Hydrophilic coating composition, hydrophilic coating reagent and preparation method of hydrophilic coating

Abstract

The invention discloses a hydrophilic coating composition, a hydrophilic coating reagent and a preparation method of a hydrophilic coating, and belongs to the technical field of hydrophilic coatings. The hydrophilic coating comprises a bottom coating which is coated on the catheter and is formed after the bottom coating is cured, and a surface coating which is coated on the bottom coating and is formed after the surface coating is cured. The prime paint comprises the following components in percentage by mass: 1-15 wt% of a cross-linking agent, 0.05-1 wt% of a second initiator, 0.5-2 wt% of a wetting agent and a solvent; the surface layer coating is prepared from the following components in percentage by weight: 1 to 15 percent of curable hydrophilic polymer, 0.02 to 0.8 percent of first initiator, 0.2 to 5 percent of adhesive, 0.01 to 0.5 percent of antioxidant and solvent. The hydrophilic coating can be firmly adhered to the surface of an instrument and has good ageing resistance and lubricity.

Description

Technical Field

[0001] The present application relates to the technical field of hydrophilic coatings, and more particularly, to a hydrophilic coating composition, a hydrophilic coating reagent, and a preparation method of a hydrophilic coating. Background Art

[0002] During interventional procedures, many instruments that come into contact with human tissues for a long or short time, such as balloon catheters, microcatheters, guidewires, etc., will rub against the contacted tissues when inserted and removed, making it difficult for the instruments to reach the designated position, which is not conducive to the actual operation of the operator. At the same time, it may cause adverse reactions such as tissue damage and inflammation.

[0003] Lubricating hydrophilic coatings are designed to provide a smooth surface for medical devices, thereby improving the lubricity of the devices during insertion, placement, and / or removal. This is because the hydrophilic coating reduces friction and allows the medical device to move through the tissue / body lumen. This coating also avoids severe wear between the surface of the instrument and the tissue / body lumen of the object being acted upon, reduces harm to human tissues, and is conducive to the operator's control of the operation.

[0004] After the medical hydrophilic coating solution in the related art is coated on the surface of a medical device and dried to form a coating, the adhesion and cohesion of the coating are poor, and it is easy to fall off under external force after aging, thus greatly reducing the lubrication and wetting effects and posing a potential safety hazard. Summary of the Invention

[0005] Based on the above deficiencies, the present application provides a hydrophilic coating composition, a hydrophilic coating reagent, and a preparation method of a hydrophilic coating to partially or completely improve the problems of poor lubrication performance and easy shedding of the hydrophilic coating in the related art.

[0006] The present application is implemented as follows:

[0007] In a first aspect, an example of the present application provides a hydrophilic coating composition. By mass percentage, the composition includes: 1-15 wt% of a curable hydrophilic polymer, 0.02-0.8 wt% of a first initiator, 0.2-5 wt% of an adhesive, 0.01-0.5 wt% of an antioxidant, and the balance is a solvent.

[0008] In the above implementation process, a composition of 1-15 wt% of a curable hydrophilic polymer, 0.02-0.8 wt% of a first initiator, 0.2-5 wt% of an adhesive, 0.01-0.5 wt% of an antioxidant, and a solvent can be used to form a hydrophilic coating, reduce the friction of the coating, improve the lubrication effect, and also enable the coating to have good anti-aging ability and adhesion, which can reduce the probability of the lubricating hydrophilic coating falling off and firmly form the lubricating hydrophilic coating on the surface of the medical device.

[0009] In combination with the first aspect, in a possible implementation manner, by mass percentage, the composition further comprises: 0.01-0.5 wt% of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0010] In the above implementation process, the combination of a specific content of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and the antioxidant in the composition can reduce the friction of the coating, improve the lubrication effect, and also enable the coating to have good anti-aging ability and adhesiveness, can reduce the probability of the lubricating hydrophilic coating falling off, and enable the lubricating hydrophilic coating to firmly form on the surface of the medical device.

[0011] In combination with the first aspect, in a possible implementation manner, the adhesive has crosslinkable functional groups and / or polymers, and the functional groups are selected from at least one of acrylate, acrylamide, and methyl methacrylate.

[0012] In combination with the first aspect, in a possible implementation manner, the adhesive is selected from at least one of trimethylolpropane triacrylate, bisphenol A dimethacrylate, bisphenol A glycerol dimethacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, tricyclo[5.2.1.0 2,6]decane diacrylate, bisphenol A ethoxymethyl dimethacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, di(trimethylolpropane) tetraacrylate, ethoxylated trimethylolpropane (1EO / OH) methyl ether diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, tetra(ethylene glycol) diacrylate, di(trimethylolpropane) tetraacrylate, poly(propylene glycol) dimethacrylate, poly(ethylene glycol) methacrylate, polypropylene glycol diacrylate, poly(ethylene glycol) diacrylate, polyethylene glycol methyl ether methacrylate, methoxypolyethylene glycol acrylate, or poly(propylene glycol) methacrylate.

[0013] Optionally, the adhesive is selected from a mixture of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.

[0014] Optionally, the number-average molecular weight of the adhesive is 200-50000 Daltons.

[0015] In the above implementation process, the adhesive has crosslinkable functional groups and / or polymers, and the functional groups are selected from at least one of acrylate, acrylamide, and methyl methacrylate, which can enable the lubricating hydrophilic coating formed by the composition to have good anti-aging ability and adhesiveness, enable the lubricating hydrophilic coating to firmly form on the surface of the medical device, and have good lubricity.

[0016] In combination with the first aspect, in a possible implementation, the first initiator is selected from photoinitiators and / or thermal initiators.

[0017] Optionally, the first initiator is selected from at least one of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, benzoin, benzophenone, methyl benzoylformate, or 1-hydroxycyclohexyl phenyl ketone.

[0018] In the above implementation process, by using a photoinitiator and / or a thermal initiator in combination with other components in the composition, the lubricating hydrophilic coating formed by the composition has good anti-aging ability and adhesiveness, improving the lubricating performance.

[0019] In combination with the first aspect, in a possible implementation, the curable hydrophilic polymer is selected from at least one of polyethers, polyvinylpyrrolidone, polyesters, polyvinyl alcohol, or polysaccharides and their copolymers.

[0020] Optionally, the curable hydrophilic polymer is selected from at least one of polyethylene glycol, polypropylene glycol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyamide, polyetherimide, polyamideamine, polyvinylpyrrolidone, polyethylene oxide, or polyurethane.

[0021] Optionally, the curable hydrophilic polymer is selected from polyvinylpyrrolidone.

[0022] Optionally, the number average molecular weight of polyvinylpyrrolidone is 20,000 - 200,000 Daltons.

[0023] In the above implementation process, the above curable hydrophilic polymer can cure to form a coating and has good hydrophilicity, which can improve the wetting and lubricating effects of the lubricating hydrophilic coating during operation.

[0024] In combination with the first aspect, in a possible implementation, the antioxidant is selected from at least one of phenolic antioxidants, ketone antioxidants, amine antioxidants, organic acid antioxidants, alcohol antioxidants, ester antioxidants, or inorganic salt antioxidants.

[0025] Optionally, the antioxidant is selected from at least one of tea polyphenols, tocopherols, flavonoids, ascorbic acid and its derivatives, butylated hydroxyanisole, dibutylhydroxytoluene, tert-butylhydroquinone, gallate, or 2,2'-methylenebis(6-tert-butyl-p-cresol).

[0026] Optionally, the antioxidant is selected from 2,2'-methylenebis(6-tert-butyl-p-cresol);

[0027] Optionally, the mass ratio of 2,2'-methylenebis(6-tert-butyl-p-cresol) to 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate is 1:0.5 - 1:1.5.

[0028] In the above implementation process, by using antioxidants such as 2,2'-methylenebis(6-tert-butyl-p-cresol) in combination with 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, the anti-aging ability of the lubricating hydrophilic coating formed by the composition can be improved, the friction of the lubricating hydrophilic coating can be reduced, and the lubricity can be enhanced.

[0029] Combined with the first aspect, in a possible implementation manner, the solvent is selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dichloromethane, chloroform, methanol, absolute ethanol, n-propanol, isopropanol or n-butanol.

[0030] In the above implementation process, by using the above solvent, a uniform hydrophilic coating composition can be obtained.

[0031] In the second aspect, the present application provides a hydrophilic coating reagent, which includes a bottom coating and a surface coating, and the surface coating is the hydrophilic coating composition provided in the first aspect.

[0032] Combined with the second aspect, in a possible implementation manner, the bottom coating, by mass percentage, contains the following components: 1 - 15 wt% of a cross-linking agent, 0.05 - 1 wt% of a second initiator, 0.5 - 2 wt% of a wetting agent, and the balance is a solvent.

[0033] Optionally, the lubricant is selected from at least one of fatty acid polyoxyethylene ether, polyol polyoxyethylene ether fatty acid ester, polyether-modified silicone, polyether-modified silicone oxide, polyether-modified polysiloxane, alkyl alcohol amide, alkylphenol polyoxyethylene ether, fatty acid methyl ester ethoxylate, polyether-modified trisiloxane, polyether, alkoxy polyethylene hydroxyethanol, sucrose ester, glycerol fatty ester, N-alkyl pyrrolidone or polyoxyethylene-polyoxypropylene copolymer.

[0034] In the above implementation process, the hydrophilic coating reagent includes a bottom coating and a surface coating, and can form a double-layer hydrophilic coating, improving the adhesion and lubricity of the hydrophilic coating on the surface of medical devices.

[0035] In the third aspect, the present application provides a method for preparing a hydrophilic coating. By using the hydrophilic coating reagent provided in the second aspect, the bottom coating is coated on the catheter to be treated, and after curing, a bottom layer coating is formed; the surface coating is coated on the bottom layer coating and cured to form a hydrophilic coating.

[0036] In the above implementation process, the bottom coating is applied to the surface of the catheter to be processed, and after curing, the surface coating is applied, so that a bottom coating and a surface coating arranged in a laminated manner can be formed on the surface of the catheter. The hydrophilic coating formed by the bottom coating and the surface coating has good anti-aging ability and adhesiveness, can firmly adhere to the surface of the catheter, and improves the lubricity of the catheter during operation. Description of the Drawings

[0037] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art.

[0038] Figure 1 Cross-sectional schematic diagram of the hydrophilic coating provided by the example of the present application;

[0039] Figure 2 Friction force-displacement curve at zero moment provided by Example 1 in the test example of the present application;

[0040] Figure 3 Friction force-displacement curve at zero moment provided by Example 2 in the test example of the present application;

[0041] Figure 4 Friction force-displacement curve at zero moment provided by Example 3 in the test example of the present application;

[0042] Figure 5 Friction force-displacement curve at zero moment provided by Comparative Example 1 in the test example of the present application;

[0043] Figure 6 One-year aging friction force-displacement curve provided by Comparative Example 1 in the test example of the present application.

[0044] Reference numerals: 100 - hydrophilic coating; 101 - bottom coating; 102 - surface coating. Detailed Description of the Embodiments

[0045] The following will describe the implementation solutions of the present application in detail in conjunction with the embodiments. However, those skilled in the art will understand that the following embodiments are only used to illustrate the present application and should not be construed as limiting the scope of the present application. For those conditions not specified in the embodiments, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified for the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0046] The "and / or" described in the description of the examples means existing simultaneously or independently. For example, A and / or B means that A exists alone, or B exists alone, or A and B exist simultaneously.

[0047] To reduce the frictional effect between medical devices such as balloon catheters, microcatheters, guidewires, etc. and the tissues of the contact object during interventional surgery, a lubricating hydrophilic coating is usually provided on the surface of the medical device.

[0048] The lubricating hydrophilic coating can reduce the frictional force and allow the medical device to move through the tissue / body lumen, avoiding severe wear between the surface of the device and the tissue / body lumen of the acting object, reducing the harm to human tissues, and facilitating the operator's control of the surgery.

[0049] However, after the medical hydrophilic coating solution in the related art is coated on the surface of the medical device and cured to form a coating, the adhesion and cohesion of the coating are poor.

[0050] The inventor found that a hydrophilic coating solution containing hydrophilic polymer polymers such as polyvinylpyrrolidone and polyhydric alcohols has good toughness in the dry state, can be evenly attached to the surface of the catheter, and is colorless and transparent; in the wet state, the coating can be activated and hydrated by water to form a colorless and transparent hydrogel, and this hydrogel coating is highly lubricating and can withstand repeated friction.

[0051] However, after the above-mentioned hydrophilic coating solution forms a coating, the coating is prone to aging. After aging, the coating is easily peeled off under the action of external force, thereby greatly reducing the lubrication and wetting effects, and easily causing safety hazards.

[0052] Therefore, the present application further improves the hydrophilic coating, so as to improve the aging problem of the hydrophilic coating to a certain extent, and improve the lubricity and safety of the hydrophilic coating. To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application.

[0053] Please refer to Figure 1 , the hydrophilic coating 100 includes a bottom layer coating 101 and a surface layer coating 102 arranged in a stacked manner. Among them, the bottom layer coating 101 is used for coating on the surface of the medical device as the inner layer; the surface layer coating 102 serves as the outer layer of the hydrophilic coating 100.

[0054] Among them, the hydrophilic coating 100 is obtained by preparing with a hydrophilic coating reagent. The hydrophilic coating reagent includes a bottom layer coating material for forming the bottom layer coating 101 and a surface layer coating material for forming the surface layer coating 102.

[0055] The bottom layer coating material and the surface layer coating material are packaged separately.

[0056] Among them, calculated by mass percentage, the raw materials of the bottom layer coating material include: 1-15 wt% of a cross-linking agent, 0.05-1 wt% of a second initiator, 0.5-2 wt% of a wetting agent, and the balance is a solvent.

[0057] In some possible embodiments, the crosslinking agent may be selected from crosslinkable functional groups and / or polymers.

[0058] Exemplarily, when the crosslinking agent has crosslinkable functional groups, the functional groups may be selected from at least one of acrylate, acrylamide, and methyl methacrylate.

[0059] In one possible embodiment, the functional groups in the crosslinking agent may be selected from acrylates.

[0060] Exemplarily, the crosslinking agent may be selected from at least one of trimethylolpropane triacrylate, bisphenol α dimethacrylate, bisphenol α glycerol dimethacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, tricyclo[5.2.1.0 2,6]decane diacrylate, bisphenol A ethoxylate dimethacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, di(trimethylolpropane) tetraacrylate, ethoxylated trimethylolpropane (1EO / OH) methyl ether diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, tetra(ethylene glycol) diacrylate, di(trimethylolpropane) tetraacrylate.

[0061] Exemplarily, when the crosslinking agent is selected from crosslinkable polymers, the polymer may be crosslinkable polyester or crosslinkable polyether.

[0062] Exemplarily, the crosslinking agent may be selected from at least one of poly(propylene glycol) dimethacrylate, poly(ethylene glycol) methacrylate, polypropylene glycol diacrylate, poly(ethylene glycol) diacrylate, polyethylene glycol methyl ether methacrylate, methoxypolyethylene glycol acrylate, or poly(propylene glycol) methacrylate.

[0063] Exemplarily, the crosslinking agent is selected from a mixture of polyethylene glycol diacrylate and ethylene glycol dimethacrylate.

[0064] Furthermore, the mass content of the crosslinking agent may be one of 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, or 15 wt% or in the range between any two of them.

[0065] In some possible embodiments, the second initiator may be selected from at least one of a photoinitiator or a thermal initiator.

[0066] Exemplarily, the second initiator may be selected from at least one of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, benzoin, benzophenone, methyl benzoylformate, or 1-hydroxycyclohexyl phenyl ketone.

[0067] Furthermore, the mass content of the second initiator may be one of 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, or 1 wt% or in the range between any two of them.

[0068] In a possible embodiment, the wetting agent may be selected from at least one of fatty acid polyoxyethylene ether, polyol polyoxyethylene ether fatty acid ester, polyether-modified silicone, polyether-modified siloxane, polyether-modified polysiloxane, alkylolamide, alkylphenol polyoxyethylene ether, fatty acid methyl ester ethoxylate, polyether-modified trisiloxane, polyether, alkoxy polyethylene hydroxyethanol, sucrose ester, glycerol fatty ester, N-alkylpyrrolidone, or polyoxyethylene-polyoxypropylene copolymer.

[0069] Furthermore, the mass content of the wetting agent may be one of 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, or 5 wt% or in the range between any two of them.

[0070] In a possible embodiment, the solvent may be selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dichloromethane, chloroform, methanol, absolute ethanol, n-propanol, isopropanol, or n-butanol.

[0071] The surface coating is a hydrophilic coating composition. By mass percentage, the raw materials of the hydrophilic coating composition include: 1-15 wt% of curable hydrophilic polymer, 0.02-0.8 wt% of the first initiator, 0.2-5 wt% of the binder, 0.01-0.5 wt% of the antioxidant, and the balance is the solvent.

[0072] In some possible embodiments, the curable hydrophilic polymer may be selected from at least one of curable polyether, polyvinylpyrrolidone, curable polyester, polyvinyl alcohol, or polysaccharide and its copolymers.

[0073] Furthermore, the number average molecular weight of the curable hydrophilic polymer may be 20,000 - 200,000 Daltons.

[0074] Exemplarily, the number average molecular weight of the curable hydrophilic polymer may be one of 20,000 Daltons, 50,000 Daltons, 100,000 Daltons, 150,000 Daltons or 200,000 Daltons or within the range between any two of them.

[0075] Exemplarily, the curable hydrophilic polymer is selected from at least one of polyethylene glycol, polypropylene glycol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyamide, polyetherimide, polypeptamide, polyvinylpyrrolidone, polyethylene oxide or polyurethane.

[0076] Exemplarily, the curable hydrophilic polymer is selected from polyvinylpyrrolidone.

[0077] Furthermore, the mass content of the curable hydrophilic polymer may be one of 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt% or 15 wt% or within the range between any two of them.

[0078] The selection range of the first initiator is the same as that of the second initiator. The first initiator may be the same as the second initiator.

[0079] Furthermore, the mass content of the first initiator may be one of 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt% or 0.8 wt% or within the range between any two of them.

[0080] The selection range of the adhesive is the same as that of the crosslinking agent. In a possible embodiment, the adhesive is the same as the crosslinking agent, both being ethylene glycol dimethacrylate.

[0081] Furthermore, the mass content of the adhesive may be one of 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt% or within the range between any two of them.

[0082] The antioxidant may be selected from at least one of phenolic antioxidants, ketone antioxidants, amine antioxidants, organic acid antioxidants, alcohol antioxidants, ester antioxidants or inorganic salt antioxidants.

[0083] In a possible embodiment, the antioxidant can be selected from phenolic antioxidants.

[0084] Exemplarily, the phenolic antioxidant can be selected from tea polyphenols, tocopherols or tert-butylhydroquinone.

[0085] In a possible embodiment, the antioxidant can be selected from ketone antioxidants.

[0086] Exemplarily, the ketone antioxidant can be selected from flavonoids or tert-butylhydroquinone.

[0087] In a possible embodiment, the antioxidant can be selected from organic acid antioxidants.

[0088] Exemplarily, the organic acid antioxidant can be selected from ascorbic acid and its derivatives.

[0089] In a possible embodiment, the antioxidant can be selected from ester antioxidants.

[0090] Exemplarily, the ester antioxidant can be selected from gallates, dilauryl thiodipropionate or distearyl thiodipropionate.

[0091] In a possible embodiment, the antioxidant can be selected from amine antioxidants.

[0092] Exemplarily, the amine antioxidant can be selected from naphthylamine, diphenylamine or p-phenylenediamine.

[0093] In a possible embodiment, the antioxidant can be selected from alcohol antioxidants.

[0094] Exemplarily, the alcohol antioxidant can be selected from mannitol or sorbitol.

[0095] In a possible embodiment, the antioxidant can be selected from phosphoric acid and its salts, phosphorous acid and its salts.

[0096] In a possible embodiment, the antioxidant can be selected from inorganic salt antioxidants.

[0097] Exemplarily, the inorganic salt antioxidant can be selected from phosphoric acid and its salts, phosphorous acid and its salts.

[0098] In some other possible embodiments, the antioxidant can also be selected from at least one of butylated hydroxyanisole, dibutylhydroxytoluene or 2,2'-methylenebis(6-tert-butyl-p-cresol).

[0099] Further, the mass content of the antioxidant can be one of 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%, or within the range between any two of them.

[0100] In the hydrophilic coating reagent provided by the examples of the present application, adding 0.01-0.5 wt% of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate to the surface coating can improve the anti-aging performance of the formed hydrophilic coating 100.

[0101] Further, the surface coating further includes 0.01-0.5 wt% of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

[0102] Exemplarily, the mass content of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate can be one of 0.01 wt%, 0.02 wt%, 0.03 wt%, 0.04 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt% or 0.5 wt%, or within the range between any two of them.

[0103] In a possible embodiment, in the surface coating, the mass ratio of 2,2'-methylenebis(6-tert-butyl-p-cresol) to 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate is 1:0.5-1:1.5.

[0104] By using the combination of 2,2'-methylenebis(6-tert-butyl-p-cresol) and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, the friction of the formed hydrophilic coating 100 can be reduced, the lubricity can be improved, and it has good anti-aging ability. The solvent can be selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dichloromethane, chloroform, methanol, absolute ethanol, n-propanol, isopropanol or n-butanol.

[0105] The present application also provides a preparation method of a hydrophilic coating reagent, which includes:

[0106] Preparation of the bottom coating: Weigh each component raw material according to the mass ratio of the bottom coating; sequentially add the solvent, the second initiator and the wetting agent to the crosslinking agent, stir in the dark for 1-3 h, and filter.

[0107] Preparation of the surface coating: Weigh each component raw material according to the mass ratio of the bottom coating; successively add a binder, a solvent, an antioxidant, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, and a first initiator to the hydrophilic polymer, stir in the dark for 1 - 3 h, and filter.

[0108] The present application example also provides a method for preparing a hydrophilic coating 100, including: coating the bottom coating on the surface of the catheter and curing to form a bottom coating 101. Coating the surface coating on the surface of the bottom coating 101 and curing to form a surface coating 102.

[0109] In a possible embodiment, the method for coating the bottom coating on the surface of the catheter includes: immersing the area to be coated of the catheter in the bottom coating for 3 - 10 s.

[0110] In a possible embodiment, the bottom coating can be uniformly coated on the surface of the catheter by dip coating, spraying, or brushing.

[0111] The method for curing the coated bottom coating can be selected as light curing or thermal curing according to the raw material type of the bottom coating. Exemplarily, the first initiator is selected from photoinitiators, and the coated bottom coating is cured by light curing.

[0112] In a possible embodiment, the method for coating the surface coating on the surface of the bottom coating 101 includes: immersing the catheter with the formed bottom coating 101 in the surface coating for 3 - 10 s.

[0113] Or, in a possible embodiment, the surface coating can be uniformly coated on the bottom coating 101 by dip coating, spraying, or brushing.

[0114] The method for curing the coated surface coating can be selected as light curing or thermal curing according to the raw material type of the surface coating. Exemplarily, the first initiator is selected from photoinitiators, and the coated surface coating is cured by light curing.

[0115] The hydrophilic coating reagent of the present application is further described in detail below in combination with embodiments.

[0116] Example 1

[0117] Example 1 provides a hydrophilic coating reagent, which consists of a bottom coating and a surface coating.

[0118] Bottom coating preparation: Weigh 12% of the mixture of polyethylene glycol diacrylate and ethylene glycol dimethacrylate, 0.44% of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 1% of alkoxypolyethylene hydroxyethanol, and 86.56% of ethanol solution according to the mass ratio of 2:1. Place them in a brown bottle, stir magnetically for 2 h, and filter through a 500-mesh nylon screen to obtain the bottom coating.

[0119] Top coating preparation: Weigh 1.2% of the mixture of polyethylene glycol diacrylate and ethylene glycol dimethacrylate, 0.05% of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 4% of polyvinylpyrrolidone, 0.1% of 2,2'-methylenebis(6-tert-butyl-p-cresol), and 94.65% of ethanol solution. Place them in a brown bottle, stir magnetically for 2 h, and filter through a 500-mesh nylon screen to obtain the top coating.

[0120] Example 2

[0121] Example 2 provides a hydrophilic coating reagent, which is different from Example 1 in that:

[0122] In the top coating, it does not contain the antioxidant 2,2'-methylenebis(6-tert-butyl-p-cresol), and the content of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate is 0.1%.

[0123] Example 3

[0124] Example 3 provides a hydrophilic coating reagent, which is different from Example 1 in that:

[0125] In the top coating, it includes 0.1% of the mixture of 2,2'-methylenebis(6-tert-butyl-p-cresol) and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate weighed according to the mass ratio of 1:1.

[0126] Comparative Example 1

[0127] Comparative Example 1 provides a hydrophilic coating reagent, which is different from Example 1 in that:

[0128] In the second coating, it does not contain 0.1% of the mixture of 2,2'-methylenebis(6-tert-butyl-p-cresol) and 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, and the content of ethanol is 94.65%.

[0129] Testing

[0130] Coat the hydrophilic coating reagents in Example 1 and Comparative Examples 1-3 on the microcatheter samples to form hydrophilic coatings. Then, after zero time and one-year aging, conduct tests according to the following test methods. The test curves are as Figures 2 - 6As shown. The test results are averaged as shown in Table 1.

[0131] Test method:

[0132] Table 1 Aging Test Data Sheet

[0133]

[0134] Result analysis: After one year of aging, the coating of Comparative Example 1 was unstable. In the friction test, the coating peeled off and the friction value increased significantly. After one year of aging, the performance of the coatings of Examples 1-3 did not change significantly. In particular, the lubricity of Example 3 was improved compared to other examples, and the friction force did not increase significantly after 10 times, indicating that the coating was firmly bonded to the substrate, had excellent durability and good stability.

[0135] At the zero moment, the difference between the friction force of Example 3 and that of Comparative Example 1 was greater than the sum of the difference between Example 1 and Comparative Example 1 and the difference between Example 2 and Comparative Example 1, indicating that compared with Comparative Example 1, the hydrophilic coating reagent provided in Example 3 of the present application, by using the cooperation of antioxidants such as 3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl ester and 2,2'-methylenebis(6-tert-butyl-p-cresol), could reduce the friction force of the coating, improve the lubricity, and obtain a lubrication effect where 1 + 1 > 2.

[0136] From the experimental data of Examples 1-3 and Comparative Example 1, it can be seen that the hydrophilic coating formed by coating the hydrophilic coating reagent provided in the examples of the present application on the catheter had no significant change in performance after one year of aging, still had a low friction force and good lubricity, and the hydrophilic coating was firmly bonded to the catheter sample, had excellent durability and good stability.

[0137] The above are only the preferred embodiments of the present application and are not used to limit the present application. For those skilled in the art, the present application can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A hydrophilic coating composition, characterized in that, by mass percentage, the composition comprises: 1-15 wt% of a curable hydrophilic polymer, 0.02-0.8 wt% of a first initiator, 0.2-5 wt% of an adhesive, 0.01-0.5 wt% of an antioxidant, and the balance is a solvent.

2. The hydrophilic coating composition according to claim 1, characterized in that, by mass percentage, the composition further comprises: 0.01-0.5 wt% of 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

3. The hydrophilic coating composition according to claim 1, characterized in that, the adhesive has crosslinkable functional groups and / or polymers, and the functional groups are selected from at least one of acrylate, acrylamide and methyl methacrylate; Optionally, the adhesive is selected from at least one of trimethylolpropane triacrylate, bisphenol A dimethacrylate, bisphenol A glycerol dimethacrylate, 1,3-butanediol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, ethylene glycol dimethacrylate, tricyclo[5.2.1.0 2,6]decane diacrylate, bisphenol A ethoxymethyl dimethacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane ethoxylate triacrylate, di(trimethylolpropane) tetraacrylate, ethoxylated trimethylolpropane (1EO / OH) methyl ether diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, tetra(ethylene glycol) diacrylate, di(trimethylolpropane) tetraacrylate, poly(propylene glycol) dimethacrylate, poly(ethylene glycol) methacrylate, polypropylene glycol diacrylate, poly(ethylene glycol) diacrylate, polyethylene glycol methyl ether methacrylate, methoxypolyethylene glycol acrylate or poly(propylene glycol) methacrylate; Optionally, the adhesive is selected from a mixture of polyethylene glycol diacrylate and ethylene glycol dimethacrylate; Optionally, the number average molecular weight of the adhesive is 200-50000 daltons.

4. The hydrophilic coating composition according to claim 1, characterized in that, the first initiator is selected from a photoinitiator and / or a thermal initiator; Optionally, the first initiator is selected from at least one of 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, benzoin, benzophenone, methyl benzoylformate or 1-hydroxycyclohexyl phenyl ketone.

5. The hydrophilic coating composition according to claim 1, characterized in that, the curable hydrophilic polymer is selected from at least one of polyether, polyvinylpyrrolidone, polyester, polyvinyl alcohol or polysaccharide and their copolymers; Optionally, the curable hydrophilic polymer is selected from at least one of polyethylene glycol, polypropylene glycol, polyethylene oxide, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polyamide, polyetherimide, polypeptamide, polyvinylpyrrolidone, polyethylene oxide or polyurethane; Optionally, the curable hydrophilic polymer is selected from polyvinylpyrrolidone; Optionally, the number average molecular weight of the polyvinylpyrrolidone is 20,000 - 200,000 Daltons.

6. The hydrophilic coating composition according to claim 2, wherein, the antioxidant is selected from at least one of phenolic antioxidants, ketone antioxidants, amine antioxidants, organic acid antioxidants, alcohol antioxidants, ester antioxidants or inorganic salt antioxidants; Optionally, the antioxidant is selected from at least one of tea polyphenols, tocopherols, flavonoids, ascorbic acid and its derivatives, butylated hydroxyanisole, dibutylhydroxytoluene, tert-butylhydroquinone, gallate or 2,2'-methylenebis(6-tert-butyl-p-cresol); Optionally, the antioxidant is selected from 2,2'-methylenebis(6-tert-butyl-p-cresol); Optionally, the mass ratio of 2,2'-methylenebis(6-tert-butyl-p-cresol) to 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate is 1:0.5 - 1:1.

5.

7. The hydrophilic coating composition according to claim 1, wherein, the solvent is selected from at least one of ethyl acetate, acetone, methyl ethyl ketone, dichloromethane, chloroform, methanol, absolute ethanol, n-propanol, isopropanol or n-butanol.

8. A hydrophilic coating reagent, wherein, it includes an undercoat and a topcoat, and the topcoat is the hydrophilic coating composition according to claims 1 - 7.

9. The hydrophilic coating reagent according to claim 8, wherein, the undercoat, by mass percentage, comprises the following components: 1 - 15 wt% of a crosslinking agent, 0.05 - 1 wt% of a second initiator, 0.5 - 2 wt% of a wetting agent, and the balance is a solvent; Optionally, the lubricant is selected from at least one of fatty acid polyoxyethylene ether, polyol polyoxyethylene ether fatty acid ester, polyether modified silicone, polyether modified silicone oxide, polyether modified polysiloxane, alkylolamide, alkylphenol polyoxyethylene ether, fatty acid methyl ester ethoxylate, polyether modified trisiloxane, polyether, alkoxy polyethylene hydroxyethanol, sucrose ester, glycerol fatty ester, N-alkylpyrrolidone or polyoxyethylene-polyoxypropylene copolymer.

10. A method for preparing a hydrophilic coating, wherein, it includes: using the hydrophilic coating reagent according to claim 8 or 9, coating the undercoat on the catheter to be treated, and curing to form an underlayer coating; coating the topcoat on the underlayer coating and curing to form a hydrophilic coating.

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