CN114699564B

CN114699564B - Adhesion-enhanced lubricating coating, application thereof and medical intervention catheter

Info

Publication number: CN114699564B
Application number: CN202210415649.4A
Authority: CN
Inventors: 周容涛; 孙振龙; 石恒冲; 孙传盛; 王楠; 张帅; 闫顺杰; 栾世方; 殷敬华
Original assignee: Weigaozhi Interventional Medical Device Technology Shandong Co ltd; Weigao Holding Co ltd; Changchun Institute of Applied Chemistry of CAS
Current assignee: Weigaozhi Interventional Medical Device Technology Shandong Co ltd; Weigao Holding Co ltd; Changchun Institute of Applied Chemistry of CAS
Priority date: 2022-04-20
Filing date: 2022-04-20
Publication date: 2023-05-23
Anticipated expiration: 2042-04-20
Also published as: CN114699564A

Abstract

The invention provides an adhesion-enhanced lubricating coating, which comprises a bottom coating and a top coating; the raw materials of the bottom coating comprise photoinitiated anion-cation complex and solvent; the photoinitiated type anion-cation complex comprises a photoinitiated type cation substance and an anion substance; the raw materials of the surface coating comprise hydrophilic monomers, hydrophilic polymers and solvents. In the primer layer of the present invention, after curing, the curable polymer and the adhesion promoter may be physically associated with each other or embedded to form an interpenetrating polymer network. The primer layer may also form covalent bonds with the surface layer to form a network coating that is stable. The invention can realize the chemical bond fixation and the internal self-crosslinking of the base coat on the surface of the base material, improve the adhesion of the base coat to the base material, and improve the self-strength, friction resistance and shearing resistance of the coating. In addition, the primer coating has long-acting antibacterial infection resistance.

Description

Adhesion-enhanced lubricating coating, application thereof and medical intervention catheter

Technical Field

The invention relates to the technical field of biological materials, in particular to an adhesive force enhanced lubricating coating, application thereof and a medical intervention catheter.

Background

The interventional medical catheter is mostly made of high polymer materials, has low surface energy, strong hydrophobicity and large friction coefficient, and is easy to generate large friction with mucous membrane, a cavity (especially blood vessel) and tissues in the human intervention process, thereby causing damage to mucous membrane of the cavity and even rupture of blood vessel wall. In order to solve the problem of overlarge friction force in the use process of the catheter, the hydrophilic lubricating coating is prepared on the surface of the catheter, so that the friction resistance in the penetration process is reduced, the damage to mucous membranes and vascular walls is lightened, the pain of patients is relieved, and the use safety is improved.

The hydrophilic coating with high adhesive force is coated on the surface of the catheter substrate material, so that the hydrophilic coating is an effective means for improving the lubricity of the interventional catheter and reducing the friction force. However, the interventional medical catheter polymer base materials are rich in variety, including but not limited to polyvinyl chloride (PVC), polyurethane (TPU), polyethylene (PE), polypropylene (PP), latex (Latex), silicone rubber, polyether block Polyamide (PEBAX), polytetrafluoroethylene (PTFE), and Fluorinated Ethylene Propylene (FEP). The large difference of the surface properties of different base materials makes it difficult for conventional coating solutions to form high-adhesion lubricating coatings on the surfaces of different materials.

At present, the application of a tackifying bottom layer on the surface of a substrate and the introduction of a hydrophilic lubricating surface layer have become the preferred solution for obtaining a stable coating. International medical coating fluid, giant Di Siman Co (DSM), in WO 2007065722, WO 2008/104573, CN101970583 and CN102947376, discloses a process for the preparation of articles having a primer layer (also known as a primary coating) and a hydrophilic top coating. The bottom layer comprises a precoating layer composed of polyurethane oligomer, polyvinylpyrrolidone (PVP) and a small molecular photoinitiator, and can form a stable and firm hydrophilic lubricating coating with the surface coating. Although polyurethane oligomer in the patent has better adhesiveness and unsaturated groups, and can realize photocuring to form a crosslinked structure, the acting force of the base coat and the substrate material in the system is mainly physical adsorption, so that the problem of low coating firmness is easy to occur. In addition, the initiator adopted by the system is a small molecular photoinitiator, and the phenomenon of easy migration exists after the curing, so that the biological safety of the coating is reduced.

The singapore jetty coating liquid company in patent WO 2016200337 and CN 107405430 discloses a tackifying coating formulation for use on a base material, which can be applied directly on different substrates, achieving a strong adhesion between the substrate and the lubricating functional layer. The formulation includes a polymeric adhesion promoter, a first monomer or polymeric crosslinker, and a photoinitiator. The polymeric adhesion promoter is a block copolymer comprising hydrophobic/hydrophilic polymer blocks and/or hydrophobic/hydrophilic functional groups, and upon curing the curable polymer and the adhesion promoter may physically bond to one another or form an interpenetrating polymer network in an entrapped manner. The primer (tie coat) may also form covalent bonds with the topcoat (lubricious coating) to form a stable network coating. The adhesion of the coating of the system is improved, but the acting force of the primer and the substrate material is mainly physical effect, and the problem of the small molecular initiator is not solved.

Patent CN 109954169 discloses a primer coating composition comprising a novel photocurable polyurethane having tertiary amine groups in the main chain and unsaturated double bond groups and photo-sensitive group units in the side chains, which photocurable polyurethane contains multiple crosslinking sites on the molecule, which can form a firm polymer film, effectively improving the adhesion of hydrophilic lubricating coatings on substrates, especially low surface energy substrates. Although the patent solves the problem of precipitation of the photoinitiator, the preparation of polyurethane with the special structure involves a complex organic synthesis process, and has long technical route and strict reaction condition, so that the technical difficulty and the comprehensive cost are high in actual production.

Disclosure of Invention

In view of the above, the technical problem to be solved by the invention is to provide the lubricating coating with enhanced adhesion, which is provided with the photosensitive structural unit, has simple construction and solves the problems of residual and migration of a small molecular photoinitiator.

The invention provides an adhesion-enhanced lubricating coating, which comprises a bottom coating and a top coating;

the raw materials of the bottom coating comprise photoinitiated anion-cation complex and solvent; the photoinitiated type anion-cation complex comprises a photoinitiated type cation substance and an anion substance;

The raw materials of the surface coating comprise hydrophilic monomers, hydrophilic polymers and solvents.

Preferably, the photoinitiating cationic species has the structure of formula a:

r is selected from

R ₁ And R is ₂ Independently selected from H or C1-C4 alkyl; r is R ₃ Selected from C8-C12 alkyl;

x-is selected from Cl-or I-.

Preferably, in the primer coating:

the photo-induced cationic substance is selected from one or more of N- (4-benzoylbenzyl) -N, N-dimethyldodecyl-1-ammonium bromide, 4- (4- (diethylamino) benzoyl) -N, N-diethyl-N-octylphenyl ammonium iodide, N-dimethyl-N-octyl-9-oxo-9H-thioxanthene-3-ammonium bromide and N-decyl-N, N-dimethyl-9, 10-dioxy-9, 10-dihydroanthracene-2-ammonium chloride;

the anionic substance is one or more of low molecular weight heparin, fondaparinux, hyaluronic acid, chondroitin, dermatan sulfate and keratan sulfate;

the low molecular weight heparin comprises one or more of dalteparin, nadroparin and enoxaparin, and the average molecular weight is 3000-5000 KD;

the molecular weight of the fondaparinux is 1700KD;

the molecular weight of the hyaluronic acid is 400000 ～ 1000000KD;

the solvent is one or more of methanol, ethanol, isopropanol, chloroform, acetone and dimethyl sulfoxide.

Preferably, the mass of the photo-induced cationic substance and the anionic substance is (20 to 85): 100;

the photoinitiated type anion-cation composite accounts for 0.02-25% of the mass of the bottom coating.

The mass ratio of the hydrophilic monomer to the hydrophilic polymer is (0.01-15): (0.01-25).

Preferably, in the top coat:

the hydrophilic monomer comprises one or more of polyethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane triacrylate; the ethoxyl linkage number of the ethoxyl trimethylolpropane triacrylate is more than 9;

the hydrophilic polymer is selected from one or more of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyacrylamide, polyacrylic acid, polyamide, polyethersulfone, polyimide, polyetherimide and polyamide;

the solvent is one or more of water, N-dimethylformamide, dimethyl sulfoxide, acetone, ethanol, methanol and isopropanol.

The invention provides application of the adhesion enhanced lubricating coating in the preparation of the medical intervention catheter surface coating.

The invention provides a medical intervention catheter coated with the adhesion-enhanced lubricating coating according to any one of the technical schemes.

The invention provides a preparation method of a medical intervention catheter coated with a lubricating coating with enhanced lubricating coating adhesion, which comprises the following steps:

a) Reacting the photoinitiated cationic substance aqueous solution with the anionic substance aqueous solution to obtain an anionic-cationic compound;

b) Dissolving the anion-cation complex in a solvent to obtain a bottom coating solution;

c) Loading the bottom coating solution on a medical intervention catheter, and performing ultraviolet curing treatment to obtain a medical catheter with a bottom coating with enhanced adhesion;

d) Mixing hydrophilic monomer solution and hydrophilic polymer solution, loading the mixture on the surface of a medical catheter with a bottom coating with enhanced adhesion, and carrying out ultraviolet curing treatment to obtain the medical interventional catheter coated with the lubricating coating with enhanced adhesion.

Preferably, the step a) specifically includes: the photoinitiated cationic substance aqueous solution is dripped into the anionic substance aqueous solution, and the precipitate is separated out, washed and freeze-dried to obtain the anionic-cationic compound.

Preferably, the concentration of the photoinitiated cationic substance in the photoinitiated cationic substance aqueous solution is 0.1-25 g/mL; the concentration of the anionic substances in the anionic substance aqueous solution is 0.1-50 g/mL; the concentration of the anion-cation compound in the bottom coating solution is 0.02-25 g/mL;

The mass concentration of the hydrophilic monomer in the hydrophilic monomer solution is 0.01% -15%; the mass concentration of the hydrophilic polymer in the hydrophilic polymer solution is 0.01% -25%;

the loading means is selected from dipping, spraying, spin coating or wiping.

Preferably, the main transmission wavelength of the ultraviolet curing in the step C) is 150-430 nm, and the ultraviolet curing treatment time is 2-15 min;

the light source of the ultraviolet light is one or more of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp and a filter.

Compared with the prior art, the invention provides a lubricating coating with enhanced adhesion, which comprises a bottom coating and a top coating; the raw materials of the bottom coating comprise photoinitiated anion-cation complex and solvent; the photoinitiated type anion-cation complex comprises a photoinitiated type cation substance and an anion substance; the raw materials of the surface coating comprise hydrophilic monomers, hydrophilic polymers and solvents. In the primer layer (tie coat) of the present invention, after curing, the curable polymer and the adhesion promoter may physically bond to each other or form an interpenetrating polymer network structure in an embedding manner. The primer (tie coat) may also form covalent bonds with the topcoat (lubricious coating) to form a stable network coating. The photoinitiated anion-cation composite bottom layer can generate Norrish II reaction and recombination reaction during curing, so that the chemical bond fixation of the bottom layer on the surface of a base material and self-crosslinking of the inside of the coating are realized, the adhesiveness of the low-level coating to the base material is effectively improved, the self-strength of the coating is improved, and the friction resistance and the shearing resistance are improved.

The photo-induced cationic substance adopted by the invention contains a photosensitive structural unit, a small molecular photo-initiator is not required to be added, and the photo-induced cationic substance is crosslinked and limited in a coating network after photo-curing, so that the industrial commonality problems of residue, migration and the like of the small molecular photo-initiator in a coating are fundamentally solved. Meanwhile, due to the existence of the photoinitiated cationic substance in the bottom layer formula, the invention can directly initiate the solidification of the hydrophilic monomer in the lubrication surface coating, so that an initiator can be not added in the surface coating formula, thereby completely solving the photoinitiating problem and ensuring the biological safety of the whole coating. Compared with the existing single-lubrication function coating formula, the cationic substance contained in the coating has high-efficiency antibacterial property, and meanwhile, the cationic substance is coated by the lubricating layer at the inner layer and the outer layer of the coating, so that the problem that the exposed antibacterial agent is deactivated by biomolecules under complex physiological conditions can be avoided, the coating has long-term anti-infection property, the occurrence of related infection of a medical catheter is reduced, and the service time of the medical catheter is prolonged.

Drawings

FIG. 1 is a schematic diagram of the construction of a coating layer of an adhesion-enhanced lubricious coating layer and a medical interventional catheter with lubricious antibacterial function;

FIG. 2 is a schematic diagram of a "normal coating" build;

FIG. 3 is a photograph of the platelet shape of an untreated medical interventional tube surface;

FIG. 4 is a photograph of a platelet shape of a medical interventional tube surface with an adhesion enhanced lubricious coating obtained in accordance with an embodiment of the present invention;

FIG. 5 is a photograph of colony culture count of untreated medical interventional tube surfaces;

FIG. 6 is a photograph showing the number of colonies cultured on the surface of a medical interventional tube having an adhesion-enhanced lubricious coating obtained in the examples of the present invention;

FIG. 7 is a photograph of bacterial adhesion and death of untreated medical intervention tube surfaces;

FIG. 8 is a photograph of bacterial adhesion and death of a control medical interventional tube surface having a lubricious top coating and a common bottom coating;

FIG. 9 is a photograph showing bacterial adhesion and death on the surface of medical interventional tubes with an adhesion-enhanced lubricious coating obtained in accordance with the examples of the present invention.

Detailed Description

The invention provides an adhesion-enhanced lubricious coating, applications thereof and a medical interventional catheter, and one skilled in the art can, in light of the disclosure herein, suitably modify the process parameters. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and they are intended to be within the scope of the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that the invention can be practiced and practiced with modification and alteration and combination of the methods and applications herein without departing from the spirit and scope of the invention.

The surface coating has a lubricating function and can resist bacterial adhesion.

The invention provides an adhesion-enhanced lubricating coating, which comprises a bottom coating.

The raw materials of the primer coating comprise photoinitiated anion-cation complex and solvent; the photoinitiated type anion-cation complex comprises a photoinitiated type cation substance and an anion substance;

the bottom coating has the cationic sterilization function of a quaternary ammonium salt structure, can perform synergistic effect with the anti-adhesion function of the surface coating, and improves the antibacterial infection effect. The cationic matter is coated by the lubricating layer and the inner layer of the coating, so that the problem that the bare antibacterial agent is deactivated by biomolecules under complex physiological conditions can be avoided, and the coating has long-term anti-infection property.

The photoinitiated cationic substance has bactericidal property; the photoinitiating cationic species itself contains a photoactive structural unit; the bottom layer coating is fixed on the surface of the substrate material through chemical bonds after photo-curing; the bottom coating realizes the internal crosslinking of the coating in a photo-curing mode. The whole double-layer structure coating has the effect of enhancing the adhesion and has the functions of lubrication and antibiosis.

According to the invention, the photo-induced cationic species has the structure of formula a:

r is selected from

x-is selected from Cl-or I-.

The photo-induced cationic species according to the present invention is preferably selected from one or more of N- (4-benzoylbenzyl) -N, N-dimethyldodecyl-1-ammonium bromide, 4- (4- (diethylamino) benzoyl) -N, N-diethyl-N-octylphenyl ammonium iodide, N-dimethyl-N-octyl-9-oxo-9H-thioxanthene-3-ammonium bromide and N-decyl-N, N-dimethyl-9, 10-dioxy-9, 10-dihydroanthracene-2-ammonium chloride.

The anionic substances are one or more of low molecular weight heparin, fondaparinux, hyaluronic acid, chondroitin, dermatan sulfate and keratan sulfate;

specifically, the low molecular weight heparin comprises one or more of dalteparin, nadroparin and enoxaparin, and the average molecular weight is 3000-5000 KD; the molecular weight of the fondaparinux is 1700KD; the molecular weight of the hyaluronic acid is 400000 ～ 1000000KD;

In the primer layer of the present invention, the solvent is preferably one or more of methanol, ethanol, isopropanol, chloroform, acetone and dimethylsulfoxide.

The photoinitiated cationic substance has bactericidal property; which itself contains a photosensitive structural unit; the bottom coating is fixed on the surface of the substrate material through chemical bonds after photo-curing; the bottom coating realizes the internal crosslinking of the coating in a photo-curing mode.

The mass of the photo-induced cationic substance and the anionic substance according to the present invention is preferably (20 to 85): 100.

The invention provides an adhesion-enhanced lubricating coating, which comprises a top-coat coating. The raw materials of the surface coating comprise hydrophilic monomers, hydrophilic polymers and solvents.

The surface coating provided by the invention has particularly good lubricating performance.

According to the present invention, the mass ratio of the hydrophilic monomer to the hydrophilic polymer is preferably (0.01 to 15): (0.01-25).

Specifically, the hydrophilic monomer comprises one or more of polyethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane triacrylate; the ethoxylated trimethylolpropane triacrylate has an ethoxy linkage number greater than 9.

The hydrophilic monomer realizes crosslinking and fixation through a photosensitive structural unit provided by a photoinitiated cationic substance.

The present invention is not limited to such medical interventional catheters, but is well known to those skilled in the art, including, but not limited to, balloon catheters, contrast catheters, microcatheters, central venous catheters, and indwelling needle cannulas.

The lubricating coating with enhanced adhesion can be coated on the surface of a medical intervention catheter, and can solve the problem of overlarge friction force in the use process of the catheter.

The lubricating coating of the present invention may include a primer layer (tie coat layer) and a top coat layer (lubricating coat layer). The basecoat is formed by curing a tackifying coating formulation comprising- -. In the primer layer (tie coat), after curing, the curable polymer and the adhesion promoter may physically bond to each other or form an interpenetrating polymer network in an embedded manner. The primer (tie coat) may also form covalent bonds with the topcoat (lubricious coating) to form a stable network coating.

The functional or lubricious coating provides lubricity to the composite coating and the tie coating provides stability to the composite coating. By adjusting the degree of hydrophobic substitution of the hydrophilic polymer in the tie coat, it is ensured that the surface of the tie coat is well connected to widely used medical device substrates, such as metals, polyurethane (PU), polyvinylchloride (PVC), rubber, nylon, polypropylene, polyethylene thermoplastic materials, polyethylene (high density polyethylene and low density polyethylene), poly perfluoroethylene propylene (FEP), poly (ethylene-tetrafluoroethylene) (ETFE), poly (ethylene terephthalate) (PET), and silicone elastomers, etc., some of which are highly hydrophobic (low surface energy), such as PP, HDPE, FEP, and ETFE, so it is difficult to spontaneously spread the hydrophilic coating solution over the surfaces of these materials. Without wishing to be bound by theory, it is understood that this problem arises because these hydrophobic base surface energies are low relative to the surface energy of the solvent (the solvent used as part of the surface coating of the substrate). This makes it difficult to effectively wet the substrate surface. For example, the surface energy of the hydrophilic coating solution is higher than that of the substrate, so the surface energy of the base surface needs to be modified in some way. In this case, the most common method to achieve good adhesion is pretreatment such as surface oxidation or plasma treatment to generate polar groups on the substrate surface. However, such a pretreated lubricious coating may be formed by curing a curable hydrophilic polymer, an initiator, and a solvent. Advantages of using curable hydrophilic polymers with cross-linkers or curable polymers: the curable hydrophilic polymer may crosslink with the crosslinking agent or the curable polymer itself, stabilizing the overall polymer network structure (due to crosslinking between the polymer components), and the volume of particles may be minimized and the shedding and migration effects may be small when the medical device is moved and placed within the body lumen of a human body.

The medical intervention catheter with the lubrication and antibacterial functions.

The adhesion-enhanced lubricious coating according to any one of the above embodiments of the present invention has been described above for clarity and will not be described in detail herein.

The invention provides a preparation method of a medical intervention catheter coated with a lubricating coating with enhanced lubricating coating adhesion, which comprises the following steps: and (3) reacting the photoinitiated cationic substance aqueous solution with the anionic substance aqueous solution to obtain the anionic-cationic compound.

The step A) of the invention is specifically as follows: the photoinitiated cationic substance aqueous solution is dripped into the anionic substance aqueous solution, and the precipitate is separated out, washed and freeze-dried to obtain the anionic-cationic compound.

A large amount of white or light yellow precipitate is separated out from the solution after dripping, the precipitate is washed by distilled water or ultrapure water, and the anion-cation complex is obtained after freeze drying.

The present invention has been described above for photoinitiated cationic and anionic materials in a clear manner and will not be described in detail herein.

According to the present invention, the concentration of the photoinitiating cationic species in the aqueous solution of the photoinitiating cationic species is preferably 0.1 to 25g/mL; more preferably 1 to 23g/mL;

the concentration of the anionic substance in the anionic substance aqueous solution is preferably 0.1-50 g/mL; more preferably 1 to 48g/mL.

Dissolving the anion-cation complex in a solvent to obtain a bottom coating solution; the concentration of the anion-cation compound in the primer coating solution is preferably 0.02-25 g/mL; more preferably 0.1 to 12g/mL.

The primer coating solution is loaded onto a medical interventional catheter. The loading means according to the invention are selected from dipping, spraying, spin coating or wiping.

The invention is not limited to the medical intervention catheter, and the medical intervention catheter is well known to the person skilled in the art; it is understood that some medical catheters are made of different materials, such as: the material of the indwelling needle sleeve, the catheter and the like can be silica gel or latex.

The coating of the invention is coated on the pipe, the whole root can be coated, or half of the coating can be coated, or the coating can be selected, and the mass of the coating can be 0.2-25% of the mass of the catheter.

And then carrying out ultraviolet curing treatment to obtain the medical catheter with the bottom coating with enhanced adhesion.

After the catheter attached with the anion-cation compound coating is obtained, the catheter attached with the compound is subjected to ultraviolet curing treatment, so that the catheter with the bottom coating with the crosslinking structure and the enhanced adhesion is obtained.

In the invention, the light source of the ultraviolet light is preferably one or more of a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp and a filter. The main transmission wavelength of ultraviolet light adopted in the ultraviolet curing treatment is preferably 150-430 nm, more preferably 200-380 nm; the time of the ultraviolet curing treatment is preferably 2 to 15 minutes, more preferably 3 to 8 minutes.

After the ultraviolet curing treatment, the ultraviolet curing treatment product is preferably washed and dried in sequence. The cleaning conditions comprise water bath, water bath oscillation and ultrasonic cleaning, and ethanol and deionized water are adopted to clean in sequence under the water bath oscillation condition to obtain the cleaned coating. In the invention, the frequency of the water bath oscillation is preferably 100-200 Hz, more preferably 120-150 Hz; the time for the ethanol cleaning is preferably 15-60 min, more preferably 30-40 min; the deionized water is preferably washed for 10 to 50 minutes, more preferably 25 to 30 minutes. The amount of the ethanol and deionized water used for the cleaning is not particularly limited in the present invention. In the present invention, the drying is preferably vacuum drying, and the drying time is preferably 12 to 30 hours, more preferably 24 to 28 hours; the drying temperature is preferably 45 to 80 ℃, more preferably 60 to 70 ℃.

The hydrophilic monomer solution is mixed with the hydrophilic polymer solution and loaded onto the surface of the medical catheter with the adhesion-enhanced primer coating.

The solvent in the hydrophilic monomer solution according to the present invention is preferably one or more of water, N-dimethylformamide, dimethyl sulfoxide, acetone, ethanol, methanol and isopropanol.

The mass concentration of the hydrophilic monomer in the hydrophilic monomer solution is 0.01-15%; more preferably 0.1 to 10g/mL. The mass concentration of the hydrophilic polymer in the hydrophilic polymer solution is 0.01% -25%; more preferably 1 to 15g/mL.

And then carrying out ultraviolet curing treatment to obtain the medical intervention catheter coated with the lubricating coating with enhanced lubricating coating adhesion.

The main transmission wavelength of ultraviolet light adopted in the ultraviolet curing treatment is preferably 150-430 nm, more preferably 200-380 nm; the time of the ultraviolet curing treatment is preferably 2 to 15 minutes, more preferably 3 to 8 minutes.

The invention provides an adhesion-enhanced lubricating coating, which comprises a bottom coating and a top coating; the raw materials of the bottom coating comprise photoinitiated anion-cation complex and solvent; the photoinitiated type anion-cation complex comprises a photoinitiated type cation substance and an anion substance; the raw materials of the surface coating comprise hydrophilic monomers, hydrophilic polymers and solvents. In the primer layer (tie coat) of the present invention, after curing, the curable polymer and the adhesion promoter may physically bond to each other or form an interpenetrating polymer network structure in an embedding manner. The primer (tie coat) may also form covalent bonds with the topcoat (lubricious coating) to form a stable network coating. The photoinitiated anion-cation composite bottom layer can generate Norrish II reaction and recombination reaction during curing, so that the chemical bond fixation of the bottom layer on the surface of a base material and self-crosslinking of the inside of the coating are realized, the adhesiveness of the low-level coating to the base material is effectively improved, the self-strength of the coating is improved, and the friction resistance and the shearing resistance are improved.

To further illustrate the present invention, the following describes in detail, with reference to examples, an adhesion-enhanced lubricious coating, its use, and a medical interventional catheter provided by the present invention.

Example 1

A) Preparing an aqueous solution of N- (4-benzoyl benzyl) -N with the concentration of 0.8g/mL, and preparing a heparin sodium solution with the concentration of 1.5 g/mL; dropwise adding the N- (4-benzoyl benzyl) -N aqueous solution into 10ml of heparin sodium solution until a large amount of white precipitate is separated out from the solution, standing for 2h, and filtering to obtain white precipitate. Washing the precipitate with ultrapure water for 3 times, and freeze-drying to obtain the anion-cation complex.

B) Dissolving the anion-cation complex obtained in the step A) in ethanol solution to prepare an anion-cation complex solution with the concentration of 8 g/mL; the polyurethane central venous catheter (weight is X0) is soaked in the compound solution for 45min, and the polyurethane central venous catheter is placed at 25 ℃ to enable the ethanol solvent to completely volatilize, so that the central venous catheter (weight is X1) with the coating of the physical adsorption anion-cation compound is obtained.

C) The central venous catheter loaded with the compound is irradiated for 5 minutes under a high-pressure mercury lamp with the wavelength of 365nm and the power of 320W, and N- (4-benzoyl benzyl) -N is combined with heparin sodium and a substrate to react under ultraviolet excitation, so that the bottom coating with the cross-linked structure and enhanced adhesion is obtained on the surface of the central venous catheter. Then cleaning the central venous catheter with ethanol and deionized water for 3 times under the water bath ultrasonic condition of 150Hz for 8min each time; then, the mixture was dried under vacuum at 60℃for 24 hours to obtain a coated central venous catheter having a crosslinked structure with a moderate modulus ((weight: X2).

D) Preparing a polyethylene glycol aqueous solution with the concentration of 0.2g/mL, preparing a diethylene glycol dimethacrylate solution with the concentration of 1g/mL, mixing the solutions, dip-coating the mixture on the surface of a central venous catheter fixed with a tackifying bottom layer, irradiating the surface of the central venous catheter for 8min by using a high-pressure mercury lamp with the wavelength of 365nm and the power of 330W, and then ultrasonically oscillating and washing the surface of the central venous catheter by using ethanol and deionized water to obtain the central venous catheter (with the weight of X3) with a double-layer coating structure comprising a lubricating top coating layer and a bottom coating layer with enhanced adhesion.

Example 2

A) Preparing an acetone solution of N-diethyl-N-octyl phenyl ammonium iodide with the concentration of 3 g/mL-and preparing a sodium hyaluronate aqueous solution with the concentration of 12 g/mL; the aqueous solution of N-diethyl-N-octyl phenyl ammonium iodide is dropwise added into 25ml of sodium hyaluronate solution until a large amount of white precipitate is precipitated in the solution, and the solution is left for 3.5 hours and filtered to obtain white precipitate. Washing the precipitate with ultrapure water for 3 times, and freeze-drying to obtain the anion-cation complex.

B) Dissolving the anion-cation complex obtained in the step A) in an acetone solution to prepare an anion-cation complex solution with the concentration of 12 g/mL; the polyurethane venous indwelling needle cannula (weight is X0) is soaked in the compound solution for 60min, and the polyurethane venous indwelling needle cannula is placed at 25 ℃ to enable the acetone solvent to be completely volatilized, so that the venous indwelling needle cannula (weight is X1) with the coating of the physical adsorption anion-cation compound is obtained.

C) And (3) irradiating the venous indwelling needle sleeve loaded with the compound for 3min under a high-pressure mercury lamp with the wavelength of 235nm and the power of 380W, and carrying out a combination reaction on the N-diethyl-N-octyl phenyl ammonium iodide, sodium hyaluronate and a substrate under ultraviolet excitation to obtain a bottom coating with a cross-linked structure, wherein the adhesion of the bottom coating is enhanced on the surface of the venous indwelling needle sleeve. Then the venous indwelling needle sleeve is washed with ethanol and deionized water for 3 times under the water bath ultrasonic condition of 120Hz for 15min each time; then, the venous indwelling needle cannula (weight is X2) with the coating of the cross-linked structure with moderate modulus is obtained after vacuum drying for 24 hours at 65 ℃.

D) Preparing 2.5g/mL polyacrylamide ethanol solution, preparing 1.8g/mL trimethylolpropane triacrylate solution, mixing the solutions, dip-coating the solution on the surface of the venous indwelling needle sleeve fixed with the tackifying bottom layer, irradiating the surface for 8min by using a high-pressure mercury lamp with the wavelength of 365nm and the power of 330W, and then ultrasonically oscillating and washing the surface by using ethanol and deionized water to obtain the venous indwelling needle sleeve (with the weight of X3) with a double-layer coating structure with a lubricating top coating and a bottom coating with enhanced adhesion.

Example 3

A) Preparing an ethanol solution of N-dimethyl dodecyl-1-ammonium bromide with the concentration of 0.5 g/mL-and preparing a methanol solution of chondroitin with the concentration of 1.5 g/mL; the aqueous solution of N-dimethyl dodecyl-1-ammonium bromide is dropwise added into 5ml of chondroitin solution until a large amount of white precipitate is precipitated in the solution, and the solution is left for 1.5h and filtered to obtain white precipitate. Washing the precipitate with ultrapure water for 3 times, and freeze-drying to obtain the anion-cation complex.

B) Dissolving the anion-cation complex obtained in the step A) in a methanol solution to prepare an anion-cation complex solution with the concentration of 0.8 g/mL; the PVC catheter (weight is X0) is soaked in the compound solution for 60min, and the PVC catheter (weight is X1) with the coating of physically adsorbed anion-cation compound is obtained after the methanol solvent is completely volatilized by standing at 25 ℃.

C) And (3) irradiating the PVC catheter loaded with the compound for 8min under a medium-pressure mercury lamp with the wavelength of 240nm and the power of 200W, and carrying out a combination reaction on the N-dimethyl dodecyl-1-ammonium bromide, chondroitin and a substrate under ultraviolet excitation to obtain the prime coating with the cross-linked structure, wherein the adhesion of the prime coating is enhanced on the surface of the PVC catheter. Then cleaning the PVC catheter with ethanol and deionized water for 3 times under the condition of 180Hz water bath ultrasonic, and 20 minutes each time; then, the PVC catheter with the coating of the cross-linked structure and moderate modulus (weight is X2) is obtained after vacuum drying for 24 hours at 50 ℃.

D) Preparing a polyvinylpyrrolidone methanol solution with the concentration of 0.3g/mL, preparing a polyethylene glycol diacrylate solution with the concentration of 1.2g/mL, mixing the solutions, dip-coating the mixture on the surface of a venous indwelling needle sleeve fixed with a tackifying bottom layer, irradiating the sleeve for 3min by using a high-pressure mercury lamp with the wavelength of 246nm and the power of 330W, and then ultrasonically oscillating and washing the sleeve by using ethanol and deionized water to obtain the PVC catheter (weight is X3) with a double-layer coating structure with a lubricating top coating and an adhesion-enhanced bottom coating.

Example 4

A) Preparing an acetone solution of N- (4-benzoyl benzyl) -N with the concentration of 1.5g/mL, and preparing a sodium hyaluronate aqueous solution with the concentration of 1.5 g/mL; the aqueous solution of N- (4-benzoyl benzyl) -N is dropwise added into 8ml of sodium hyaluronate solution until a large amount of white precipitate is precipitated in the solution, and the solution is left stand for 2 hours and filtered to obtain white precipitate. Washing the precipitate with ultrapure water for 3 times, and freeze-drying to obtain the anion-cation complex.

B) Dissolving the anion-cation complex obtained in the step A) in ethanol solution to prepare an anion-cation complex solution with the concentration of 8 g/mL; the polyurethane venous indwelling needle cannula (weight is X0) is soaked in the compound solution for 60min, and the solution is placed at 25 ℃ to enable the ethanol solvent to be completely volatilized, so that the venous indwelling needle cannula (weight is X1) with the coating of the physical adsorption anion-cation compound is obtained.

C) The venous indwelling needle cannula loaded with the compound is placed under a high-pressure mercury lamp with the wavelength of 365nm and the power of 320W to irradiate for 3min, and N- (4-benzoyl benzyl) -N is subjected to combination reaction with sodium hyaluronate and a substrate under ultraviolet excitation, so that a prime coating with a cross-linked structure and enhanced adhesion is obtained on the surface of the venous indwelling needle cannula. Then cleaning the venous indwelling needle sleeve with ethanol and deionized water for 3 times under the water bath ultrasonic condition of 150Hz for 8min each time; then, the mixture was dried under vacuum at 60℃for 24 hours to obtain a coating layer having a crosslinked structure and having a moderate modulus ((weight: X2).

D) Preparing polyvinylpyrrolidone isopropanol solution with the concentration of 3.5g/mL, preparing diethylene glycol dimethacrylate solution with the concentration of 1g/mL, mixing the solutions, dip-coating the mixture on a venous indwelling needle sleeve fixed with a tackifying bottom layer, irradiating the venous indwelling needle sleeve for 10min by using a high-pressure mercury lamp with the wavelength of 365nm and the power of 330W, and then ultrasonically oscillating and washing the venous indwelling needle sleeve by using ethanol and deionized water to obtain the venous indwelling needle sleeve with a double-layer coating structure with a lubricating top coating and a bottom coating with enhanced adhesion (the weight is X3).

Example 5 Performance test

1) Coating adhesion test:

the medical intervention catheter (weight X1) carrying the anionic and cationic compound intermediate coating, the medical intervention catheter (weight X2) carrying the primary coating of the crosslinking structure with enhanced adhesion, the medical intervention catheter (weight X3) carrying the double-layer coating structure of the lubricating top coating and the primary coating with enhanced adhesion, and the medical intervention catheter (weight Y1) carrying the common coating of the control group are respectively processed in an ultrasonic cleaning machine for 10min and 60min, and then are dried in vacuum for 24h at 60 ℃, and then weighed (the weights are X4, X5, X6 and Y2). The coating retention rate is calculated, and the calculation formula of the medical intervention catheter loaded with the intermediate coating is as follows: coating retention 1 (%) = (X4-X0/X1-X0) ×100%; the calculation formula of the medical intervention catheter for the undercoating layer of the crosslinking structure with the enhanced load adhesion is as follows: coating retention 2 (%) = (X5-W0/X2-W0) ×100%; the calculation formula of the medical intervention catheter with a double-layer coating structure of a supported lubricating top coating and an adhesion enhanced bottom coating is as follows: coating retention 3 (%) = (X6-W0/X3-W0) ×100%; for the medical intervention catheter loaded with the common coating in the control group, the calculation formula is as follows: coating retention 4 (%) = (Y2-W0/Y1-W0) ×100%. The results are shown in Table 1, table 1 shows the coating residence ratios of the medical interventional catheters having a two-layer coating structure with a lubricious top coating and an adhesion-enhancing primer coating obtained in examples 1-4 of the present invention.

Table 1 coating persistence of medical interventional catheters with double layer coating structure of lubricious top coating and adhesion enhanced primer coating obtained in examples 1-4 of the present invention

As can be seen from table 1, the coating retention rates of the medical intervention catheter with the double-layer coating structure of the lubricating top coating and the adhesion enhanced primer coating provided by the invention are respectively up to 99.5% and 98.8% after 10min and 60min of ultrasound, while the retention rates of the indwelling needle cannula coated with the intermediate coating only loaded in a physical manner are respectively 43.2% and 26.1% respectively, wherein the coating retention rates of the medical intervention catheter loaded with the common coating in a comparison group are respectively 62.1% and 46.4%, which indicates that the double-layer coating structure of the lubricating top coating and the adhesion enhanced primer coating provided by the invention has higher substrate adhesion and stability of the coating itself.

2) Coating lubricity test 1:

the present invention uses MXD-02 friction coefficient meter to test the friction coefficient of the medical intervention catheter (example group) of the double-layer coating structure having the lubricating top coating and the adhesion-enhanced primer coating in example 1, the medical intervention catheter (control group) of the double-layer coating structure having the same lubricating top coating and the common primer coating, and the unmodified medical intervention catheter (unmodified group). Firstly, respectively ultrasonically cleaning the 3 groups of medical intervention catheters for 3 times, 15 minutes each time, then fixing the catheters on a groove plate, and injecting water into a water storage tank until the sample is completely soaked in the catheters. 200g of standard sliding block is lightly placed above a sample, the sliding block is dragged by a sensor connecting rod to move at the speed of 100mm/min, the dynamic friction coefficient is measured, the steps are repeated, and the results are shown in tables 2-1 and 2-2, wherein the tables 2-1 and 2-2 are the adhesion-enhanced lubrication coating and the friction coefficient of the medical intervention catheter with the lubrication and antibacterial functions.

TABLE 2-1 adhesion enhanced lubricating coating and medical intervention catheter having lubricating and antimicrobial properties coefficient of friction (first wash)

TABLE 2-2 adhesion enhanced lubricating coating and medical intervention catheter with lubricating and antimicrobial properties coefficient of friction (second wash)

Experimental results show that the repeated ultrasonic cleaning and water soaking have no influence on the adhesion and the lubricating performance of the lubricating coating with enhanced adhesion and the medical intervention catheter coating with lubricating and antibacterial functions of the embodiment 1, the friction coefficient has no obvious change, and the friction coefficient of the lubricating coating with enhanced adhesion and the medical intervention catheter with lubricating and antibacterial functions is only about one percent of that of a common catheter, which indicates that the lubricating coating is firmly combined with the catheter wall and has strong coating stability. After ultrasonic cleaning for many times, the common base coating is low in adhesion, so that the lubricating surface coating is separated due to infirm coating, the lubricating performance is reduced and the friction coefficient is gradually increased along with the increase of ultrasonic cleaning times.

3) Coating lubricity test 2:

the present invention uses MXD-02 friction coefficient apparatus to test friction coefficients for the medical intervention catheter of example 1 (example group) having a double-layer coating structure of the lubricating top coating and the adhesion-enhanced primer coating, the single-layer coated medical intervention catheter having only the adhesion-enhanced primer coating (control group), and the unmodified medical intervention catheter (unmodified group). Firstly, respectively soaking the 3 groups of medical intervention catheters with clear water for 30s, then fixing the catheters on a groove plate, and injecting water into a water storage tank until the sample is completely soaked in the catheters. 200g of standard slide block is lightly placed above a sample, the slide block is dragged by a sensor connecting rod to move at the speed of 100mm/min, and the dynamic friction coefficient is measured, and the result is shown in table 3, wherein table 3 shows the friction coefficient of a medical intervention catheter with a double-layer coating structure of a lubricating top coating layer and an adhesion-enhanced bottom coating layer and a single-layer coating medical intervention catheter with only the adhesion-enhanced bottom coating layer.

Table 3 coefficient of friction for medical intervention-like catheters with a two-layer coating structure of a lubricious top coating and an adhesion-enhancing primer coating and single-layer coated medical intervention-like catheters with only an adhesion-enhancing primer coating

Experimental results show that the single-layer coating medical intervention catheter with the adhesion-enhanced primer coating does not have good lubricating performance, and the friction coefficient is not obviously changed compared with an unmodified sample. The medical intervention catheter with the double-layer coating structure of the lubricating top coating and the adhesion enhanced bottom coating has good lubricating performance, and the lubricating coating is firmly combined with the catheter wall through the bottom coating effect, and the lubricating top coating and the adhesion enhanced bottom coating have obvious difference in lubricating performance.

4) Coating safety test

The medical intervention catheters (example group) with the double-layer coating structure of the lubricating top coating and the adhesion enhanced bottom coating prepared in examples 1-4, the medical intervention catheters (control group) with the same lubricating top coating and the common bottom coating, and the unmodified medical intervention catheters (unmodified group) are subjected to an initiator precipitation detection test. Wherein, the medical intervention catheter (control group) loaded with the same lubricating top coating and common bottom coating is fixed on the surface of the catheter through a small molecular photoinitiator. Respectively soaking the 3 groups of samples in aqueous solution for 6 hours under the ultrasonic condition of 60 ℃ and 200w power, taking the soaked solution, detecting the absorbance condition of each group of samples by an infrared spectrophotometer, and judging the precipitation condition of the small molecular photoinitiator according to the peak change. Table 4 is the initiator precipitation profile for medical interventional catheters having a two-layer coating structure with a lubricious top coating and an adhesion enhanced primer coating

TABLE 4 initiator precipitation of medical interventional catheters with double layer coating structure of lubricious top coating and adhesion enhanced primer coating

Experimental results show that the medical intervention catheter with a double-layer coating structure with a lubricating top coating and an adhesion enhanced bottom coating is free of initiator precipitation after long-time soaking, and the photoinitiated type anion-cation composite bottom layer can generate Norrish II reaction and recombination reaction during curing, so that the chemical bond fixation of the bottom coating on the surface of a base material and the self-crosslinking of the inside of the coating are realized, the adhesion of the low coating to the base material is effectively improved, the self-strength of the coating is also improved, and the safety performance of the coating is improved.

5) Anticoagulation test:

the medical intervention catheter with the double-layer coating structure prepared in the examples 1-4 is incubated for 60min at 37 ℃ in freshly prepared platelet-rich plasma, and then the platelet morphology of the surface of the needle placement sleeve is photographed by adopting a scanning electron microscope. To ensure the authenticity and credibility of the experiment, the average value of 3 repeated experiments was performed to obtain data, wherein the untreated indwelling needle cannula was used as a negative control group (manufacturer: shandong West high group medical Polymer products Co., ltd.). As a result, as shown in FIGS. 3 to 4, FIG. 3 is a photograph showing the appearance of platelets on the surface of an untreated cannula, and FIG. 4 is a photograph showing the appearance of platelets on the surface of an indwelling needle cannula having a double-layer coating structure obtained in example 2 of the present invention.

As can be seen from fig. 3 to 4, a large number of platelets adhere to the surface of the untreated indwelling needle cannula, and the platelets assume a spread, fully spread activated state. The indwelling needle cannula with a double-layer coating structure obtained in example 2 of the present invention had few platelets adhered to the surface thereof, and the platelets exhibited a round, fusiform inactive state. Considering that platelet adhesion and activation play an important role in the coagulation process, it is illustrated that the double-layer coating structure indwelling needle cannula with the lubricating top coating and the adhesion enhanced bottom coating provided by the invention can reduce the occurrence probability of coagulation phenomenon.

6) Antibacterial test 1:

sterilizing the medical intervention catheter with the double-layer coating structure and the medical intervention catheter without the coating treatment prepared in the examples 1-4, and under the aseptic experimental condition, carrying out concentration of 1X10 ⁶ culturing cfu/mL staphylococcus aureus in LB nutrient solution for 24 hours, then taking out the catheter, performing low-power ultrasonic treatment and dilution, taking diluted bacterial liquid, culturing for 12 hours at 37 ℃ in solid LB plate culture, counting bacterial colonies on a plate culture medium, and determining the bacterial number on the surface of a medical catheter, wherein the bacterial colony situation after the medical catheter is subjected to uncoated treatment is shown in FIG. 5, and the bacterial colony situation after the medical interventional catheter is cultured with a double-layer coating structure is shown in FIG. 6. The results of 3 replicates were averaged and are shown in table 4.

TABLE 5 number of viable bacteria on medical catheter surfaces

It can be seen from table 5 that the adhesion-enhanced lubricious coating and the medical interventional catheter having the lubricious antibacterial function can effectively reduce the number of living bacteria on the catheter surface even without adding the lubricating oil. After the lubricating coating with enhanced adhesion and the medical intervention catheter with lubricating and antibacterial functions are injected with lubricating oil, the number of living bacteria on the surface of the medical catheter is further reduced and maintained at a very low level.

7) Antimicrobial test 2:

in a sterile test operating environment, staphylococcus aureus was cultured at 37℃and the double-layer coated medical intervention catheter (example group) having the lubricious top coating and the adhesion-enhanced primer coating described in example 1, the double-layer coated medical intervention catheter (control group) having the lubricious top coating and the common primer coating, and the uncoated medical intervention catheter (unmodified group) were immersed in a 1X 10 concentration of Staphylococcus aureus ⁶ In cfu/mL LB solution, culturing at 37 ℃ for 6 hours, taking out, fixing with 4% paraformaldehyde for 4 hours, and observing the adhesion and death of bacteria on the surfaces of the medical intervention catheters of the example group and the control group by adopting a scanning electron microscope after ethanol gradient dehydration, as shown in figures 7, 8 and 9.

The experimental results show that the bacteria on the surface of the medical catheter in the unmodified group adhere to and die, and the results show that a large amount of bacteria are adhered to the surface of the medical catheter which is not coated with the coating, and the medical catheter is in the form of living bacteria; FIG. 8 shows the surface bacteria of a medical interventional catheter with a double-layer coating structure of a lubricating top coating and a common bottom coating in a control group, and the result shows that the lubricating top coating effectively inhibits the adhesion of bacteria, only a small amount of bacteria adhere to the surface of the catheter, and the bottom coating has no sterilization function, so that the adhered bacteria are completely living bacteria, and the surface coating of the catheter of the surface control group has only anti-adhesion function; fig. 9 shows the case of bacteria on the surface of a medical intervention catheter having a double-layer coating structure of a lubricious top coating and an adhesion-enhanced bottom coating, and shows that the lubricious top coating effectively inhibits the adhesion of bacteria, only a small amount of bacteria adhere to the surface of the catheter, and the bottom coating has a bactericidal function, so that the adhered bacteria form breaks into dead bacteria, and the surface coating of the catheter of the example set is an anti-bactericidal binding surface.

The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims

1. An adhesion-enhanced lubricious coating comprising a primer coating and a topcoat coating;

the raw materials of the bottom coating are photoinitiated anion-cation complex and solvent; the photoinitiated type anion-cation complex consists of photoinitiated type cation substances and anion substances;

the raw materials of the surface coating are hydrophilic monomers, hydrophilic polymers and solvents;

in the surface coating:

the hydrophilic monomer comprises one or more of polyethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and ethoxylated trimethylolpropane triacrylate; the ethoxyl connection number of the ethoxyl trimethylolpropane triacrylate is more than 9;

the hydrophilic polymer is selected from one or more of polyvinylpyrrolidone (PVP), polyethylene glycol (PEG), polyvinyl alcohol (PVA), polyacrylamide, polyacrylic acid, polyethersulfone, polyimide, polyetherimide and polyamide; the photoinitiating cationic species has the structure of formula a:

formula A;

r is selected from

Or->

；

X ^- selected from Cl ^- Or I ^- 。

2. The lubricious coating of claim 1 wherein in the primer coating:

the molecular weight of the fondaparinux is 1700KD;

the molecular weight of the hyaluronic acid is 400000~1000000 KD;

3. The lubricious coating of claim 1 wherein the photo-induced cationic species and anionic species are present in a mass ratio of (20-85): 100;

The photoinitiated type anion-cation compound accounts for 0.02% -25% of the mass of the bottom coating;

the mass ratio of the hydrophilic monomer to the hydrophilic polymer is (0.01-15): (0.01 to 25).

4. The lubricating coating of claim 1, wherein the lubricant is,

the solvent of the surface coating is one or more of water, N-dimethylformamide, dimethyl sulfoxide, acetone, ethanol, methanol and isopropanol.

5. The use of the adhesion-enhanced lubricious coating of any one of claims 1-4 in the preparation of a medical interventional catheter surface coating.

6. A medical intervention catheter coated with the adhesion enhanced lubricious coating of any of claims 1-5.

7. A method of preparing a medical intervention catheter as in claim 6, comprising:

8. The method according to claim 7, wherein the step a) is specifically: the photoinitiated cationic substance aqueous solution is dripped into the anionic substance aqueous solution, and the precipitate is separated out, washed and freeze-dried to obtain the anionic-cationic compound.

9. The method according to claim 7, wherein the concentration of the photoinitiated cationic substance in the aqueous solution of the photoinitiated cationic substance is 0.1 to 25g/mL; the concentration of the anionic substances in the anionic substance aqueous solution is 0.1-50 g/mL; the concentration of the anion-cation compound in the bottom layer coating solution is 0.02-25 g/mL;

the loading means is selected from dipping, spraying, spin coating or wiping.

10. The method according to claim 7, wherein the main transmission wavelength of the ultraviolet curing in the step C) is 150-430 nm, and the ultraviolet curing treatment time is 2-15 min;

The light source of ultraviolet light used in the ultraviolet curing is one or more of a low-pressure mercury lamp, a medium-pressure mercury lamp and a high-pressure mercury lamp.