Medical hydrophilic coating solution and coating method thereof

Abstract

The invention provides a medical hydrophilic coating solution and a coating method, aiming at solving the problems in the prior art and improving the coating performance of medical equipment. By improving the structure of the silane coupling agent in the finish paint composition, the compounding compatibility between the primer composition and the finish paint composition is increased, and the adhesiveness between the primer composition and the finish paint composition is increased, so that the coating structure is more stable and stronger in adhesive force, and the wettability of the hydrophilic coating is not influenced.

Description

Technical Field

[0001] The invention belongs to the technical field of medical device coatings, and in particular relates to a hydrophilic coating solution for medical devices and a coating method thereof. Background Art

[0002] In the field of interventional medical devices, hydrophilic coatings have been widely studied and applied due to their excellent lubricity and biocompatibility. However, existing technologies have some limitations in the preparation and application of hydrophilic coatings, especially in the bonding strength between the primer and topcoat and the overall performance of the coating.

[0003] Medical hydrophilic coating is a technology used for surface modification of medical devices. It meets medical standards and is a functional coating with good biocompatibility. It can reduce the friction between medical devices and the human body, which helps to reduce the difficulty of doctors' operations and reduce the pain of patients. Therefore, it has been studied specifically for the surface modification of horn expanders.

[0004] The medical hydrophilic coating solution in the related technology discloses a hydrophilic coating liquid containing hydrophilic polymers such as polyvinyl pyrrolidone and polyols. In the dry state, the coating has good toughness, can be evenly adhered to the surface of the horn expander, and is colorless and transparent, and difficult to be observed with the naked eye; in the wet state, the coating can be quickly activated and hydrated by water to form a colorless and transparent hydrogel. The hydrogel coating is highly lubricated and can withstand repeated friction, thereby giving the surface of the horn expander excellent lubricity and wettability.

[0005] Although the above-mentioned medical hydrophilic coating solution can meet people's basic application needs and has excellent lubrication and wetting properties, it generally has poor adhesion and adhesion. The cured coating is prone to peeling under internal stress or external force, thereby greatly reducing the lubrication and wetting effects.

[0006] There are many types of existing medical hydrophilic coatings. For example, Chinese patent application CN106421934A discloses a hydrophilic coating liquid containing polyvinyl pyrrolidone, polyol, isocyanate, etc. The solvent of the coating liquid is a volatile and toxic organic solvent such as dichloromethane. It has a short storage time, strict requirements on the use environment, is inconvenient to use, and has serious harm to the health of operators.

[0007] For another example, Chinese patent application CN103418033A discloses a hydrophilic coating for medical catheters, the ingredients of which include: hydrophilic polymers, polysaccharide polymers, hydroxypropyl-cyclodextrin, betaine, hydroxypropyl methylcellulose, silk fibroin, poloxamer, ε-polylysine. Although the hydrophilic coating liquid is simple and convenient to use, can be evenly applied, and ensures lubricity, its components are numerous and complex, and the preparation steps of the coating liquid are many, which increases the cost of the coating liquid.

[0008] Chinese patent application CN115120788A discloses a medical hydrophilic coating solution and a coating method thereof, which is composed of a primer and a topcoat. The primer is composed of a water-based adhesive base, a first photoinitiator, a crosslinker, and a first solvent; the topcoat is composed of a hydrophilic polyurethane, polyvinyl pyrrolidone, a silane coupling agent, nano-silica, a second photoinitiator, and a second solvent. Although the medical hydrophilic coating provided by this coating scheme improves adhesion and is not prone to peeling while ensuring the lubrication and wetting effects of the coating, the bonding strength between the primer and the topcoat is still insufficient.

[0009] The invention further improves the adhesion between the hydrophilic coating and the substrate by selecting a silane coupling agent with a specific structure. Summary of the invention

[0010] The present invention aims to provide an improved hydrophilic coating solution to solve the problems existing in the prior art and improve the coating performance of medical devices.

[0011] The present invention provides a medical hydrophilic coating solution, which is composed of a primer composition and a topcoat composition;

[0012] The primer composition is composed of the following components: a water-based bonding base, a first photoinitiator, a cross-linking agent, a first solvent, and nano-silicon dioxide;

[0013] The topcoat composition is composed of the following components: hydrophilic polyurethane, polyvinyl pyrrolidone, silane coupling agent, second photoinitiator, and second solvent;

[0014] Wherein, the silane coupling agent has the following structure:

[0015] X is halogen; Y is S, O; R is alkyl, n and m are 0, 1, 2, 3, and n and m can be the same or different;

[0016] The silane coupling agent is hydrolyzed when in contact with water, and the silyl group of the triazole silane compound is hydrolyzed, that is, the trialkoxysilyl group is gradually changed into a dialkoxyhydroxysilyl group, a dihydroxyalkoxysilyl group, and a trihydroxysilyl group.

[0017] The silane coupling agent is prepared by a group structure modification method, and is obtained by reacting isocyanate silane with a mercapto compound, and the steps are as follows:

[0018] Triazole with a substituent and dibutyltin diacetate are added to gamma-isocyanate propyl alkoxysilane, and the mixture is heated and kept to react for a certain period of time. After the reaction is completed, insoluble matter is removed by filtering, and the mixture is separated by column chromatography to collect and obtain a silane coupling agent.

[0019] The silane coupling agent can be selected from compounds having the following structure:

[0020]

[0021] Furthermore, the water-based adhesive base is prepared by blending and modifying saturated polyester resin, unsaturated acrylic resin, polyamide wax and polyamide-imide.

[0022] Furthermore, the usage ratio of saturated polyester resin, unsaturated acrylic resin, polyamide wax and polyamide-imide is 1:(0.5-2):(0.1-0.5):(0.1-0.8).

[0023] Furthermore, the first photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, diphenyl acetone, and 2,4-dihydroxybenzophenone.

[0024] Furthermore, the cross-linking agent is one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, and 1,4-butylene glycol diacrylate.

[0025] Furthermore, the second photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, diphenyl acetone, and 2,4-dihydroxybenzophenone.

[0026] Furthermore, in the structural formula of the silane coupling agent, X is F, Cl, Br, I; Y is S; and R is selected from a C1-6 alkyl group.

[0027] Furthermore, the C1-6 alkyl group is selected from the group consisting of: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0028] Further, the first solvent and the second solvent are selected from: methanol, ethanol, propanol, 2-propanol, butanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, preferably ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, acetone, tetrahydrofuran, dioxane, and acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, formic acid, acetic acid, propionic acid, triethylamine, pyridine and other substances freely mixed with water. It should be noted that in the implementation of the present invention, two or more selected from them can be used in combination.

[0029] Further, the first solvent is one or more of ethanol, glycerol, and ethyl acetate;

[0030] Furthermore, the second solvent consists of two or more of ethanol, isopropanol, ethyl acetate and water.

[0031] The present invention also provides a method for coating a medical hydrophilic coating solution, comprising the following coating steps:

[0032] S1, first immerse the horn expander to be coated in the primer composition, and after the primer composition is coated, pull the horn expander to be coated and irradiate and cure it under a UV lamp, so as to obtain a horn expander coated with a base layer;

[0033] S2. Immerse the horn dilator coated with the base layer in the topcoat composition again. After the topcoat composition is applied, lift the horn dilator coated with the base layer and cure it under a UV lamp for secondary irradiation to obtain a horn dilator coated with a hydrophilic coating.

[0034] Furthermore, the irradiation curing time in step S1 is 50-100s.

[0035] Furthermore, the irradiation curing time in step S2 is 80-200s.

[0036] This application has the following beneficial effects:

[0037] It is known that the substance with alkoxysilyl in the molecule plays a role as a silane coupling agent. The triazole trialkoxy silane compound used in the implementation of the present invention has a triazole ring and an alkoxysilyl group (-Si-OR) in the molecule, and it is presumed that the triazole ring interacts with the resin to form a chemical bond. In addition, the alkoxysilyl group is hydrolyzed and converted into a hydroxysilyl group (-Si-OH), and it is presumed that the hydroxysilyl group is chemically bonded to silicon dioxide. The chemical conversion film from the triazole silane compound shown in the chemical formula (I) is formed by bonding with the triazole ring and the hydroxysilyl group. In the case of forming a resin layer on the surface of the chemical conversion film, the adhesion between the two items is increased, and the effect shown is that the coating structure is more stable and the adhesion is stronger, the wettability of the hydrophilic coating is not affected, and the coating structure is more stable to the environment. At the same time, the compatibility of the primer composition and the topcoat composition is increased. DETAILED DESCRIPTION

[0038] The present invention is further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the embodiments of the present invention are conventionally purchased raw materials and reagents.

[0039] The present application is further described in detail below with reference to the embodiments.

[0040] The raw materials used in the examples are commercially available except for the following special instructions:

[0041] 1. Hydrophilic polyurethane, brand WanSpongeFPT;

[0042] 2. Polyvinylpyrrolidone, CAS registration number 9003-39-8;

[0043] 3. Saturated polyester resin, brand polyester resin 930, model CW-Zn-002;

[0044] 4. Polyamide wax, brand DuPont;

[0045] 5. Polyamide-imide, brand 4301;

[0046] 6. Unsaturated acrylic resin, model ALK150-2;

[0047] 7. Polyethylene glycol diacrylate, CAS 26570-48-9;

[0048] 8. Nano-silicon dioxide, average particle size is 20nm, specific surface area is 200m 2 / g.

[0049] Preparation Example 1

[0050] Silane coupling agent Preparation

[0051] Add 5-chloro-3-mercapto-1,2,4-triazole (0.12 mol) and 0.18 g of dibutyltin diacetate to γ-isocyanatepropyltriethoxysilane (0.1 mol), heat to 80°C and react for 5 hours. After the reaction is completed, filter to remove insoluble matter, separate by column chromatography, use ethyl acetate and petroleum ether as eluents, collect the eluent and distill under reduced pressure to recover the organic solvent to obtain a silane coupling agent with a yield of 80% and a purity of 99.1%.

[0052] Preparation Example 2

[0053] Silane coupling agent Preparation

[0054] To γ-isocyanatepropyltriethoxysilane (24.7 g, 0.1 mol) were added 3-mercapto-1,2,4-triazole (12.13 g, 0.12 mol) and 0.16 g of dibutyltin diacetate, and the mixture was heated to 60°C for 4 hours. After the reaction was completed, the insoluble matter was removed by filtration, and the mixture was separated by column chromatography using ethyl acetate and petroleum ether as eluents. The eluent was collected and the organic solvent was recovered by distillation under reduced pressure to obtain a silane coupling agent with a yield of 87% and a purity of 99.2%. 1H NMR (DMSO-d6, 400MHz), δ: 1.05 (2H, t, J = 7.7Hz), 1.31 (9H, t, J = 6.9Hz), 1.82 (2 H,tt,J=7.7,7.5Hz), 3.04(2H,t,J=7.5Hz), 3.45(6H,q,J=6.9Hz), 8.24(1H,s).

[0055] Example 1

[0056] The medical hydrophilic coating solution comprises a primer composition and a topcoat composition, and the components and weight proportions of the primer composition and the topcoat composition are as follows:

[0057] The primer composition comprises the following components:

[0058] Water-based adhesive base 20g

[0059] First photoinitiator 0.2g

[0060] Crosslinking agent 2.2g

[0061] First solvent 73g

[0062] Nano silicon dioxide 2.2g

[0063] The topcoat composition comprises the following components:

[0064] Hydrophilic polyurethane 10g

[0065] Polyvinyl pyrrolidone 7g

[0066] Silane coupling agent 1.2g

[0067] Second photoinitiator 0.2g

[0068] Second solvent 75g

[0069] The water-based adhesive base material is composed of saturated polyester resin, unsaturated acrylic resin, polyamide wax and polyamide-imide in a weight ratio of 1:0.6:0.15:0.3;

[0070] The first photoinitiator and the second photoinitiator are diacetophenone;

[0071] The crosslinking agent is ethylene glycol dimethacrylate;

[0072] The silane coupling agent is the compound prepared in Preparation Example 1;

[0073] The first solvent is ethanol; the second solvent is composed of ethanol and ethyl acetate in a weight ratio of 1:0.5.

[0074] The medical hydrophilic coating solution is prepared by the following preparation steps: the components in the primer composition and the topcoat composition are stirred and mixed into a homogenous slurry.

[0075] Example 2

[0076] A medical hydrophilic coating solution is the same as Example 1 except that the first photoinitiator is 1-hydroxycyclohexyl phenyl ketone and the second photoinitiator is diphenyl acetone.

[0077] Example 3

[0078] A medical hydrophilic coating solution is the same as Example 1 except that the cross-linking agent is polyethylene glycol diacrylate.

[0079] Example 4

[0080] A medical hydrophilic coating solution, except that the first solvent is glycerol; the second solvent is composed of isopropanol and water in a weight ratio of 1:0.2, and the rest is the same as Example 1.

[0081] Example 5

[0082] A medical hydrophilic coating solution is the same as Example 1 except that the aqueous adhesive base material is composed of saturated polyester resin, unsaturated acrylic resin, polyamide wax and polyamide-imide in a weight ratio of 1:2:05:0.8.

[0083] Comparative Example 1

[0084] The silane coupling agent was replaced with KH-550, and the rest was the same as in Example 1.

[0085] Comparative Example 2

[0086] The silane coupling agent was replaced by the silane coupling agent obtained in Preparation Example 2, and the rest was the same as in Example 1.

[0087] Application Example 1

[0088] A method for coating a medical hydrophilic coating solution, using the medical hydrophilic coating solution prepared in Example 1, comprises the following coating steps:

[0089] S1. Soak the horn dilator to be coated in the primer composition for 30 seconds. After the primer composition is coated, take out the horn dilator to be coated at a uniform speed of 1.0 cm / s and cure it under a 900W ultraviolet lamp for 50 seconds to obtain a horn dilator coated with a bottom layer.

[0090] S2. Soak the horn dilator coated with the base layer in the topcoat composition for 20 seconds. After the topcoat composition is applied, take out the horn dilator coated with the base layer at a uniform speed of 1.0 cm / s and cure it under a 700 W ultraviolet lamp for 100 seconds to complete the coating, and obtain a horn dilator coated with a hydrophilic coating.

[0091] Application Example 2

[0092] The medical hydrophilic coating solution was replaced by that of Example 2, and the rest remained unchanged.

[0093] Application Example 3

[0094] The medical hydrophilic coating solution was replaced by that of Example 3, and the rest remained unchanged.

[0095] Application Example 4

[0096] The medical hydrophilic coating solution was replaced by that of Example 4, and the rest remained unchanged.

[0097] Application Example 5

[0098] The medical hydrophilic coating solution was replaced by that of Example 5, and the rest remained unchanged.

[0099] Application Comparative Example 1

[0100] The medical hydrophilic coating solution was replaced by that of Comparative Example 1, and the rest remained unchanged.

[0101] Application Comparative Example 2

[0102] The medical hydrophilic coating solution was replaced by that of Comparative Example 2, and the rest remained unchanged.

[0103] Results test:

[0104] 1) Adhesion test

[0105] According to the provisions of GB / T 5210-2006, a test column with a diameter of 20 mm is used, and the upper and lower test columns are coaxially connected to the test plate for testing. Three groups of medical hydrophilic coating solutions are set up in parallel, and the test results are recorded as the average value.

[0106] 2) Hydrophilic wettability (coating contact angle)

[0107] The test was carried out in accordance with the provisions of DB44 / T 1232-2013. Three groups were set up in parallel in each group. After pure water was dropped onto the surface of the horn expander, the contact points of the liquid, solid and gas phases and the inner angle between the baseline and the tangent were recorded. The average value was taken as the coating contact angle to characterize the hydrophilic wetting properties of the coating.

[0108] The test results are as follows:

[0109]

[0110] It can be seen that by improving the structure of the silane coupling agent in the topcoat composition, the compatibility between the primer composition and the topcoat composition can be increased, the coating structure is more stable and the adhesion is stronger, the wettability of the hydrophilic coating is not affected, and the coating structure is more stable to the environment.

[0111] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention.

Claims

1. A medical hydrophilic coating solution, consisting of a primer composition and a topcoat composition; The primer composition consists of the following components: Aqueous bonding base, a first photoinitiator, a cross-linking agent, a first solvent, and nano-silicon dioxide; The topcoat composition is composed of the following components: hydrophilic polyurethane, polyvinyl pyrrolidone, silane coupling agent, second photoinitiator, and second solvent; Wherein, the silane coupling agent has the following structure: X is halogen; Y is S or O; R is alkyl, and the values ​​of n and m are 0, 1, 2 or 3, and n and m may be the same or different.

2. The medical hydrophilic coating solution according to claim 1, characterized in that: The water-based adhesive base material is prepared by blending and modifying saturated polyester resin, unsaturated acrylic resin, polyamide wax and polyamide-imide.

3. The medical hydrophilic coating solution as claimed in claim 2, characterized in that: The usage ratio of saturated polyester resin, unsaturated acrylic resin, polyamide wax and polyamide-imide is 1:(0.5-2):(0.1-0.5):(0.1-0.8).

4. The medical hydrophilic coating solution according to claim 1, characterized in that: The first photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, diphenyl acetone, and 2,4-dihydroxybenzophenone.

5. The medical hydrophilic coating solution according to claim 1, characterized in that: The crosslinking agent is one or more of ethylene glycol dimethacrylate, polyethylene glycol diacrylate, and 1,4-butylene glycol diacrylate.

6. The medical hydrophilic coating solution according to claim 1, characterized in that: The second photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, diphenyl acetone, and 2,4-dihydroxybenzophenone.

7. The medical hydrophilic coating solution according to claim 1, characterized in that: In the structural formula of the silane coupling agent, X is F, Cl, Br, I; Y is S; and R is selected from a C1-6 alkyl group.

8. The medical hydrophilic coating solution according to claim 1, characterized in that: The first solvent is one or more of ethanol, glycerol, and ethyl acetate; the second solvent is composed of two or more of ethanol, isopropanol, ethyl acetate and water.

9. The method for coating a medical hydrophilic coating solution according to any one of claims 1 to 8, characterized in that: The coating steps include: S1, first immerse the horn expander to be coated in the primer composition, and after the primer composition is coated, pull the horn expander to be coated and irradiate and cure it under a UV lamp, so as to obtain a horn expander coated with a base layer; S2. Immerse the horn dilator coated with the base layer in the topcoat composition again. After the topcoat composition is applied, lift the horn dilator coated with the base layer and cure it under a UV lamp for secondary irradiation to obtain a horn dilator coated with a hydrophilic coating.

10. The coating method according to claim 9, characterized in that: The irradiation curing time in step S1 is 50-100 seconds.

11. The coating method according to claim 9, characterized in that: The irradiation curing time in step S2 is 80-200s.

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