crosslinking agent is used to crosslink the first repeating unit and / or the second repeating unit with the substrate.

[0008] In some embodiments, the first crosslinking agent contains one or more groups selected from diazide groups and amino groups.

[0009] In some embodiments, the first crosslinking agent includes one or more of sodium 4,4'-diazidostilbene-2,2'-disulfonate and diethylenetriamine.

[0010] In some embodiments, the second crosslinking agent contains one or more groups selected from isocyanate groups and acrylate groups.

[0011] In some embodiments, the second crosslinking agent includes one or more of diphenylmethane diisocyanate and polyethylene glycol diacrylate.

[0012] In some embodiments, the molar ratio of the first repeating unit, the second repeating unit, and the third repeating unit in the terpolymer is (2~10):1:(3~5).

[0013] In some embodiments, R1 and R2 are both methyl groups, and R3 is hydrogen.

[0014] In some embodiments, the hydrophilic polymer includes one or more of polyvinylpyrrolidone, poly(N-vinyl-2-piperidone), and polyvinylimidazolium.

[0015] In some embodiments, a third crosslinking agent in the form of 0.1 to 0.5 parts by weight is further included, the third crosslinking agent being used to crosslink the hydrophilic polymer and the substrate.

[0016] In some embodiments, the third crosslinking agent contains a first active group and a second active group, wherein the first active group includes a siloxy group and the second active group includes one or more of an amino group, an epoxy group, and a carbonyl group.

[0017] In some embodiments, the third crosslinking agent includes one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, (3-aminopropyl)triethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0018] In some embodiments, the coating composition further includes 0.5 to 2 parts by weight of an additive, which includes one or more of surfactants and antioxidants.

[0019] In some embodiments, the additives include one or more of sodium lauryl ether sulfate and 2,6-di-tert-butyl-4-methylphenol.

[0020] In some embodiments, the coating composition further includes 83 to 94 parts by weight of solvent.

[0021] A method for preparing a lubricating coating includes the following steps:

[0022] A coating composition is applied to the surface of a substrate to form a lubricating coating; wherein the coating composition is as described above;

[0023] The lubricating coating is heated to crosslink the hydrophilic polymer and the third repeating unit of the terpolymer in the lubricating coating, and to crosslink the substrate with the first and / or second repeating units of the terpolymer, and to cure the lubricating coating.

[0024] In some embodiments, the heating step of the lubricating coating is performed at a temperature of 50°C to 85°C for a time of 2 hours to 6 hours.

[0025] A medical material includes a substrate and a lubricating coating disposed on the surface of the substrate, the lubricating coating being prepared by the preparation method described above.

[0026] Traditional coating compositions include solutions of hydrophilic polymers. These hydrophilic polymers possess lubricating properties by binding with water molecules, thus improving the lubricity of the prepared coating. However, the adhesion between the hydrophilic polymer and the substrate is weak, making the coating prone to peeling. In contrast, some embodiments of this application provide coating compositions that further incorporate a terpolymer, a first crosslinking agent, and a second crosslinking agent into the hydrophilic polymer solution. The terpolymer comprises a first repeating unit, a second repeating unit, and a third repeating unit. The hydrophobic portions of the first and second repeating units can bond to the hydrophobic substrate surface via the second crosslinking agent. Furthermore, the second repeating unit, due to the presence of benzene rings, enhances the attractive force of the cyclic structure in the hydrophilic groups, resulting in a denser network structure. The hydrophilic portion of the third repeating unit in the terpolymer can bond with the hydrophilic polymer via the first crosslinking agent and can also be entangled with the hydrophilic polymer through intermolecular forces, thereby improving the adhesion between the prepared coating and the substrate. Attached Figure Description

[0027] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0028] Figure 1 This is a process flow diagram of a method for preparing a lubricating coating in some embodiments of this application. Detailed Implementation

[0029] To facilitate understanding of this application, a more comprehensive description of the application will be provided below in conjunction with specific embodiments. Preferred embodiments of the application are given in the specific embodiments. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the specification of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0031] Unless otherwise stated or in case of conflict, the terms or phrases used in this application shall have the following meanings:

[0032] In this application, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined with "first" and "second" may explicitly or implicitly include at least one of those features.

[0033] In the description of this application, "multiple" means at least two, such as two, three, etc., unless otherwise expressly and specifically limited.

[0034] In this application, "one or more" refers to any one, any two, or any two or more of the listed items. "Several" refers to any two or more.

[0035] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0036] The terms "optionally" and similar expressions used in this application refer to embodiments of this application that may provide certain beneficial effects under certain circumstances. However, other embodiments may also be optional in the same or other circumstances. Furthermore, the description of one or more optional embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this application.

[0037] When a numerical range is disclosed in this application, the range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed in this application should be understood to include any and all subranges to which they are included.

[0038] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0039] The terms "comprising" and "having," and any variations thereof, used in the embodiments of this application, are intended to cover non-exclusive inclusion. For example, a process, method, system, product, or device that includes a series of steps or units is not limited to the steps or units listed, but may optionally include steps or units not listed, or may optionally include other steps or components inherent to such processes, methods, products, or devices.

[0040] In this application, the reference to "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The appearance of this phrase in various places in the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described in this application can be combined with other embodiments.

[0041] The first aspect of this application provides a coating composition comprising, by weight parts: 1 to 5 parts of a hydrophilic polymer, 2 to 8 parts of a terpolymer, 0.2 to 0.5 parts of a first crosslinking agent, and 0.2 to 1 part of a second crosslinking agent;

[0042] The terpolymer comprises a first repeating unit, a second repeating unit, and a third repeating unit connected by covalent bonds. The structural formula of the first repeating unit is as follows: The structural formula of the second repeating unit is The structural formula of the third repeating unit is as follows: R1 and R2 are each independently a C1-C3 alkyl group, and R3 is hydrogen or methyl;

[0043] The first crosslinking agent is used to crosslink the hydrophilic polymer with the third repeating unit, and the second crosslinking agent is used to crosslink the first repeating unit and / or the second repeating unit.

[0044] Some embodiments of this application address the issue of hydrophilic lubricating coatings being prone to peeling by providing a coating composition. This composition includes a terpolymer, a first crosslinking agent, and a second crosslinking agent added to a solution containing a hydrophilic polymer. The terpolymer comprises a first repeating unit, a second repeating unit, and a third repeating unit, forming a three-dimensional network structure. The hydrophobic portions of the first and second repeating units can bond to the hydrophobic substrate surface through the second crosslinking agent. Furthermore, the second repeating unit, containing a benzene ring, enhances the attractive force between the cyclic structure in the hydrophilic group, resulting in a tighter network structure. The hydrophilic portion of the third repeating unit in the terpolymer can bond to the hydrophilic polymer through the first crosslinking agent and can also be entangled with the hydrophilic polymer through intermolecular forces, thereby improving the adhesion between the prepared coating and the substrate.

[0045] In an optional example, the mass fractions of the hydrophilic polymer in the coating composition may be, but are not limited to, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or any combination of these values.

[0046] In some embodiments, the hydrophilic polymer includes one or more of polyvinylpyrrolidone, poly(N-vinyl-2-piperidinone), and polyvinylimidazolium. The hydrophilic polymer is beneficial for improving the lubricity of water molecules. Furthermore, the hydrophilic polymer is entangled with the terpolymer through intermolecular forces such as hydrogen bonding and covalent bonding by the first crosslinking agent.

[0047] In an optional example, the mass fractions of the terpolymer in the coating composition may be, but are not limited to, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, or any combination of these values.

[0048] In some embodiments, the molar ratio of the first repeating unit, the second repeating unit, and the third repeating unit in the terpolymer is (2~10):1:(3~5). In a specific example, the molar ratio of the first repeating unit, the second repeating unit, and the third repeating unit in the terpolymer is 2:1:3.

[0049] The aforementioned ternary copolymer comprises a first repeating unit, a second repeating unit, and a third repeating unit. The hydrophobic portions of the first and second repeating units can bond to the hydrophobic substrate surface via a second crosslinking agent. The second repeating unit, due to the presence of benzene rings, enhances the network structure by combining with the attractive force of the cyclic structure in the hydrophilic group. The hydrophilic portion of the third repeating unit in the ternary copolymer can bond to the hydrophilic polymer via the first crosslinking agent and can also entangle with the hydrophilic polymer through intermolecular forces, thereby improving the adhesion between the prepared coating and the substrate. Experiments have shown that using a binary copolymer or replacing components such as the second repeating unit in the ternary copolymer with chain-like polyolefins reduces coating adhesion.

[0050] In some embodiments, R1 and R2 are each independently methyl, ethyl, propyl, etc. Specifically, the monomer corresponding to the first repeating unit includes one or more of dimethylacrylamide, diethylacrylamide, and N-ethyl-2-methylacrylamide.

[0051] In some embodiments, R3 is hydrogen or methyl. Specifically, the monomer corresponding to the second repeating unit includes one or more of styrene and methylstyrene. In one embodiment, the monomer corresponding to the second repeating unit includes styrene.

[0052] In some embodiments, the monomer corresponding to the third repeating unit includes one or more of ethylene glycol and ethylene oxide.

[0053] In some embodiments, the monomers for preparing the terpolymer include dimethacrylamide, styrene, and ethylene glycol; or, the monomers for preparing the terpolymer include dimethacrylamide, styrene, and ethylene oxide. Specifically, the monomers for preparing the terpolymer include dimethacrylamide, styrene, and ethylene glycol in a molar ratio of (2~10):1:(3~5); or, the monomers for preparing the terpolymer include dimethacrylamide, styrene, and ethylene oxide in a molar ratio of (2~10):1:(3~5).

[0054] In some embodiments, the preparation steps of the terpolymer include: weighing the monomers corresponding to the first repeating unit, the second repeating unit and the third repeating unit in a molar ratio of (2~10):1:(3~5) and dissolving them in an organic solvent, and carrying out a heating reaction under the action of an initiator, a chain extender and nitrogen protection.

[0055] It is understandable that in the polymerization process of the three monomers, there may be two connection methods: Method a: the first repeating unit and the second repeating unit are connected, and then the second repeating unit is connected to the third repeating unit; Method b: the second repeating unit is connected to the third repeating unit, and then the third repeating unit is connected to the first repeating unit. Under the above reaction process, Method a accounts for 30% to 80%.

[0056] In a specific example, the organic solvents include acetone and ethanol. The initiator includes a peroxide initiator, such as ammonium persulfate. The chain extender includes polyethylene glycol diacrylate.

[0057] In a specific example, the temperature of the heating reaction is 60℃~70℃, and the heating reaction time is 15h~18h.

[0058] In one specific example, the heating reaction is followed by a step of washing and drying with anhydrous ethanol.

[0059] In a specific example, the preparation steps of the terpolymer include: weighing the monomers corresponding to the first, second, and third repeating units in a molar ratio of (2~10):1:(3~5) and dissolving them in a mixed solution of acetone and ethanol; and heating the mixture at 60℃~70℃ for 15h~18h under the action of an initiator and a chain extender, and under nitrogen protection. After the reaction is complete, the mixture is washed with anhydrous ethanol and dried to obtain the terpolymer. Specifically, the initiator includes a peroxide initiator, such as ammonium persulfate, and the chain extender includes polyethylene glycol diacrylate.

[0060] In an optional example, the mass fraction of the first crosslinking agent in the coating composition may be, but is not limited to, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts, 0.5 parts, or any combination of these values.

[0061] In some embodiments, the first crosslinking agent contains one or more groups selected from diazide groups and amino groups. In one example, the first crosslinking agent includes one or more of sodium 4,4'-diazidostilbene-2,2'-disulfonate and diethylenetriamine. The first crosslinking agent containing diazide groups is capable of thermal decomposition, generating highly reactive free radicals that insert into the polymer chain to achieve crosslinking with hydrophilic polymers and terpolymers. The first crosslinking agent containing amino groups is capable of crosslinking with hydrophilic polymers through hydrogen bonding and with terpolymers through covalent bonds.

[0062] In an optional example, the mass fraction of the second crosslinking agent in the coating composition may be, but is not limited to, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, or any combination of these values.

[0063] In some embodiments, the second crosslinking agent contains one or more groups selected from isocyanate groups and acrylate groups. Specifically, the second crosslinking agent includes one or more selected from diphenylmethane diisocyanate and polyethylene glycol diacrylate. The second crosslinking agent is linked to the substrate by reacting with polar groups such as hydroxyl and carboxyl groups on the surface of the substrate, and is linked to the terpolymer by reacting with hydroxyl groups or unsaturated groups in the terpolymer.

[0064] In some embodiments, the coating composition further includes a third crosslinking agent, which is used to crosslink the hydrophilic polymer and the substrate. Specifically, the third crosslinking agent contains a first active group and a second active group. The first active group includes a siloxy group, and the second active group includes one or more of amino, epoxy, and carbonyl groups. The third crosslinking agent mainly connects the substrate interface and the hydrophilic polymer, bonding to the substrate surface through its first group and to the hydrophilic polymer through its second group. Adding a third crosslinking agent to the coating composition is beneficial for further improving the adhesion and bonding strength between the coating and the substrate.

[0065] In one example, the third crosslinking agent includes one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, (3-aminopropyl)triethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0066] In some embodiments, the third crosslinking agent is present in the coating composition in parts by mass of 0.1 to 0.5. For example, in an optional example, the mass percentage of the third crosslinking agent in the coating composition may be, but is not limited to, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, or any combination of these values.

[0067] By using three crosslinking agents in combination, the bonding force between the hydrophilic polymer and the terpolymer, the terpolymer and the substrate, and the hydrophilic polymer and the substrate surface is improved, which greatly enhances the adhesion of the prepared coating and makes it less likely to fall off.

[0068] In some embodiments, the coating composition further includes additives. Additives include one or more of surfactants and antioxidants. In some embodiments, the additives include one or more of sodium lauryl ether sulfate and 2,6-di-tert-butyl-4-methylphenol. It is understood that only two commonly used additives are given above, but the composition is not limited to these and can be adjusted according to actual needs.

[0069] In some embodiments, the additives in the coating composition are 0.5 to 2 parts by weight. For example, the additives in the coating composition may be, but are not limited to, 0.5, 0.6, 0.8, 1, 1.2, 1.4, 1.5, 1.6, 1.8, 2 parts by weight, or any combination of these values. In an optional example, the additives in the coating composition include 0.5 parts by weight of sodium lauryl polyoxyethylene ether sulfate and 0.5 parts by weight of 2,6-di-tert-butyl-4-methylphenol.

[0070] In some embodiments, the coating composition comprises, by weight parts, 1 to 5 parts of a hydrophilic polymer, 2 to 8 parts of a terpolymer, 0.2 to 0.5 parts of a first crosslinking agent, 0.2 to 1 part of a second crosslinking agent, 0.1 to 0.5 parts of a third crosslinking agent, and 0.5 to 2 parts of an additive.

[0071] In some embodiments, the coating composition further includes 83 to 94 parts by weight of solvent. For example, the parts by weight of solvent may be, but are not limited to, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94 parts or any combination of these values.

[0072] In some embodiments, the solvent includes one or more of ethanol, acetone, butanone, and ethyl acetate. In one example, the solvent includes ethanol and butanone.

[0073] In some embodiments, the coating composition comprises, by weight parts, 1 to 5 parts of hydrophilic polymer, 2 to 8 parts of terpolymer, 0.2 to 0.5 parts of first crosslinking agent, 0.2 to 1 part of second crosslinking agent, 0.1 to 0.5 parts of third crosslinking agent, 0.5 to 2 parts of additives, and 83 to 94 parts of solvent.

[0074] In some embodiments, the preparation steps of the coating composition include:

[0075] Weigh out the following raw materials by mass: 1 to 5 parts hydrophilic polymer, 2 to 8 parts terpolymer, 0.2 to 0.5 parts first crosslinking agent, 0.2 to 1 part second crosslinking agent, 0.1 to 0.5 parts optional third crosslinking agent, 83 to 94 parts solvent, and 0.5 to 2 parts optional additives;

[0076] Mix and stir the raw materials to prepare a coating composition.

[0077] It is understood that in some other embodiments, the coating composition may not contain a solvent. When using it, the components in the coating composition are mixed with a solvent to form a solution. That is, before use, the components in the coating composition are independent components, and the solvent is added and mixed when using it.

[0078] The second aspect of this application provides a method for preparing a lubricating coating; please refer to [link to relevant documentation]. Figure 1 It includes the following steps:

[0079] Step S210: Apply the coating composition to the substrate surface to form a lubricating coating.

[0080] The coating composition is as described above.

[0081] In some embodiments, the coating composition is applied to the surface of a substrate by dip coating. Specifically, the substrate is immersed in a solution in which the coating composition is dispersed for 10 to 20 seconds, and the solvent in the solution in which the coating composition is dispersed includes one or more of ethanol, acetone, butanone, and ethyl acetate.

[0082] In some embodiments, the substrate material includes one or more of polyurethane, polyvinyl chloride, silicone, and nylon.

[0083] Step S220: Heating the lubricating coating to crosslink the hydrophilic polymer and the third repeating unit of the terpolymer in the lubricating coating, and to crosslink the substrate with the first and / or second repeating units of the terpolymer, and to cure the lubricating coating.

[0084] In some embodiments, the heating step of the lubricating coating is performed at a temperature of 50°C to 85°C for a time of 2 hours to 6 hours. For example, the curing temperature can be, but is not limited to, 50°C, 52°C, 55°C, 58°C, 60°C, 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 82°C, 85°C, or any combination of these values. The curing time can be, but is not limited to, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, or any combination of these values.

[0085] A third aspect of this application provides a medical material comprising a substrate and a lubricating coating disposed on the surface of the substrate, wherein the lubricating coating is prepared by the preparation method of the second aspect described above.

[0086] In some embodiments, the medical material may be, but is not limited to, a medical catheter.

[0087] To make the objectives and advantages of this application clearer, the coating composition and its effects of this application are further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are only for explaining this application and should not be used to limit this application. Unless otherwise specified, the following embodiments do not include components other than unavoidable impurities. Unless otherwise specified, the drugs and instruments used in the embodiments are conventional choices in the art. Experimental methods in the embodiments that do not specify specific conditions are implemented according to conventional conditions, such as those described in literature, books, or methods recommended by the manufacturer.

[0088] The preparation steps of the terpolymers in the following examples and comparative examples are as follows: Each monomer raw material was obtained according to the monomer and molar ratio used in each example and comparative example. It was dissolved in a mixed solution of acetone and ethanol, and reacted at 60°C for 15 hours under the action of ammonium persulfate initiator, polyethylene glycol diacrylate chain extender, and nitrogen protection. After the reaction was completed, the copolymer was removed, washed with anhydrous ethanol, and dried to obtain the terpolymer.

[0089] Example 1

[0090] This embodiment provides a coating composition, comprising, by weight parts: 2 parts polyvinylpyrrolidone, 3 parts a terpolymer of dimethacrylamide, styrene, and ethylene glycol, 0.25 parts sodium 4,4'-diazidostilbene-2,2'-disulfonate, 0.3 parts diphenylmethane diisocyanate, 0.2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.5 parts sodium lauryl ether sulfate, 0.5 parts 2,6-di-tert-butyl-4-methylphenol, 53.25 parts ethanol, and 40 parts butanone. The molar ratio of dimethacrylamide, styrene, and ethylene glycol in the terpolymer is 2:1:3.

[0091] The preparation steps of the coating composition in this embodiment are as follows: Mix and stir the above raw materials for half an hour to obtain the coating composition.

[0092] Example 2

[0093] This embodiment provides a coating composition, comprising, by weight parts: 2 parts polyvinylpyrrolidone, 3 parts a terpolymer of dimethacrylamide, styrene, and ethylene glycol, 0.25 parts diethylenetriamine, 0.4 parts polyethylene glycol diacrylate, 0.2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.5 parts sodium lauryl ether sulfate, 0.5 parts 2,6-di-tert-butyl-4-methylphenol, 53.15 parts ethanol, and 40 parts butanone. The molar ratio of dimethacrylamide, styrene, and ethylene glycol in the terpolymer is 2:1:3.

[0094] The preparation steps of the coating composition in this embodiment are as follows: Mix and stir the above raw materials for half an hour to obtain the coating composition.

[0095] Example 3

[0096] This embodiment provides a coating composition, comprising, by weight parts: 2 parts polyvinylpyrrolidone, 2.8 parts a terpolymer of dimethacrylamide, styrene, and ethylene oxide, 0.25 parts sodium 4,4'-diazidostilbene-2,2'-disulfonate, 0.3 parts diphenylmethane diisocyanate, 0.2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.5 parts sodium lauryl ether sulfate, 0.5 parts 2,6-di-tert-butyl-4-methylphenol, 53.45 parts ethanol, and 40 parts butanone. The molar ratio of dimethacrylamide, styrene, and ethylene oxide in the terpolymer is 2:1:3.

[0097] The preparation steps of the coating composition in this embodiment are as follows: Mix and stir the above raw materials for half an hour to obtain the coating composition.

[0098] Example 4

[0099] This embodiment provides a coating composition similar to that of Example 1, except that it does not contain a third crosslinking agent. Specifically, by weight, it comprises: 2 parts polyvinylpyrrolidone, 3 parts a terpolymer of dimethacrylamide, styrene, and ethylene glycol, 0.25 parts sodium 4,4'-diazidostilbene-2,2'-disulfonate, 0.3 parts diphenylmethane diisocyanate, 0.5 parts sodium lauryl ether sulfate, 0.5 parts 2,6-di-tert-butyl-4-methylphenol, 53.45 parts ethanol, and 40 parts butanone.

[0100] Comparative Example 1

[0101] Comparative Example 1 is a hydrophilic lubricated medical catheter from a certain brand on the market.

[0102] Comparative Example 2

[0103] Comparative Example 2 provides a coating composition similar to that of Example 1, except that it does not contain a first crosslinking agent. Specifically, by weight parts, it comprises: 2 parts polyvinylpyrrolidone, 3 parts a terpolymer of dimethacrylamide, styrene, and ethylene glycol, 0.3 parts diphenylmethane diisocyanate, 0.2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.5 parts sodium lauryl ether sulfate, 0.5 parts 2,6-di-tert-butyl-4-methylphenol, 53.5 parts ethanol, and 40 parts butanone.

[0104] Comparative Example 3

[0105] Comparative Example 3 provides a coating composition similar to that of Example 1, except that it does not contain a second crosslinking agent. Specifically, by weight parts, it comprises: 2 parts polyvinylpyrrolidone, 3 parts a terpolymer of dimethacrylamide, styrene, and ethylene glycol, 0.25 parts sodium 4,4'-diazidostilbene-2,2'-disulfonate, 0.2 parts γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 0.5 parts sodium lauryl ether sulfate, 0.5 parts 2,6-di-tert-butyl-4-methylphenol, 53.55 parts ethanol, and 40 parts butanone.

[0106] Comparative Example 4

[0107] Comparative Example 4 provides a coating composition similar to that of Example 1, except that the terpolymer is different. In Comparative Example 4, the terpolymer is a terpolymer of dimethacrylamide, ethylene, and ethylene glycol.

[0108] Comparative Example 5

[0109] Comparative Example 5 provides a coating composition similar to that of Example 1, except that a binary copolymer is used instead of a terpolymer. In Comparative Example 5, the copolymer is a binary copolymer of dimethacrylamide and ethylene glycol in a molar ratio of 2:3.

[0110] The medical catheter was immersed in the coating composition of each of the above embodiments and comparative examples for 15 seconds, and then removed and cured at 70°C for 5 hours to form a lubricating coating on the surface of the medical catheter.

[0111] The medical catheters with lubricating coatings obtained from the above embodiments and comparative examples were subjected to frictional cycle tests and Congo red staining comparison experiments.

[0112] The friction force cyclic test method is as follows:

[0113] (1) Experimental principle: The lubricated catheter in a hydrophilic state is tested by using an axial tension device and a longitudinal clamping device according to a set speed to obtain its sliding friction after hydrophilization.

[0114] (2) Test apparatus: axial tension device, longitudinal clamping device (equipped with a silicone pad with a Shore A hardness of 60±10), constant temperature water bath (water temperature 37±2℃, using secondary test water that conforms to GB / T 6682-2008).

[0115] (3) Experimental steps:

[0116] 1. Immerse the medical catheter in the water tank, ensuring the part being tested is submerged. Adjust the longitudinal clamping device so that the water just covers the silicone pad, and immerse in the water for at least 30 seconds.

[0117] 2. Use the clamps of the stretching device to clamp the upper end of the medical catheter, keeping the sample vertical, and pass the lower end through the middle of the two clamps of the longitudinal clamping device. The two clamps of the longitudinal clamping device close to clamp the medical catheter and apply a clamping force of 300g.

[0118] 3. Start the tensioning device at a tensioning speed of 10 mm / s and a test displacement of 100 mm. Throughout the process, the friction force-displacement curve or friction coefficient-displacement curve of the catheter passing through the catheter clamp is automatically recorded.

[0119] 4. The number of iterations required for the test.

[0120] The experimental results are shown in Table 1 below.

[0121] Table 1

[0122]

[0123] As can be seen from the table above, when the medical catheter coated with the coating composition of the embodiment was subjected to a friction cycle test of 50 times, the coefficient of friction decreased from about 0.06 in the first test to less than or equal to 0.06 in the fiftieth test; and when stained with a Congo red aqueous solution with a mass fraction of 1 part, the surface was uniformly red, proving that the coating did not peel off.

[0124] Commercially available hydrophilic lubricated medical catheters (Comparative Example 1) typically withstand 25 wear cycles. After 25 cycles, the coefficient of friction gradually increases, from 0.06 at the first cycle to 0.09 after the 30th cycle, and reaching approximately 0.20 at the 50th cycle. Staining with a 1 part by mass of Congo red aqueous solution resulted in some areas of the surface failing to stain, indicating coating peeling. The coefficient of friction, wear resistance, and coating peeling of the medical catheters in Comparative Examples 2-5 are shown in the table above, and their performance is inferior to that of the examples.

[0125] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0126] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A coating composition, characterized in that, Used to form a coating on a substrate, comprising, by weight parts: 1 to 5 parts of hydrophilic polymer, 2 to 8 parts of terpolymer, 0.2 to 0.5 parts of first crosslinking agent and 0.2 to 1 part of second crosslinking agent; The terpolymer comprises a first repeating unit, a second repeating unit, and a third repeating unit connected by covalent bonds. The structural formula of the first repeating unit is as follows: The structural formula of the second repeating unit is The structural formula of the third repeating unit is as follows: R1 and R2 are each independently a C1-C3 alkyl group, and R3 is hydrogen or methyl; The first crosslinking agent is used to crosslink the hydrophilic polymer with the third repeating unit, and the second crosslinking agent is used to crosslink the first repeating unit and / or the second repeating unit with the substrate. The first crosslinking agent contains one or two groups selected from diazide groups and amino groups, and the second crosslinking agent contains one or two groups selected from isocyanate groups and acrylate groups. The coating composition further includes a third crosslinking agent for crosslinking the hydrophilic polymer and the substrate. The third crosslinking agent contains a first active group and a second active group. The first active group includes a siloxy group, and the second active group includes one or more of amino, epoxy, and carbonyl groups.

2. The coating composition according to claim 1, characterized in that, The first crosslinking agent includes one or two of sodium 4,4'-diazidostilbene-2,2'-disulfonate and diethylenetriamine.

3. The coating composition according to claim 1, characterized in that, The second crosslinking agent includes one or both of diphenylmethane diisocyanate and polyethylene glycol diacrylate.

4. The coating composition according to claim 1, characterized in that, In the terpolymer, the molar ratio of the first repeating unit, the second repeating unit and the third repeating unit is (2~10):1:(3~5).

5. The coating composition according to claim 1, characterized in that, Both R1 and R2 are methyl groups, and R3 is hydrogen.

6. The coating composition according to claim 1, characterized in that, The hydrophilic polymer includes one or more of polyvinylpyrrolidone, poly(N-vinyl-2-piperidinone), and polyvinylimidazolium.

7. The coating composition according to any one of claims 1 to 6, characterized in that, In the coating composition, the third crosslinking agent is present in a mass fraction of 0.1 to 0.5 parts.

8. The coating composition according to claim 1, characterized in that, The third crosslinking agent includes one or more of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, (3-aminopropyl)triethoxysilane and γ-methacryloxypropyltrimethoxysilane.

9. The coating composition according to any one of claims 1 to 6 and 8, characterized in that, The coating composition further includes 0.5 to 2 parts by weight of an additive, which includes one or two of surfactants and antioxidants.

10. The coating composition according to claim 9, characterized in that, The additives include one or both of sodium lauryl ether sulfate and 2,6-di-tert-butyl-4-methylphenol.

11. The coating composition according to any one of claims 1 to 6 and 8, characterized in that, The coating composition further includes 83 to 94 parts by weight of solvent.

12. A method for preparing a lubricating coating, characterized in that, Includes the following steps: A coating composition is applied to a substrate surface to form a lubricating coating; wherein the coating composition is as described in any one of claims 1 to 11; The lubricating coating is heated to crosslink the hydrophilic polymer and the third repeating unit of the terpolymer in the lubricating coating, and to crosslink the substrate with the first and / or second repeating units of the terpolymer, and to cure the lubricating coating.

13. The method for preparing the lubricating coating according to claim 12, characterized in that, In the step of heating the lubricating coating, the temperature is 50℃~85℃ and the time is 2h~6h.

14. A medical material, characterized in that, It includes a substrate and a lubricating coating disposed on the surface of the substrate, the lubricating coating being prepared by the preparation method according to any one of claims 12 to 13.

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