Paint, paint combination, coating and product
Patent Information
- Application Number
- CN202411405220.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-09
- Publication Date
- 2025-01-10
AI Technical Summary
In the prior art, the primer layer of the polymer substrate is insufficient in bonding with the polymer substrate, which leads to the coating being easily peeled off during use and lacks long-term stability.
A coating containing a photosensitive crosslinking agent containing an azide compound and a polyester acrylate and other components is used to form chemical bonds to connect to the polymer substrate through photoinitiation, thereby improving the bonding strength of the primer layer.
It significantly improves the stability and reliability of the coating, reduces the risk of coating peeling, and enhances the safety of the use of the catheter.
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Figure CN119280497A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of preparation of medical devices, and in particular relates to a coating, a coating combination, a coating and a product. Background Art
[0002] Catheters are important tools in interventional treatment. The catheters in the prior art include a polymer substrate and a hydrophilic lubricating coating coated on the outer surface of the polymer substrate. The reason for this is that the polymer substrate is usually made of a polymer such as silicone, polyurethane, nylon, and polyester. The outer surface energy of these materials is low, the hydrophobicity is strong, and the friction coefficient is large. If the polymer substrate is directly inserted into the human body cavity, it is easy to cause complications such as damage to the blood vessel wall and cavity mucosa. Providing a hydrophilic lubricating coating on the outer surface of the polymer substrate can not only maintain the pushing performance of the polymer substrate itself, but also enhance the lubricity of the outer surface of the catheter, reduce the friction resistance of the catheter during use, and improve the safety of the catheter.
[0003] At present, a two-step method is generally used to set a hydrophilic lubricating coating on the outer surface of a polymer substrate. The specific operation is: first, a strong base coating is applied to the outer surface of the polymer substrate, and then a top coating with good hydrophilic lubricity is applied on the base coating. Among them, the bonding strength between the base coating and the polymer substrate is very important. Once the base coating and the polymer substrate are not firmly bonded, the coating is easy to fall off or be damaged from the outer surface of the polymer substrate, resulting in a lack of long-term stability of the hydrophilic lubricating effect of the coating.
[0004] In the prior art, when a hydrophilic lubricating coating is formed on the outer surface of a polymer substrate based on a two-step method, the primer layer is mostly combined with the polymer substrate by physical action, and the firmness of the combination is poor. Summary of the invention
[0005] The object of the present invention is to provide a coating, a coating combination, a coating and a product, aiming to improve the bonding firmness between the primer layer of the product and the polymer substrate, thereby improving the reliability of the coating of the product.
[0006] To achieve the above objectives, the present invention provides a coating comprising polyester acrylate, a first photoinitiator, a photosensitive crosslinker, a wetting agent, a reactive diluent, and a first solvent, wherein the photosensitive crosslinker comprises an azidobenzene compound, and the azidobenzene compound contains at least two azido groups.
[0007] Optionally, in percentage by mass, the content of polyester acrylate is 1%-5.5%, the content of the first photoinitiator is 5%-10.5%, the content of the photosensitive crosslinker is 1%-5.5%, the content of the wetting agent is 0.5%-2%, the content of the active diluent is 0.5%-2%, and the content of the first solvent is 75%-90%.
[0008] Optionally, the photosensitive crosslinking agent includes at least one of sodium 4,4'-diazidine diphenylethylene-2,2'-disulfonate, 4,4'-diazidine diphenylethylene, and 3,3'-dimethoxy-4,4'-diazidine diphenol.
[0009] Optionally, the first photoinitiator is at least one of benzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyldiphenylphosphine, and benzoin dimethyl ether; and / or, the wetting agent is a polyether-modified silicone oil or a polyether-modified silicone defoamer emulsion; and / or, the active diluent is at least one of β-hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and vinyl pyrrolidone.
[0010] To achieve the above object, the present invention also provides a coating, which is formed by curing the coating as described above.
[0011] To achieve the above object, the present invention also provides a coating combination, including a primer coating and a surface coating, wherein the primer coating is the coating as described above; and the surface coating includes a water-soluble polymer.
[0012] Optionally, the surface coating also includes a second solvent, a second photoinitiator, a cross-linked macromolecular compound, and an external surfactant; in terms of mass percentage, the content of the water-soluble high molecular polymer is 4.5%-10%, the content of the second solvent is 75%-95%, the content of the second photoinitiator is 1%-5%, the content of the cross-linked macromolecular compound is 1.8%-5.5%, and the content of the external surfactant is 1.8%-5.5%.
[0013] To achieve the above-mentioned purpose, the present invention also provides a coating, which is formed based on the aforementioned coating combination, and the coating includes a primer and a topcoat, and the topcoat is coated on at least a portion of the outer surface of the primer; the primer is formed by curing the primer, and the topcoat is formed by curing the topcoat.
[0014] To achieve the above object, the present invention further provides a product, comprising a polymer substrate and the coating as described above, wherein the coating is coated on at least a portion of the outer surface of the polymer substrate.
[0015] Optionally, the article comprises an invasive medical device.
[0016] Compared with the prior art, the coating, coating combination, coating and product of the present invention have the following advantages: the aforementioned coating comprises polyester acrylate, a first photoinitiator, a photosensitive crosslinker, a wetting agent, a reactive diluent, and a first solvent; the photosensitive crosslinker comprises an azidobenzene compound, and the azidobenzene compound comprises at least two azido groups. The coating can be used as a primer coating to form a primer coating on at least part of the outer surface of the polymer substrate of the product, and the primer coating is connected to the substrate by a chemical bond, has a strong connection strength, can effectively improve the stability and reliability of the coating, and reduce or even avoid the coating from falling off. BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The accompanying drawings are used to better understand the present invention and shall not constitute improper limitations of the present invention.
[0018] Figure 1 Schematic diagram of friction coefficient curves of coatings provided in different embodiments of the present invention. DETAILED DESCRIPTION
[0019] The following is an explanation of the embodiments of the present invention by specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that the illustrations provided in the present embodiment only illustrate the basic concept of the present invention in a schematic manner, and only the components related to the present invention are shown in the figure instead of being drawn according to the number, shape and size of the components in the actual implementation. The type, quantity and proportion of each component in the actual implementation can be a random change, and the component layout type may also be more complicated.
[0020] In addition, each embodiment of the following description has one or more technical features, but this does not mean that the user of the present invention must implement all the technical features in any embodiment at the same time, or can only implement part or all of the technical features in different embodiments separately. In other words, under the premise that implementation is possible, those skilled in the art can selectively implement part or all of the technical features in any embodiment according to the disclosure of the present invention and according to the design specifications or implementation requirements, or selectively implement a combination of part or all of the technical features in multiple embodiments, thereby increasing the flexibility of the implementation of the present invention.
[0021] As used in this specification, the singular forms "a", "an" and "the" include plural objects, and the plural form "a plurality" includes more than two objects, unless the content clearly indicates otherwise. As used in this specification, the term "or" is generally used to include the meaning of "and / or", unless the content clearly indicates otherwise, for ordinary technicians in the field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.
[0022] The coating provided by the embodiment of the present invention comprises polyester acrylate, a first photoinitiator, a photosensitive crosslinking agent, a wetting agent, a reactive diluent, and a first solvent, wherein the photosensitive crosslinking agent comprises an azidobenzene compound, and the azidobenzene compound comprises at least two azido groups.
[0023] The coating can be used to form a primer on at least part of the outer surface of the polymer substrate of the product. In the process of forming the primer on the coating applied on at least part of the outer surface of the polymer substrate, the azidobenzene compound is denitrified under light such as ultraviolet light to form a highly active nitrous compound intermediate, and then the nitrous compound intermediate inserts with the CH bond in the polymer substrate and the CH of the primer polymer in the coating, so that the primer is reliably connected to the polymer substrate through a chemical bond, and thus, the primer is not easy to peel off from the polymer substrate. The polymer substrate here can be prepared using any suitable polymer material, and the optional polymer material includes but is not limited to any one of polyether block amide (Pebax), polyurethane (TPU), nylon (Nylon), and polydimethylsiloxane (PDMS).
[0024] The primer polymer includes a cross-linked product formed by cross-linking of the various components in the coating under the action of a photoinitiator. In practice, the polyester acrylate participates in the cross-linking reaction and becomes a part of the cross-linked product, and the photoinitiator can also participate in the cross-linking reaction and become a part of the cross-linked product.
[0025] In addition, it should be noted that if the primer polymer includes an NH bond, the nitrous compound intermediate also undergoes an insertion reaction with the NH bond of the primer polymer to form a chemical bond; similarly, if the polymer substrate includes an NH bond, the nitrous compound intermediate also undergoes an insertion reaction with the NH bond of the polymer substrate to form a chemical bond.
[0026] It should also be noted that the azidobenzene compound refers to a compound containing an azidobenzene group, wherein at least one azido group formed by denitrogenation under light is used to react with the polymer substrate, and at least one azido group formed by denitrogenation under light is used to connect with the primer polymer. In an embodiment of the present invention, the photosensitive crosslinker includes but is not limited to one or more of 4,4'-diazide diphenylethylene-2,2'-disulfonate sodium, 4,4'-diazide diphenylethylene, and 3,3'-dimethoxy-4,4'-diazide diphenol. It should be noted that triazide compounds containing azidobenzene groups and tetraazide compounds containing azidobenzene groups can also be used as the photosensitive crosslinker, but those skilled in the art know that the more azide groups a compound contains, the more unstable it is, and accidents are prone to occur. Therefore, in an embodiment of the present invention, it is preferred that the photosensitive crosslinker includes a diazide compound containing an azidobenzene group.
[0027] The photosensitive crosslinking agent includes sodium 4,4'-bis(azidophenylethylene)-2,2'-disulfonate (structural formula: ) is used as an example to illustrate the reaction of the azide benzene compound with the polymer substrate and the primer polymer. The reaction process of sodium 4,4'-bis(azidophenylethylene)-2,2'-disulfonate with the polymer substrate and the primer polymer is:
[0028]
[0029] In addition, the wetting agent is used to reduce the outer surface tension of the polymer substrate when the polymer substrate is dip-coated, so that the coating can be evenly attached to the outer surface of the polymer substrate, so that during photocuring, the photosensitive crosslinking agent can react with the polymer substrate to form a chemical bond between the two. The reactive diluent is used to adjust the viscosity of the coating so that the various components of the coating are evenly mixed.
[0030] Polyester acrylate is a hydrophilic aliphatic resin with unsaturated functionality, and specifically may include at least one of 1-functionality polyester acrylate, 2-functionality polyester acrylate, 3-functionality polyester acrylate, 4-functionality polyester acrylate, and 6-functionality polyester acrylate. Since 1-functionality polyester acrylate has a higher cost, multifunctional polyester acrylate is preferred.
[0031] The first photoinitiator includes but is not limited to at least one of benzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyldiphenoxyphosphine, and benzoin dimethyl ether.
[0032] The wetting agent includes at least one of polyether-modified silicone oil and polyether-modified silicone defoaming agent.
[0033] The active diluent includes but is not limited to at least one of β-hydroxyethyl methacrylate, 1,6-hexanediol diacrylate, and vinyl pyrrolidone.
[0034] The first solvent includes alcohol, and the optional alcohol includes but is not limited to at least one of ethanol and isopropanol.
[0035] In the coating, the content of polyester acrylate is 1%-5.5% by mass, such as 1%, 1.5%, 2%, 2.4%, 3%, 3.5%, 4%, 4.6%, 5%, 5.5%, etc.; the content of the first photoinitiator is 5%-10.5%, such as 5%, 5.6%, 6%, 7%, 8.2%, 9%, 9.7%, 10%, 10.5%, etc.; the content of the photosensitive crosslinker is 1%-5.5%, such as 1%, 2%, 3%, 4% , 5%, 5.5%, etc.; the content of the wetting agent is 0.5%-2%, for example 0.5%, 0.6%, 8%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, etc.; the content of the active diluent is 0.5%-2%, for example 0.5%, 0.6%, 8%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, etc.; the content of the first solvent is 75%-90%, for example 75%, 80%, 83%, 84%, 88%, 90%, etc.
[0036] The preparation process of the coating is as follows: first, polyester acrylate, the first photoinitiator, the photosensitive crosslinker, the wetting agent, the reactive diluent, and the first solvent are weighed in proportion; then, polyester acrylate, the first solvent, the first photoinitiator, the photosensitive crosslinker, the wetting agent, and the reactive diluent are mixed at room temperature and in the dark; finally, the coating is filtered to remove insoluble matter to obtain the coating. The coating needs to be stored in the dark.
[0037] Further, the coating is used to constitute a part of a coating combination. The coating combination includes a primer coating and a surface coating, the primer coating is the aforementioned coating, and the surface coating includes a water-soluble polymer. The water-soluble polymer here refers to a highly hydrophilic polymer material, which contains a large number of hydrophilic groups in its molecular structure. Thus, the coating combination can be used to form a hydrophilic lubricating coating on at least part of the outer surface of the polymer substrate of the product. The hydrophilic lubricating coating includes a primer and a surface coating, and the surface coating is coated on at least part of the outer surface of the primer. Wherein, the primer is formed by curing the primer coated on at least part of the outer surface of the polymer substrate, and the surface coating is formed by curing the surface coating coated on the outer surface of the primer. For the convenience of description, the portion of the polymer substrate to which the hydrophilic lubricating coating needs to be coated is referred to as the target area hereinafter, that is, the coating combination forms the hydrophilic lubricating coating on the target area of the polymer substrate.
[0038] The optional water-soluble polymer includes but is not limited to at least one of polyvinyl pyrrolidone, polyvinyl alcohol, and polyacrylamide. When forming the topcoat layer, under the initiation of an initiator, chemical crosslinking is carried out with the aid of the crosslinking macromolecules, so that the structure from polyester acrylate in the base coat layer and the water-soluble polymer form a high-density crosslinking network, thereby effectively connecting the topcoat layer with the base coat layer, thereby improving the stability of the topcoat layer.
[0039] Furthermore, the surface coating also includes a second solvent, a second photoinitiator, a cross-linking macromolecule, and an external surfactant. In the surface coating, the content of the water-soluble polymer is 4.5%-10% by mass, such as 4.5%, 5%, 5.5%, 6%, 6.7%, 7.1%, 8%, 8.3%, 9%, 9.5%, 10%, etc.; the content of the second solvent is 75%-95%, such as 75%, 76%, 78%, 80%, 81%, 82.5%, 84%, 85%, 87%, 90%, 91%, 92%, 94%, 95%, etc.; the content of the second photoinitiator is 1%-5%, such as 1 %, 1.2%, 1.5%, 1.7%, 2%, 2.5%, 2.8%, 3%, 3.5%, 4%, 4.2%, 4.5%, 4.7%, 5% and the like; the content of the cross-linked macromolecule is 1.8%-5.5%, for example, 1.8%, 2%, 2.2%, 2.9%, 3.5%, 4%, 4.5%, 5%, 5.5% and the like; the content of the external surfactant is 1.8%-5.5%, for example, 1.8%, 2%, 2.2%, 2.9%, 3.5%, 4%, 4.5%, 5%, 5.5% and the like.
[0040] The second solvent is alcohol, and specifically may be at least one of ethanol and isopropanol.
[0041] The second photoinitiator includes at least one of benzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyldiphenylphosphine, and benzoin dimethyl ether. Preferably, the second photoinitiator is the same as the first photoinitiator. The reason for this is that the same photocuring device is generally used to cure the primer and the surface coating, and the curing parameters of the primer and the surface coating are equivalent. Therefore, when the first photoinitiator and the second photoinitiator are the same, the primer and the surface coating can have substantially the same degree of crosslinking, which is beneficial to improving the firmness and stability of the entire hydrophilic lubricating coating.
[0042] The cross-linked macromolecules include but are not limited to waterborne polyurethane.
[0043] The external surfactant is a water-soluble nonionic polymer, and can be specifically selected from at least one of polyethylene glycol and polyethylene oxide.
[0044] The preparation process of the surface coating is as follows: first, weigh the water-soluble polymer, the second solvent, the second photoinitiator, the cross-linked macromolecule, and the external surfactant in proportion; then, mix the water-soluble polymer, the second solvent, the cross-linked macromolecule, the external surfactant, and the second photoinitiator at room temperature and in the dark; finally, filter to remove insoluble matter to obtain the surface coating. The surface coating should be stored in the dark.
[0045] The operation of forming the hydrophilic lubricating coating on the polymer substrate using the coating combination includes: first, applying the primer coating on the outer surface of the polymer substrate; then, using a photocuring device to cure the primer coating applied on the outer surface of the polymer substrate to form the primer coating; thereafter, applying the topcoat coating on the outer surface of the primer coating; finally, using the photocuring device to cure the topcoat coating applied on the outer surface of the primer coating to form the topcoat.
[0046] In practice, the primer coating can be applied to the outer surface of the polymer substrate in any suitable manner such as dipping; and the top coating can be applied to the outer surface of the primer coating in any suitable manner such as dipping.
[0047] The products mentioned in the embodiments of the present invention include but are not limited to interventional medical devices, such as medical catheters, medical guidewires, medical balloons, etc.
[0048] In order to make the objects, advantages and features of the present invention more clear, the present invention is further described in detail below in conjunction with specific embodiments.
[0049] In the coating combination provided in Example 1 of the present invention, the primer coating includes trifunctional polyester acrylate, ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, sodium 4,4'-bis(azidophenylethylene)-2,2'-disulfonate, polyether-modified silicone oil, and β-hydroxyethyl methacrylate. The surface coating includes polyvinyl pyrrolidone, ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, waterborne polyurethane, and polyethylene glycol.
[0050] The operation of preparing the primer coating is as follows: weigh 1.5g of trifunctional polyester acrylate, 30g of ethanol, 3.8g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 1.9g of sodium 4,4'-bis(azidophenylethylene)-2,2'-disulfonate, 0.2g of polyether-modified silicone oil, and 0.2g of β-hydroxyethyl methacrylate; then put the trifunctional polyester acrylate in a brown glass bottle, and then put ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, sodium 4,4'-bis(azidophenylethylene)-2,2'-disulfonate, polyether-modified silicone oil, and β-hydroxyethyl methacrylate in a brown glass bottle, continue magnetic stirring at room temperature, and finally filter with nylon gauze to obtain the primer coating.
[0051] The operation of preparing the surface coating is as follows: weigh 3.0 g of polyvinyl pyrrolidone, 30 g of ethanol, 0.8 g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 1.9 g of waterborne polyurethane, and 1.9 g of polyethylene glycol; then, put the polyvinyl pyrrolidone, ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, waterborne polyurethane, and polyethylene glycol in a brown glass bottle, continuously stir magnetically at room temperature, and finally filter with a nylon mesh to obtain the surface coating.
[0052] The medical catheter is prepared based on the coating combination provided in this embodiment, and the specific operation includes: first, providing a polymer substrate, the material of the polymer substrate is polyether block amide, and the polymer substrate has a slender tubular structure. Then, the primer coating is applied to the outer surface of the target area of the polymer substrate, and cured to form the primer coating; then, the top coating is applied to the outer surface of the primer coating, and cured to form the top coating.
[0053] In the coating combination provided in the second embodiment of the present invention, the primer coating comprises 6-functional polyester acrylate, ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 3,3'-dimethoxy-4,4'-diazide diphenol, polyether-modified silicone oil, and β-hydroxyethyl methacrylate. The surface coating comprises polyvinyl pyrrolidone, ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, waterborne polyurethane, and polyethylene oxide.
[0054] The operation of preparing the primer coating comprises: weighing 1.9 g of 6-functional polyester acrylate, 30 g of ethanol, 3.8 g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 1.9 g of 3,3'-dimethoxy-4,4'-diazide biphenol, 0.2 g of polyether-modified silicone oil, and 0.2 g of β-hydroxyethyl methacrylate, placing the 6-functional polyester acrylate, ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 3,3'-dimethoxy-4,4'-diazide biphenol, polyether-modified silicone oil, and β-hydroxyethyl methacrylate in a brown glass bottle, and continuously stirring with magnetic force at room temperature; finally, filtering with a nylon mesh to obtain the primer coating.
[0055] The operation of preparing the surface coating comprises: weighing 3.7 g of polyvinyl pyrrolidone, 30 g of ethanol, 0.7 g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 1.8 g of waterborne polyurethane, and 1.8 g of polyethylene oxide; placing polyvinyl pyrrolidone, ethanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, waterborne polyurethane, and polyethylene oxide in a brown glass bottle, and continuously stirring magnetically at room temperature; and finally filtering with a nylon mesh to obtain the surface coating.
[0056] The medical catheter is prepared based on the coating combination provided in this embodiment, and the specific operation includes: first, providing a polymer substrate, the material of the polymer substrate is polyurethane, and the polymer substrate has a slender tubular structure. Then, the primer coating is applied to the outer surface of the target area of the polymer substrate, and cured to form the primer coating; then, the top coating is applied to the outer surface of the primer coating, and cured to form the top coating.
[0057] In the coating combination provided in the third embodiment of the present invention, the primer coating comprises 4-functional polyester acrylate, ethanol, 2-hydroxy-2-methylpropiophenone, 4,4'-bis(azido)stilbene-2,2'-disulfonic acid sodium, polyether-modified silicone oil, and 1,6-hexanediol diacrylate. The surface coating comprises polyacrylamide, ethanol, 2-hydroxy-2-methylpropiophenone, waterborne polyurethane, and polyethylene glycol.
[0058] The operation of preparing the primer coating comprises: weighing 1.8 g of 4-functional polyester acrylate, 30 g of ethanol, 2.5 g of 2-hydroxy-2-methylpropiophenone, 0.7 g of 4,4'-bis(azidophenylethylene)-2,2'-disulfonic acid sodium, 0.2 g of polyether-modified silicone oil, and 0.2 g of 1,6-hexanediol diacrylate; placing the 4-functional polyester acrylate, ethanol, 2-hydroxy-2-methylpropiophenone, 4,4'-bis(azidophenylethylene)-2,2'-disulfonic acid sodium, polyether-modified silicone oil, and 1,6-hexanediol diacrylate in a brown glass bottle, and continuously stirring with magnetic force at room temperature; and finally filtering with nylon gauze to obtain the primer coating.
[0059] The operation of preparing the surface coating comprises: weighing 3.5 g of polyacrylamide, 30 g of ethanol, 0.4 g of 2-hydroxy-2-methylpropiophenone, 0.7 g of waterborne polyurethane, and 0.7 g of polyethylene glycol; placing the polyacrylamide, ethanol, 2-hydroxy-2-methylpropiophenone, waterborne polyurethane, and polyethylene glycol in a brown glass bottle, continuously stirring with magnetic force at room temperature, and finally filtering with a nylon mesh to obtain the surface coating.
[0060] The medical catheter is prepared based on the coating combination provided in this embodiment, and the specific operation includes: first, providing a polymer substrate, the material of the polymer substrate is nylon, and the polymer substrate has a slender tubular structure. Then, the primer coating is applied to the outer surface of the target area of the polymer substrate, and cured to form the primer coating; then, the top coating is applied to the outer surface of the primer coating, and cured to form the top coating.
[0061] In the coating combination provided in the fourth embodiment of the present invention, the primer coating comprises: 2-functional polyester acrylate, isopropyl alcohol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 4,4'-diazidostilbene-2,2'-sodium disulfonate, polyether-modified silicone oil, and 1,6-hexanediol diacrylate. The surface coating comprises: polyacrylamide, isopropyl alcohol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, waterborne polyurethane, and polyethylene oxide.
[0062] The operation of preparing the primer coating comprises: weighing 1.9 g of 2-functional polyester acrylate, 30 g of isopropyl alcohol, 2.6 g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 1.9 g of sodium 4,4'-bis(azidophenylethylene)-2,2'-disulfonate, 0.6 g of polyether-modified silicone oil, and 0.6 g of 1,6-hexanediol diacrylate; placing the 2-functional polyester acrylate, isopropyl alcohol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, sodium 4,4'-bis(azidophenylethylene)-2,2'-disulfonate, polyether-modified silicone oil, and 1,6-hexanediol diacrylate in a brown glass bottle, and continuously stirring with magnetic force at room temperature; and finally filtering with a nylon mesh to obtain the primer coating.
[0063] The operation of preparing the surface coating comprises: weighing 1.7 g of polyacrylamide, 30 g of isopropanol, 0.7 g of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 0.9 g of waterborne polyurethane, and 0.9 g of polyethylene oxide; placing polyacrylamide, isopropanol, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, waterborne polyurethane, and polyethylene oxide in a brown glass bottle, and continuously stirring with magnetic force at room temperature; and finally filtering with a nylon mesh to obtain the surface coating.
[0064] The medical catheter is prepared based on the coating combination provided in this embodiment, and the specific operation includes: first, providing a polymer substrate, the material of the polymer substrate is polydimethylsiloxane, and the polymer substrate has a slender tubular structure. Then, the primer coating is applied on the outer surface of the target area of the polymer substrate, and cured to form the primer coating; then, the top coating is applied on the outer surface of the primer coating, and cured to form the top coating.
[0065] Next, the performance of the medical catheters prepared in Examples 1 to 4 was tested.
[0066] Water contact angle test: The water contact angle of the outer surface of the hydrophilic lubricating coating of the medical catheter provided in Examples 1 to 4 (i.e., the outer surface of the medical catheter corresponding to the target area of the polymer substrate) was measured, and the water contact angle of the outer surface of the target area of the polymer substrate used in Examples 1 to 4 was measured. The water contact angle of the outer surface of the hydrophilic lubricating coating of the medical catheter prepared in each example and the minimum water contact angle of the target area of the polymer substrate used in each example are listed in Table 1. It can be seen from Table 1 that, compared with the target area of the polymer substrate, the water contact angle of the outer surface of the hydrophilic lubricating coating of the medical catheter prepared in Examples 1 to 4 is significantly reduced, showing excellent hydrophilic lubricity.
[0067] Table 1
[0068]
[0069] Coating friction test: The medical catheters prepared in Examples 1 to 4 were vertically fixed in a constant temperature water tank of a friction tester, and the corresponding operating parameters were set to perform friction tests. The results are shown in Tables 2 and Figure 1 shown.
[0070] Table 2
[0071]
[0072] The friction coefficient of the outer surface of the polymer substrate is not less than 1.0. Figure 1 It can be seen that the friction coefficient of the outer surface of the medical catheter prepared in Examples 1 to 4 during the friction test is in the range of 0.014-0.025, that is, the friction coefficient of the outer surface of the medical catheter prepared in the embodiment of the present invention is reduced by more than 95% relative to the polymer substrate. Moreover, in 20 friction test cycles, the friction coefficient of the outer surface of any of the medical catheters prepared in Examples 1 to 4 remains substantially unchanged, indicating that the hydrophilic lubricating coating prepared in the embodiment of the present invention has high stability and reliability.
[0073] It should be noted that, although the above embodiments take the prepared medical catheter as an example to illustrate the properties of the hydrophilic lubricating coating formed by the coating combination, in practice, interventional devices such as medical guidewires and medical balloons can also be prepared.
[0074] Although the present invention is disclosed as above, it is not limited thereto. Those skilled in the art may make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.
Claims
1. A coating, characterized in that: The invention comprises polyester acrylate, a first photoinitiator, a photosensitive crosslinking agent, a wetting agent, a reactive diluent, and a first solvent, wherein the photosensitive crosslinking agent comprises an azidobenzene compound, and the azidobenzene compound contains at least two azido groups.
2. The coating according to claim 1, characterized in that In terms of mass percentage, the content of polyester acrylate is 1%-5.5%, the content of the first photoinitiator is 5%-10.5%, the content of the photosensitive crosslinker is 1%-5.5%, the content of the wetting agent is 0.5%-2%, the content of the active diluent is 0.5%-2%, and the content of the first solvent is 75%-90%.
3. The coating according to claim 1, characterized in that The photosensitive crosslinking agent includes at least one of 4,4'-diazide stilbene-2,2'-disulfonate sodium, 4,4'-diazide stilbene, and 3,3'-dimethoxy-4,4'-diazide biphenol.
4. The coating according to claim 1, characterized in that The first photoinitiator is at least one of benzophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 2,4,6-trimethylbenzoyldiphenoxyphosphine, and benzoin dimethyl ether; and / or, The wetting agent is polyether-modified silicone oil or polyether-modified silicone defoamer emulsion; and / or, The active diluent is at least one of β-hydroxyethyl methacrylate, 1,6-hexanediol diacrylate and vinyl pyrrolidone.
5. A coating, characterized in that: The coating layer is formed by curing the coating material according to any one of claims 1 to 4.
6. A coating composition, characterized in that: It comprises a primer coating and a surface coating, wherein the primer coating is the coating as described in any one of claims 1 to 4; The surface coating material comprises a water-soluble polymer.
7. The coating composition according to claim 6, characterized in that: The surface coating also includes a second solvent, a second photoinitiator, a cross-linked macromolecular compound, and an external surfactant; in terms of mass percentage, the content of the water-soluble high molecular polymer is 4.5%-10%, the content of the second solvent is 75%-95%, the content of the second photoinitiator is 1%-5%, the content of the cross-linked macromolecular compound is 1.8%-5.5%, and the content of the external surfactant is 1.8%-5.5%.
8. A coating formed based on the coating composition according to claim 7, characterized in that: The coating comprises a base coating and a top coating, wherein the top coating is coated on at least a portion of the outer surface of the base coating; The base coating layer is formed by curing the base coating material, and the top coating layer is formed by curing the top coating material.
9. A product, characterized in that The method comprises a polymer substrate and the coating as claimed in claim 8, wherein the coating is coated on at least a portion of the outer surface of the polymer substrate.
10. The product according to claim 9, characterized in that The articles include invasive medical devices.