A high-adhesion and high-moisturizing lubricating coating and its preparation method and coating adhesion test method

Abstract

The invention relates to the technical field of medical devices, and specifically discloses a high-adhesion and high-moisturizing lubricating coating, a preparation method thereof, and a coating adhesion testing method. The coating comprises a bottom coating and a surface coating, wherein the bottom coating is a base layer, and is highly adhered to a substrate through chemical bonds or intermolecular forces, and the surface coating is a functional layer, and has a hydrophilic lubricating effect, and has high lubricity, strong moisture retention, and strong wear resistance; the bottom coating comprises a photocurable resin, an active diluent, a photoinitiator, a perfluorosilane coupling agent, an auxiliary agent, and a solvent, and the surface coating comprises a photocurable resin, an active diluent, a photoinitiator, a lubricant, a moisturizing agent, a perfluorosilane coupling agent, and a solvent; the high-adhesion and high-moisturizing lubricating coating prepared by the invention has good biological safety, and is suitable for the application of a perfluoroethylene-propylene copolymer tube body and an ethylene-tetrafluoroethylene copolymer tube body.

Description

Technical Field

[0001] The present invention relates to the field of medical devices, and in particular to a high-adhesion and high-moisturizing lubricating coating, a preparation method thereof, and a coating adhesion testing method. Background Art

[0002] The surface tension of polymer materials commonly used to make medical devices ranges from 20dyn / cm to 40dyn / cm. Medical devices made of these materials have strong hydrophobicity and a certain surface roughness. When these medical devices enter the natural cavity or blood vessels of the human body during clinical application, they will cause damage to the human mucosa or adhesion of plasma proteins, platelets, etc. on the surface of the product, causing damage to blood cells and blood vessel walls, etc. Therefore, it is necessary to modify the surface of these medical devices to be hydrophilic and lubricating, so that they have a biofilm similar to the surface of loach, significantly reduce their friction, play a good lubricating role, effectively reduce the discomfort of patients and avoid various complications caused by damage to mucosa and tissue cells during entry into the human body.

[0003] For example, the catheter sheath made of extremely low surface tension perfluoroethylene propylene copolymer (FEP) material has a surface tension of only about 20dyn / cm to 22dyn / cm, and is extremely hydrophobic. It is difficult for ordinary coatings to effectively adhere to its surface. First, the bottom coating needs to have excellent adhesion to the substrate surface before the top layer can be hydrophilically lubricated on the basis of the bottom coating. The moisture retention of hydrophilic lubricating coatings is also an important characteristic. At present, there are no reports on methods to improve the moisture retention of lubricating coatings.

[0004] Among the existing test methods, more attention is paid to the friction coefficient of the hydrophilic lubricating coating of medical devices after wetting, whether the insoluble particles and reducing substances and ultraviolet absorbance are qualified after multiple frictions. These are only tests for the firmness (cohesion) of the coating itself, and these tests are used to reflect the integrity and partial safety of the coating. High adhesion connection between the coating and the substrate is the prerequisite for achieving a series of functionalities and safety of the coating. After coating, medical device products need to be packaged, sterilized and transported in a dry state. During these processes, the surface coating of the product will collide and rub with the outer packaging box in a dry state. Therefore, it is necessary to test the adhesion between the coating and the product substrate in a dry state and the integrity of the coating in a wet state. At present, the surface adhesion test of medical products is only proved by the cross-cutting method after coating with a flat substrate of the same material. There is a big difference between the flat substrate coating and the product curved surface coating. There is currently no suitable test method for the actual adhesion of the coating on the curved tube product. Summary of the invention

[0005] Based on this, the purpose of the present invention is to provide a high-adhesion and high-moisturizing lubricating coating in view of the deficiencies of the prior art, comprising a base coating and a surface coating, wherein the base coating is a base layer, and is highly adhered to the substrate through chemical bonds or intermolecular forces, and the surface coating is a functional layer, which has a hydrophilic lubricating effect, and has high lubricity and strong wear resistance;

[0006] The bottom coating liquid includes the following components by weight: 1%-10% of light-curable resin, 1%-5% of active diluent, 0.1%-1% of photoinitiator, 0.5%-2% of perfluorosilane coupling agent, 0.1%-0.5% of auxiliary agent, and 81.5%-97.3% of solvent;

[0007] The surface coating liquid includes the following components by weight: 0.1%-1% of photocurable resin, 0.1%-1% of active diluent, 0.01%-1% of photoinitiator, 1%-5% of lubricant, 0.5%-2% of moisturizer, 0.6%-3% of perfluorosilane coupling agent and 87%-97.69% of solvent.

[0008] As a further improvement of the present invention, the perfluorosilane coupling agent includes any one or more of nonafluorohexyltrimethoxysilane, tridecafluorooctyltriethoxysilane, and tridecafluorooctyltrimethoxysilane.

[0009] As a further improvement of the present invention, the auxiliary agent includes Obaodi U502 water-based polyurethane resin, and the Obaodi U502 water-based polyurethane resin can enhance the adhesion between the bottom coating and the substrate, so that the bottom coating is more firmly attached to the surface of the substrate.

[0010] As a further improvement of the present invention, the moisturizing agent includes any one or more of ceramide, hyaluronic acid, and β-glucan.

[0011] The present invention also provides a method for preparing a high-adhesion and high-moisturizing lubricating coating, which is characterized by mainly comprising the following steps:

[0012] S1 Preparation of base coating liquid

[0013] Add the photocurable resin, reactive diluent and solvent into the reaction container in sequence, stir on a magnetic stirrer until completely dissolved, add the auxiliary agent and continue to stir until completely dissolved, then add the perfluorosilane coupling agent and the photoinitiator in sequence until completely dissolved, to obtain a bottom coating liquid;

[0014] S2 Preparation of surface coating liquid

[0015] Adding a photocurable resin, a reactive diluent, and a solvent into a reaction container in sequence, placing the container on a magnetic stirrer and stirring until completely dissolved, then adding a perfluorosilane coupling agent, a moisturizer, and a lubricant in sequence and stirring until completely dissolved, and then adding a photoinitiator and stirring until completely dissolved, to obtain a surface coating liquid;

[0016] S3 Fluorine-containing substrate tube pretreatment

[0017] After cleaning the surface of the fluorine-containing substrate tube body with anhydrous ethanol and drying it, the fluorine-containing substrate tube body is subjected to plasma treatment; the gas used for the plasma treatment includes any one or more of oxygen, argon, nitrogen, and hydrogen, the gas flow rate is 150sccm-200sccm, the processing power is 300W-400W, and the processing time is 10min-20min;

[0018] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0019] The pre-treated fluorine-containing substrate tube is hung on the medical coating curing machine, dipped in the base coating liquid for 10-40 seconds, dried at room temperature for 60-150 seconds, and heated at 150-600 mJ / cm 2 Then, the fluorine-containing substrate tube body with the bottom coating cured is dipped in the surface coating liquid for 10-40 seconds, dried at room temperature for 100-300 seconds, and then heated at 150-600mJ / cm 2 Rotate and cure under UV light for 100-300s.

[0020] As a further improvement of the present invention, the photocurable resin includes any one or two of epoxy acrylate, acrylate, and polyurethane acrylate.

[0021] As a further improvement of the present invention, the reactive diluent includes any one or two of monofunctional acrylate, difunctional acrylate and trifunctional acrylate.

[0022] As a further improvement of the present invention, the photoinitiator includes any one or two of 1-hydroxycyclohexyl benzophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-isopropylthioxanthone, and benzophenone.

[0023] As a further improvement of the present invention, the lubricant includes any one or more of polyacrylamide, polyvinyl pyrrolidone, and polyvinyl alcohol.

[0024] As a further improvement of the present invention, the solvent includes any one or more of ethanol, methanol, isopropanol and water.

[0025] As a further improvement of the present invention, the fluorine-containing substrate tube body includes a main tube of a catheter sheath, a vascular sheath and other products, and the material mainly includes perfluoroethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer and the like.

[0026] The present invention also provides a coating adhesion testing method, which mainly comprises the following steps:

[0027] S5 staining

[0028] The coated tube is stained with 1% Congo red for 1 min to 3 min;

[0029] S6 Rinse and dry

[0030] Rinse the stained tube with clean water to remove the unbound Congo red dye on the surface, and dry it;

[0031] S7 peel test

[0032] Adhere the 3M tape to the surface of the tube with uniform force and perform a peel test;

[0033] S8 Observation Results

[0034] Observe the integrity of the tube coating and whether the coating on the 3M tape surface has fallen off under a microscope.

[0035] 1. The present invention adds a perfluorosilane coupling agent to the coating so that the bottom coating can be similarly compatible with the surface of the fluorine-containing substrate or molecularly reorganized and chemically cross-linked, thereby enhancing the adhesion between the coating and the substrate and between the coatings.

[0036] 2. The present invention adds an auxiliary agent, Oubaodi U502 water-based polyurethane resin, to the base coating, which can wet and further anchor the base coating and the substrate, thereby increasing the bonding force between the base and the difficult-to-attach substrate.

[0037] 3. The present invention adds macromolecular moisturizers such as ceramide, hyaluronic acid, β-glucan, etc. with strong water-binding ability to the surface coating, which can form an interpenetrating network structure with the coating, which is not easy to dissolve or fall off, and can improve the moisture retention of the coating, and prevent the coating from rapidly dehydrating in the air and losing its lubricating function in a short time.

[0038] 4. The present invention improves the national standard adhesion test method, uses 3M tape to directly bond the coated catheter sheath body in a dry state, and conducts a peeling experiment to prove the adhesion of the coating directly combined with the product (rather than using the cross-cutting method to prove the adhesion after the coating is coated with a flat substrate of the same material. The flat substrate and the tube body are very different, and it does not indicate whether the coating has fallen off by measuring the increase in the friction coefficient in multiple tests); the coating firmness and stability (cohesion) are reflected by testing the friction coefficient of the hydrophilic coating in a wet state and calculating the variance of multiple test data.

[0039] 5. The coating prepared by the present invention has high lubricity, strong wear resistance and good uniformity after being hydrophilic. The adhesion test method of the present invention is simple and easy to operate. The coating liquid has low solid content, moderate viscosity, extremely low cost, high biosafety and great industrial value. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0041] Attached Figure 1 This is a schematic diagram of the product coating process.

[0042] Attached Figure 2 The figures are the staining results of Examples 1-8 and Comparative Examples 1-4 after Congo red coating.

[0043] Attached Figure 3 The following are the results of the peeling test after coating of Examples 1-8 and Comparative Examples 1-4.

[0044] Attached Figure 4 This is a comparison chart of the friction coefficient before and after coating of Examples 1-8 and Comparative Examples 1-4.

[0045] Attached Figure 5 This is a graph showing the results of 30 friction coefficient tests on the coatings of Examples 1-8 after coating.

[0046] Attached Figure 6 This is a graph showing the results of 30 friction coefficient tests on the coatings of Comparative Examples 1-4 after coating. DETAILED DESCRIPTION

[0047] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0048] The fluorine-containing substrate tube body in the present invention includes the main body tube of products such as catheter sheaths and vascular sheaths, and the material mainly includes perfluoroethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, etc. The embodiment of the present invention is described by taking the catheter sheath product as an example. Example

[0049] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0050] S1 Preparation of base coating liquid

[0051] 4.2 parts of acrylate, 2.6 parts of hexanediol diacrylate and 91.8 parts of ethanol were added into the reaction container in sequence, and stirred on a magnetic stirrer for 3 hours until completely dissolved. Then, 0.17 parts of Oubaodi U502 waterborne polyurethane resin was added and stirred until completely dissolved. Then, 1.05 parts of nonafluorohexyltrimethoxysilane and 0.35 parts of benzophenone were added in sequence and stirred until completely dissolved to obtain a base coating liquid.

[0052] S2 Preparation of surface coating liquid

[0053] 0.45 parts of acrylate, 0.7 parts of hexanediol diacrylate, 46.8 parts of ethanol and 46.8 parts of water were added to a reaction container in sequence, placed on a magnetic stirrer and stirred for 2 hours until completely dissolved, then 0.9 parts of nonafluorohexyltrimethoxysilane, 0.9 parts of ceramide and 3.34 parts of polyvinylpyrrolidone were added in sequence, stirred until completely dissolved, and 0.11 parts of benzophenone was added until completely dissolved to obtain a surface coating liquid.

[0054] S3 catheter sheath pretreatment

[0055] The surface of the catheter sheath was cleaned with anhydrous ethanol, dried, and then plasma treated. The gas used for the plasma treatment was oxygen, the gas flow rate was 150 sccm, the treatment power was 300 W, and the treatment time was 10 min.

[0056] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0057] The pretreated catheter sheath was hung on a medical coating curing machine, the ambient temperature was controlled at 25℃±5℃, the humidity was controlled at 30%Rh±5%Rh, it was dipped in the base coating liquid for 10s, dried at room temperature for 120s, and then heated at 300mJ / cm 2The catheter sheath was cured at room temperature under a UV lamp for 100 s; then the catheter sheath with the bottom coating cured was dipped in the top coating liquid for 10 s, dried at room temperature for 180 s, and then cured at 300 mJ / cm 2 Rotate and cure at room temperature under UV light for 200 seconds. Example

[0058] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0059] S1 Preparation of base coating liquid

[0060] Add 5 parts of acrylate, 2.97 parts of tripropylene glycol diacrylate and 90.8 parts of isopropanol into the reaction container in sequence, place it on a magnetic stirrer and stir for 3 hours until it is completely dissolved, then add 0.17 parts of Oubaodi U502 water-based polyurethane resin and continue stirring until it is completely dissolved, then add 0.58 parts of tridecafluorooctyl triethoxysilane and 0.5 parts of 1-hydroxycyclohexyl benzophenone in sequence and stir until it is completely dissolved to obtain a base coating liquid.

[0061] S2 Preparation of surface coating liquid

[0062] 0.62 parts of acrylate, 0.41 parts of tripropylene glycol diacrylate, 51.3 parts of isopropanol and 41 parts of water were added to a reaction container in sequence, placed on a magnetic stirrer and stirred for 2 hours until completely dissolved, then 2.1 parts of tridecafluorooctyl triethoxysilane, 0.82 parts of hyaluronic acid and 3.7 parts of polyvinyl pyrrolidone were added in sequence and stirred to completely dissolve, and then 0.06 parts of 1-hydroxycyclohexyl benzophenone was added and stirred until completely dissolved to obtain a surface coating liquid.

[0063] S3 catheter sheath pretreatment

[0064] The surface of the catheter sheath was cleaned with anhydrous ethanol, dried, and plasma treated. The gas used for the plasma treatment was argon gas, the gas flow rate was 150 sccm, the treatment power was 300 W, and the treatment time was 15 min.

[0065] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0066] The pretreated catheter sheath was hung on a medical coating curing machine, the ambient temperature was controlled at 25℃±5℃, the humidity was controlled at 30%Rh±5%Rh, it was dipped in the base coating liquid for 20s, dried at room temperature for 110s, and then heated at 300mJ / cm 2 The catheter sheath was cured at room temperature under a UV lamp for 100 seconds, and then the catheter sheath with the bottom coating cured was dipped in the top coating liquid for 20 seconds, dried at room temperature for 190 seconds, and then cured at 300mJ / cm 2 Rotate and cure at room temperature under UV light for 200 seconds. Example

[0067] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0068] S1 Preparation of base coating liquid

[0069] 1.5 parts of polyurethane acrylate, 1.5 parts of 2-hydroxyethyl methacrylate, 1.5 parts of hexanediol diacrylate, 46.3 parts of ethanol and 46.3 parts of isopropanol were added into a reaction container in sequence and placed on a magnetic stirrer and stirred for 3 hours until completely dissolved. Then, 0.46 parts of Oubaodi U502 waterborne polyurethane resin was added and continued to stir until completely dissolved. Then, 1.85 parts of tridecafluorooctyltrimethoxysilane, 0.31 parts of 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone and 0.31 parts of 2-isopropylthioxanthone were added in sequence until completely dissolved by stirring to obtain a base coating liquid.

[0070] S2 Preparation of surface coating liquid

[0071] 0.11 parts of polyurethane acrylate, 0.11 parts of 2-hydroxyethyl methacrylate, 0.11 parts of hexanediol diacrylate, 30.8 parts of ethanol, 30.8 parts of isopropanol and 30.8 parts of water were added into a reaction container in sequence and placed on a magnetic stirrer and stirred for 2 hours until completely dissolved. Then 3 parts of tridecafluorooctyltrimethoxysilane, 0.89 parts of β-glucan and 3.3 parts of polyacrylamide were added in sequence and stirred to completely dissolve. Then 0.04 parts of 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone and 0.04 parts of 2-isopropylthioxanthone were added until completely dissolved to obtain a surface coating liquid.

[0072] S3 catheter sheath pretreatment

[0073] Clean the surface of the catheter sheath with anhydrous ethanol and dry it. It needs to be plasma treated before coating. The gas used is nitrogen, the gas flow rate is 180sccm, the processing power is 400W, and the processing time is 10min.

[0074] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0075] The cleaned catheter sheath was hung on a medical coating curing machine, and the ambient temperature was controlled at 25°C ± 5°C and the humidity was controlled at 30%Rh ± 5%Rh. The catheter sheath was dipped in the base coating for 40 seconds, dried at room temperature for 100 seconds, and heated at 600mJ / cm 2 The catheter sheath was cured at room temperature under a UV lamp for 60 seconds, and then the catheter sheath with the bottom coating cured was dipped in the top coating for 40 seconds, dried at room temperature for 180 seconds, and then heated at 600 mJ / cm 2 Rotate and cure at room temperature under UV light for 100s. Example

[0076] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0077] S1 Preparation of base coating liquid

[0078] 6.25 parts of polyurethane acrylate, 2.1 parts of dipropylene glycol diacrylate, 2.1 parts of ethoxylated trimethylolpropane triacrylate, 43.75 parts of isopropanol and 43.75 parts of methanol were added into a reaction container in sequence and stirred on a magnetic stirrer for 3 hours until completely dissolved. Then, 0.42 parts of Oubaodi U502 waterborne polyurethane resin was added and continued to stir until completely dissolved. Then, 0.63 parts of nonafluorohexyltrimethoxysilane, 0.63 parts of tridecafluorooctyltriethoxysilane, 0.21 parts of 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone and 0.21 parts of 2-isopropylthioxanthone were added in sequence until completely dissolved by stirring to obtain a base coating liquid.

[0079] S2 Preparation of surface coating liquid

[0080] 0.66 parts of polyurethane acrylate, 0.44 parts of dipropylene glycol diacrylate, 0.22 parts of ethoxylated trimethylolpropane triacrylate, 46.2 parts of isopropanol and 46.2 parts of water were added into a reaction container in sequence, placed on a magnetic stirrer and stirred for 2 hours until completely dissolved, then 0.44 parts of nonafluorohexyltrimethoxysilane, 0.66 parts of tridecafluorooctyltriethoxysilane, 1.98 parts of ceramide, 1.65 parts of polyvinyl pyrrolidone and 1.65 parts of polyvinyl alcohol were added in sequence, stirred to completely dissolve, and then 0.044 parts of 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone and 0.044 parts of 2-isopropylthioxanthone were added until completely dissolved to obtain a surface coating liquid.

[0081] S3 catheter sheath pretreatment

[0082] The surface of the catheter sheath was cleaned with anhydrous ethanol and dried. It was necessary to perform plasma treatment before coating. The gas used was hydrogen, the gas flow rate was 200sccm, the processing power was 400W, and the processing time was 20min.

[0083] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0084] The cleaned catheter sheath was hung on a medical coating curing machine, and the ambient temperature was controlled at 25°C ± 5°C and the humidity was controlled at 25%Rh ± 5%Rh. The catheter sheath was dipped in the base coating for 40 seconds, dried at room temperature for 120 seconds, and then heated at 600mJ / cm 2 The catheter sheath was cured at room temperature under a UV lamp for 80 seconds, and then the catheter sheath with the bottom coating cured was dipped in the top coating for 40 seconds, dried at room temperature for 180 seconds, and then heated at 600 mJ / cm 2 Rotate and cure for 170 seconds at room temperature under UV light. Example

[0085] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0086] S1 Preparation of base coating liquid

[0087] 4.93 parts of epoxy acrylate, 2.96 parts of tripropylene glycol diacrylate and 90.5 parts of methanol were added into a reaction container in sequence, placed on a magnetic stirrer and stirred for 3 hours until completely dissolved, then 0.33 parts of Oubaodi U502 waterborne polyurethane resin was added and continued to be stirred until completely dissolved, then 0.82 parts of tridecafluorooctyl triethoxysilane and 0.5 parts of 1-hydroxycyclohexyl benzophenone were added in sequence until completely dissolved, to obtain a base coating liquid.

[0088] S2 Preparation of surface coating liquid

[0089] 0.62 parts of epoxy acrylate, 0.41 parts of tripropylene glycol diacrylate, 51.3 parts of methanol and 41.1 parts of water were added into a reaction container in sequence, placed on a magnetic stirrer and stirred for 2 hours until completely dissolved. Then 1.1 parts of tridecafluorooctyl triethoxysilane, 1.85 parts of hyaluronic acid and 3.7 parts of polyvinyl alcohol were added in sequence and stirred until completely dissolved. Then 0.06 parts of 1-hydroxycyclohexyl benzophenone was added until completely dissolved to obtain a surface coating liquid.

[0090] S3 catheter sheath pretreatment

[0091] Clean the surface of the catheter sheath with anhydrous ethanol and dry it. It needs to be plasma treated before coating. The gases used are oxygen and argon, the gas flow ratio is 1:1, the total flow is 150sccm, the processing power is 300W, and the processing time is 15min.

[0092] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0093] The cleaned catheter sheath was hung on a medical coating curing machine, and the ambient temperature was controlled at 25°C ± 5°C and the humidity was controlled at 40%Rh ± 5%Rh. The catheter sheath was dipped in the base coating for 20 seconds, dried at room temperature for 100 seconds, and then heated at 300mJ / cm 2 The catheter sheath was cured at room temperature under a UV lamp for 100 seconds, and then the catheter sheath with the bottom coating cured was dipped in the top coating for 20 seconds, dried at room temperature for 150 seconds, and then cured at 300 mJ / cm 2 Rotate and cure at room temperature under UV light for 200 seconds. Example

[0094] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0095] S1 Preparation of base coating liquid

[0096] 4.2 parts of epoxy acrylate, 1.58 parts of 2-hydroxyethyl methacrylate, 1.58 parts of ethoxylated trimethylolpropane triacrylate, 45.6 parts of methanol and 45.6 parts of ethanol were added into a reaction container in sequence and stirred on a magnetic stirrer for 3 hours until completely dissolved. Then, 0.18 parts of Oubaodi U502 waterborne polyurethane resin was added and continued to be stirred until completely dissolved. Then, 0.88 parts of nonafluorohexyltrimethoxysilane and 0.53 parts of benzophenone were added in sequence until completely dissolved by stirring to obtain a base coating liquid.

[0097] S2 Preparation of surface coating liquid

[0098] 0.4 parts of epoxy acrylate, 0.2 parts of 2-hydroxyethyl methacrylate, 0.2 parts of ethoxylated trimethylolpropane triacrylate, 46.4 parts of methanol and 46.4 parts of water were added in sequence into a reaction container, placed on a magnetic stirrer and stirred for 2 hours until completely dissolved. Then, 1 part of nonafluorohexyltrimethoxysilane, 1.8 parts of β-glucan and 3.6 parts of polyacrylamide were added in sequence and stirred until completely dissolved. Then, 0.08 parts of benzophenone was added until completely dissolved to obtain a surface coating liquid.

[0099] S3 catheter sheath pretreatment

[0100] Clean the surface of the catheter sheath with anhydrous ethanol and dry it. It needs to be plasma treated before coating. The gases used are oxygen and nitrogen, the gas flow ratio is 1:1, the total flow is 160sccm, the processing power is 400W, and the processing time is 15min.

[0101] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0102] The cleaned catheter sheath was hung on a medical coating curing machine, and the ambient temperature was controlled at 25°C ± 5°C and the humidity was controlled at 30%Rh ± 5%Rh. The catheter sheath was dipped in the base coating for 20 seconds, dried at room temperature for 80 seconds, and then heated at 300mJ / cm 2 The catheter sheath was cured at room temperature under a UV lamp for 120 seconds, and then the catheter sheath with the bottom coating cured was dipped in the top coating for 20 seconds, dried at room temperature for 120 seconds, and then cured at 300mJ / cm 2 Rotate and cure at room temperature under UV light for 240 seconds. Example

[0103] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0104] S1 Preparation of base coating liquid

[0105] 2.1 parts of acrylate, 2.1 parts of polyurethane acrylate, 3.2 parts of 2-hydroxyethyl methacrylate and 91.1 parts of ethanol were added into a reaction container in sequence and stirred on a magnetic stirrer for 3 hours until completely dissolved. Then, 0.18 parts of Oubaodi U502 waterborne polyurethane resin was added and continued to be stirred until completely dissolved. Then, 0.88 parts of tridecafluorooctyltrimethoxysilane and 0.53 parts of benzophenone were added in sequence until completely dissolved by stirring to obtain a base coating liquid.

[0106] S2 Preparation of surface coating liquid

[0107] 0.2 parts of acrylate, 0.2 parts of polyurethane acrylate, 0.2 parts of 2-hydroxyethyl methacrylate, 46.5 parts of ethanol and 46.5 parts of water were added into a reaction container in sequence and placed on a magnetic stirrer and stirred for 2 hours until completely dissolved. Then 1 part of tridecafluorooctyltrimethoxysilane, 1.82 parts of β-glucan and 3.6 parts of polyacrylamide were added in sequence and stirred until completely dissolved. Then 0.06 parts of benzophenone was added until completely dissolved to obtain a surface coating liquid.

[0108] S3 catheter sheath pretreatment

[0109] Clean the surface of the catheter sheath with anhydrous ethanol and dry it. It needs to be plasma treated before coating. The gases used are nitrogen and hydrogen, the gas flow ratio is 1:1, the total flow is 160sccm, the processing power is 400W, and the processing time is 15min.

[0110] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0111] The cleaned catheter sheath was hung on a medical coating curing machine, and the ambient temperature was controlled at 25°C ± 5°C and the humidity was controlled at 50%Rh ± 5%Rh. The catheter sheath was dipped in the base coating for 20 seconds, dried at room temperature for 150 seconds, and heated at 300mJ / cm 2 The catheter sheath was cured at room temperature under a UV lamp for 140 seconds, and then the catheter sheath with the bottom coating cured was dipped in the top coating for 20 seconds, dried at room temperature for 220 seconds, and then heated at 300 mJ / cm 2 Rotate and cure at room temperature under UV light for 240 seconds. Example

[0112] The preparation process of high adhesion and high moisturizing lubricating coating is as follows:

[0113] S1 Preparation of base coating liquid

[0114] 1.8 parts of epoxy acrylate, 1.8 parts of ethoxylated trimethylolpropane triacrylate and 94.5 parts of isopropyl alcohol were added into a reaction container in sequence and stirred on a magnetic stirrer for 3 hours until completely dissolved. Then, 0.5 parts of Oubaodi U502 waterborne polyurethane resin was added and continued to be stirred until completely dissolved. Then, 0.91 parts of tridecafluorooctyl triethoxysilane and 0.55 parts of benzophenone were added in sequence until completely dissolved to obtain a base coating liquid.

[0115] S2 Preparation of surface coating liquid

[0116] 0.61 parts of epoxy acrylate, 0.23 parts of ethoxylated trimethylolpropane triacrylate, 46.8 parts of isopropyl alcohol and 46.8 parts of water were added into a reaction container in sequence, placed on a magnetic stirrer and stirred for 2 hours until completely dissolved. Then, 1 part of tridecafluorooctyl triethoxysilane, 0.8 parts of hyaluronic acid and 3.7 parts of polyvinyl alcohol were added in sequence and stirred until completely dissolved. Then, 0.06 parts of benzophenone was added until completely dissolved to obtain a surface coating liquid.

[0117] S3 catheter sheath pretreatment

[0118] The surface of the catheter sheath was cleaned with anhydrous ethanol and dried. It was necessary to perform plasma treatment before coating. The gas used was argon, the gas flow rate was 150sccm, the processing power was 300W, and the processing time was 15min.

[0119] S4 Preparation of high adhesion and high moisturizing lubricating coating

[0120] The cleaned catheter sheath was hung on a medical coating curing machine, and the ambient temperature was controlled at 25°C ± 5°C and the humidity was around 50%Rh ± 5%Rh. The catheter sheath was dipped in the base coating for 10 seconds, dried at room temperature for 150 seconds, and heated at 300mJ / cm 2 The coating was cured at room temperature for 100 s under a UV lamp, and then the catheter sheath with the bottom coating cured was dipped in the top coating for 10 s, dried at room temperature for 250 s, and then heated at 300 mJ / cm 2 Rotate and cure at room temperature under UV light for 200 seconds.

[0121] Comparative Example 1

[0122] Compared with Example 1, this comparative example does not add Obaodi U502 water-based polyurethane resin to the bottom coating prepared in S1, and does not add ceramide to the surface coating prepared in S2. Other steps are exactly the same as those in Example 1.

[0123] Comparative Example 2

[0124] Compared with Example 2, this comparative example does not add tridecafluorooctyl triethoxysilane to the bottom coating prepared in S1, and does not add hyaluronic acid to the surface coating prepared in S2. Other steps are completely consistent with Example 1.

[0125] Comparative Example 3

[0126] Compared with Example 3, this comparative example does not add Oubaodi U502 waterborne polyurethane resin in S1 to prepare the base coating, and does not add β-glucan in S2 to prepare the surface coating. Other steps are exactly the same as those in Example 3.

[0127] Comparative Example 4

[0128] Compared with Example 4, except that nonafluorohexyltrimethoxysilane and tridecafluorooctyltriethoxysilane are not added to the base coating prepared in S1, and ceramide is not added to the surface coating prepared in S2, the other steps and the types and contents of added components are exactly the same as those in Example 4, and the product coating processing procedure is also exactly the same as that in Example 4.

[0129] For Examples 1 to 8 and Comparative Examples 1 to 4, Figure 1 The product coating process schematic diagram is shown in the operation diagram. The prepared light-cured coating catheter sheath is tested using the following method:

[0130] 1. Sample coating uniformity and adhesion test

[0131] The coated catheter sheath was stained with Congo red. Figure 2 As shown, it shows that the coating can be evenly coated on the product surface. The coated catheter sheath is directly bonded and pulled apart using 3M tape, with a bonding pressure of 10N. Figure 3 It can be seen from the test result that the catheter sheaths of Examples 1 to 8 did not fall off after being bonded and pulled apart with 3M tape, proving that the coating has strong adhesion to the substrate. The catheter sheaths of Comparative Examples 1 to 4 all fell off to varying degrees after being bonded and pulled apart with 3M tape, indicating that the combined use of perfluorosilane coupling agent and Oubaodi U502 waterborne polyurethane resin can improve the bonding strength between the coating and the difficult-to-attach fluoroplastic substrate.

[0132] 2. Sample coating lubricity test

[0133] The coated guide sheath is tested according to the test method specified in "TCAMDI 021-2019 Disposable Hydrophilic Coated Guidewire".

[0134] Depend on Figure 4 It can be seen from the test results that after the catheter sheath is coated, the friction coefficient of both the embodiment and the comparative example is significantly reduced compared with the uncoated product, indicating that the coating has high lubricity after being hydrophilic.

[0135] 3. Calculation of sample coating firmness

[0136] The standard deviation of the sample's 50 times friction coefficient is used to represent the firmness and stability (cohesion) of the surface coating. The smaller the value, the stronger the firmness of the surface coating.

[0137]

[0138] Depend on Figure 5 , Figure 6 From the test results of 50 friction coefficients of the products after coating of the embodiments and comparative examples in Table 1 and the calculation results of the standard deviation, it can be seen that the friction coefficients of embodiments 1 to 8 are stable for 50 times without any increase, and the σ values ​​are between 0.00032 and 0.00092, indicating that the coatings have good wear resistance and strong cohesion.

[0139] The friction coefficient of comparative examples 1 to 4 increases at 50 times, indicating that the coating begins to be damaged and has poor wear resistance. The σ value is between 0.00066 and 0.00152. Compared with the σ value of embodiments 1 to 8, it is found that the standard deviation of the comparative examples is larger than the standard deviation of the embodiments, which directly indicates that the friction coefficient data is discrete, reflecting the poor stability of the comparative coating.

[0140] 4. Sample coating moisture retention and cytotoxicity and insoluble particle testing

[0141] Moisture retention test method: soak the coated catheter sheath in water for 5 minutes, take it out, test the weight, dry it for 10 minutes at an ambient temperature of 22°C and a relative air humidity of 30Rh%, and test its water content and friction coefficient once after 10 minutes.

[0142] Table 2 shows the test results of moisture retention and first friction coefficient after coating of the coatings of Examples 1-8 and Comparative Examples 1-4. After the catheter sheaths shown in Table 2 were coated according to Examples 1 to 8 and Comparative Examples 1 to 4, moisture retention tests were performed. The results showed that the moisture retention of the embodiments was significantly higher than that of the comparative examples at 10 min, and the first friction coefficient was lower than that of the comparative examples. The friction coefficients of the embodiments were all less than 0.05, indicating that there was an obvious lubricating effect. The friction coefficients of the comparative examples were all greater than 0.05, and the lubricating effect was not obvious, indicating that the coatings of the embodiments had strong moisture retention.

[0143] Cytotoxicity test is carried out in accordance with GB / T 16886.5-2017 Part 5: In vitro cytotoxicity test method. Insoluble particle test: First cut the coated sample into 1 cm long segments, take an appropriate amount of injection water and put it in the reaction container, immerse all the sample segments in the reaction container, seal the reaction container with plastic wrap, and place it on a 37°C water bath oscillator with an oscillation frequency of 300 times / min and an oscillation time of 24h.

[0144] Table 3 shows the cytotoxicity test results of Examples 1-8 and Comparative Examples 1-4 after coating. As shown in Table 3, the cytotoxicity test results show that the cytotoxicity of the Examples and Comparative Examples is between 85% and 93%, which is greater than 75%, indicating that the coatings have no obvious cytotoxicity. The insoluble particle test results show that the number of insoluble particles greater than 10 μm in Examples 1 to 8 is between 54 and 86, indicating that the coatings not only have a strong bond with the substrate, but also have a strong cohesive force after being damaged, and are not prone to collapse. The number of insoluble particles greater than 10 μm in Comparative Examples 1 to 4 is between 297 and 385, indicating that the integrity of the coating is destroyed after the coated product is sheared, and the coating is damaged after being shaken in a water bath, with a large number of insoluble particles precipitated.

[0145] Table 1 Standard deviations of Examples 1-8 and Comparative Examples 1-4

[0146] Serial number example Standard Deviation 1 Example 1 0.00041 2 Example 2 0.00048 3 Example 3 0.00032 4 Example 4 0.00046 5 Example 5 0.00060 6 Example 6 0.00072 7 Example 7 0.00092 8 Example 8 0.00088 9 Comparative Example 1 0.00152 10 Comparative Example 2 0.00182 11 Comparative Example 3 0.00146 12 Comparative Example 4 0.00100

[0147] Table 2 Test results of moisture retention and first friction coefficient of coatings of Examples 1-8 and Comparative Examples 1-4 after coating

[0148] Serial number example Moisturizing Friction coefficient 1 Example 1 0.028g 0.043 2 Example 2 0.031g 0.038 3 Example 3 0.026g 0.047 4 Example 4 0.033g 0.037 5 Example 5 0.030g 0.044 6 Example 6 0.032g 0.040 7 Example 7 0.024g 0.049 8 Example 8 0.022g 0.048 9 Comparative Example 1 0.013g 0.075 10 Comparative Example 2 0.010g 0.078 11 Comparative Example 3 0.014g 0.070 12 Comparative Example 4 0.011g 0.071

[0149] Table 3 Cytotoxicity test results after coating of Examples 1-8 and Comparative Examples 1-4

[0150] Serial number example Cytotoxicity Insoluble particles (>10μm) 1 Example 1 89.5% 73 2 Example 2 92.8% 61 3 Example 3 91.4% 67 4 Example 4 87.8% 59 5 Example 5 86.6% 86 6 Example 6 90.3% 79 7 Example 7 91.4% 54 8 Example 8 88.9% 65 9 Comparative Example 1 88.6% 385 10 Comparative Example 2 90.1% 356 11 Comparative Example 3 85.9% 332 12 Comparative Example 4 92.2% 297

[0151] Finally, it should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprise a ..." do not exclude the presence of other identical elements in the process, method, article or device including the elements.

[0152] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0153] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

[0154] The above is an implementation method of the embodiment of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the embodiment of the present application. These improvements and modifications are also considered to be within the scope of protection of the present application.

Claims

1. A high-adhesion and high-moisturizing lubricating coating, comprising a base coating and a surface coating, It is characterized in that The bottom coating is a base layer, which is highly adhered to the substrate through chemical bonds or intermolecular forces, and the surface coating is a functional layer, which has a hydrophilic lubricating effect, and has high lubricity, strong moisture retention and strong wear resistance; The bottom coating liquid includes the following components by weight: 1%-10% of light-curable resin, 1%-5% of active diluent, 0.1%-1% of photoinitiator, 0.5%-2% of perfluorosilane coupling agent, 0.1%-0.5% of auxiliary agent, and 81.5%-97.3% of solvent; The auxiliary agent includes Oubaodi U502 water-based polyurethane resin; The surface coating liquid includes the following components by weight: 0.1%-1% of photocurable resin, 0.1%-1% of active diluent, 0.01%-1% of photoinitiator, 1%-5% of lubricant, 0.5%-2% of moisturizer, 0.6%-3% of perfluorosilane coupling agent and 87%-97.69% of solvent.

2. The high-adhesion and high-moisturizing lubricating coating according to claim 1, It is characterized in that The perfluorosilane coupling agent includes any one or more of nonafluorohexyltrimethoxysilane, tridecafluorooctyltriethoxysilane, and tridecafluorooctyltrimethoxysilane.

3. The high-adhesion and high-moisturizing lubricating coating according to claim 1, It is characterized in that The moisturizing agent includes any one or more of ceramide, hyaluronic acid, and β-glucan.

4. A method for preparing the high-adhesion and high-moisturizing lubricating coating according to any one of claims 1 to 3, It is characterized in that The main steps include: S1 Preparation of base coating liquid Add the photocurable resin, reactive diluent and solvent into the reaction container in sequence, stir on a magnetic stirrer until completely dissolved, add the auxiliary agent and continue to stir until completely dissolved, then add the perfluorosilane coupling agent and the photoinitiator in sequence until completely dissolved, to obtain a bottom coating liquid; S2 Preparation of surface coating liquid Adding a photocurable resin, a reactive diluent, and a solvent into a reaction container in sequence, placing the container on a magnetic stirrer and stirring until completely dissolved, then adding a perfluorosilane coupling agent, a moisturizer, and a lubricant in sequence and stirring until completely dissolved, and then adding a photoinitiator and stirring until completely dissolved, to obtain a surface coating liquid; S3 Fluorine-containing substrate tube pretreatment After cleaning the surface of the fluorine-containing substrate tube body with anhydrous ethanol and drying it, the fluorine-containing substrate tube body is subjected to plasma treatment; the gas used for the plasma treatment includes any one or more of oxygen, argon, nitrogen, and hydrogen, the gas flow rate is 150sccm-200sccm, the processing power is 300W-400W, and the processing time is 10min-20min; S4 Preparation of high adhesion and high moisturizing lubricating coating The pre-treated fluorine-containing substrate tube is hung on the medical coating curing machine, dipped in the bottom coating liquid for 10-40s, dried at room temperature for 60-150s, and then heated at 150-600mJ / cm 2 The fluorine-containing substrate tube body with the bottom coating cured is then dipped in the surface coating liquid for 10-40 seconds, dried at room temperature for 100-300 seconds, and then heated to 150-600 mJ / cm 2 Rotate and cure under UV light for 100-300s.

5. The method for preparing the high-adhesion and high-moisturizing lubricating coating according to claim 4, It is characterized in that The photocurable resin includes any one or two of epoxy acrylate, acrylate and polyurethane acrylate.

6. The method for preparing the high-adhesion and high-moisturizing lubricating coating according to claim 4, It is characterized in that The reactive diluent includes any one or two of monofunctional acrylate, difunctional acrylate and trifunctional acrylate.

7. The method for preparing the high-adhesion and high-moisturizing lubricating coating according to claim 4, It is characterized in that The photoinitiator includes any one or two of 1-hydroxycyclohexyl benzophenone, 2-methyl-1-[4-methylthiophenyl]-2-morpholinyl-1-propanone, 2-isopropylthioxanthone, and benzophenone; the lubricant includes any one or more of polyacrylamide, polyvinyl pyrrolidone, and polyvinyl alcohol; and the solvent includes any one or more of ethanol, methanol, isopropanol, and water.

8. The method for preparing the high-adhesion and high-moisturizing lubricating coating according to claim 4, It is characterized in that The material of the fluorine-containing substrate tube body includes any one of perfluoroethylene-propylene copolymer and ethylene-tetrafluoroethylene copolymer.

9. A method for testing the adhesion of the high-adhesion and high-moisturizing lubricating coating according to any one of claims 1 to 3, It is characterized in that The main steps include: S5 staining The coated tube is stained with 1% Congo red for 1 min to 3 min; S6 Rinse and dry Rinse the stained tube with clean water to remove the unbound Congo red dye on the surface, and dry it; S7 peel test Adhere the 3M tape to the surface of the tube with uniform force and perform a peel test; S8 Observation Results Observe the integrity of the tube coating and whether the coating on the 3M tape surface has fallen off under a microscope.

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