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CN119405912A - A hydrophilic coating and its preparation method and application - Google Patents

A hydrophilic coating and its preparation method and application Download PDF

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Publication number
CN119405912A
CN119405912A CN202510012083.4A CN202510012083A CN119405912A CN 119405912 A CN119405912 A CN 119405912A CN 202510012083 A CN202510012083 A CN 202510012083A CN 119405912 A CN119405912 A CN 119405912A
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CN
China
Prior art keywords
hydrophilic coating
solution
irgacure
photoinitiator
cross
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Pending
Application number
CN202510012083.4A
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Chinese (zh)
Inventor
李亚伟
杨宇霆
谢松然
许永松
崔巍
于仕轩
严园
毛秋硕
王欢
王家奇
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Beijing Taijieweiye Technology Co ltd
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Beijing Taijieweiye Technology Co ltd
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Priority to CN202510012083.4A priority Critical patent/CN119405912A/en
Publication of CN119405912A publication Critical patent/CN119405912A/en
Pending legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/08Materials for coatings
    • A61L31/10Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/08Materials for coatings
    • A61L29/085Macromolecular materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L29/00Materials for catheters, medical tubing, cannulae, or endoscopes or for coating catheters
    • A61L29/14Materials characterised by their function or physical properties, e.g. lubricating compositions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L31/00Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
    • A61L31/14Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
    • A61L2300/452Lubricants
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/60Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
    • A61L2300/606Coatings

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  • Health & Medical Sciences (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Heart & Thoracic Surgery (AREA)
  • Surgery (AREA)
  • Vascular Medicine (AREA)
  • Materials For Medical Uses (AREA)

Abstract

本发明实施例涉及一种亲水涂层及其制备方法和应用,其中亲水涂层包括结合层和润滑层;结合层用于与待润滑物的表面进行粘合,结合层的成分包括:5%‑12%的预聚物、0.3%‑2.5%的第一交联剂,0.05%‑0.8%的第一光引发剂和85%‑94%的第一溶剂;润滑层覆盖于结合层之上,润滑层的成分包括:2%‑7%的亲水化合物、1%‑5%的第二交联剂、0%‑0.3%的稳定剂、0.05%‑0.8%的第二光引发剂和88%‑96%的第二溶剂;其中第一交联剂与第二交联剂相同。该亲水涂层具有较好的润滑性和牢固性。

The embodiment of the present invention relates to a hydrophilic coating and a preparation method and application thereof, wherein the hydrophilic coating comprises a bonding layer and a lubricating layer; the bonding layer is used to bond with the surface of the lubricated object, and the components of the bonding layer include: 5%-12% of prepolymer, 0.3%-2.5% of the first cross-linking agent, 0.05%-0.8% of the first photoinitiator and 85%-94% of the first solvent; the lubricating layer covers the bonding layer, and the components of the lubricating layer include: 2%-7% of the hydrophilic compound, 1%-5% of the second cross-linking agent, 0%-0.3% of the stabilizer, 0.05%-0.8% of the second photoinitiator and 88%-96% of the second solvent; wherein the first cross-linking agent is the same as the second cross-linking agent. The hydrophilic coating has good lubricity and firmness.

Description

Hydrophilic coating and preparation method and application thereof
Technical Field
The invention relates to the technical field of medical materials, in particular to a hydrophilic coating, a preparation method and application thereof.
Background
In vascular interventional therapy, an interventional guide wire and a catheter are key instruments for introducing and delivering instruments to a focus part, and the outer layers of the guide wire and the catheter are basically made of high polymer materials such as Polyurethane (PU), thermoplastic Polyurethane (TPU), polyether amide (Pebax) and the like. Most of these materials are hydrophobic, and the surface friction coefficient is high, when the guide wire or catheter moves in and out of the blood vessel and in the blood vessel, the hydrophobic surface can cause astringency when the product is used, the conveying function of the device is affected, and serious damage to blood cells and the blood vessel wall can be caused, so that the interference to blood flow is generated, and then the coagulation reaction occurs.
The hydrophilic coating is coated on the surfaces of the high polymer materials, so that the surface friction coefficient can be effectively reduced, the operation is easy, the damage to blood vessels can be reduced when the product moves in the blood vessels, and the coagulation reaction can be effectively avoided.
In the actual use process, the guide wire and the catheter can be accurately positioned only through multiple adjustment, and the hydrophilic coating with poor firmness is easy to fall off in the adjustment process, so that not only can the friction coefficient be increased to generate pushing difficulty, but also thrombus can be formed in a blood vessel by the fallen hydrophilic coating, and therefore, the lubricity and the firmness of the hydrophilic coating are always the key and difficult point of the development of the hydrophilic coating technology.
Most of the hydrophilic coatings at present cannot guarantee long-term stability of the product in the use process, the preparation method is complex, and the coating process is time-consuming and labor-consuming.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art and provides a hydrophilic coating, a preparation method and application thereof, wherein the hydrophilic coating has better lubricity and firmness.
To achieve the above object, in a first aspect, the present invention provides a hydrophilic coating comprising a bonding layer and a lubricating layer;
The composition of the bonding layer comprises 5% -12% of prepolymer, 0.3% -2.5% of first cross-linking agent, 0.05% -0.8% of first photoinitiator and 85% -94% of first solvent;
The lubricating layer is covered on the bonding layer, and the lubricating layer comprises 2% -7% of hydrophilic compound, 1% -5% of second cross-linking agent, 0% -0.3% of stabilizing agent, 0.05% -0.8% of second photoinitiator and 88% -96% of second solvent, wherein the first cross-linking agent and the second cross-linking agent are the same.
Preferably, the molecular weight of the prepolymer is 1000-50000, and the prepolymer comprises one or more of polyester acrylate, unsaturated polyester, polyurethane acrylate, epoxy acrylate, polyether acrylate, polyene mercaptan system and aqueous acrylate.
Preferably, the molecular weight of the first cross-linking agent is 100-2000, and the first cross-linking agent comprises one or more of polyethylene glycol diacrylate, diethylenetriamine and ethylene glycol dimethacrylate, and the molecular weight of the second cross-linking agent is 100-2000, and the second cross-linking agent comprises one or more of polyethylene glycol diacrylate, diethylenetriamine and ethylene glycol dimethacrylate.
Preferably, the first photoinitiator comprises one or more of Irgacure 127, irgacure 1173, irgacure 2959, benzophenone, irgacure 2022, (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide TP0, and the second photoinitiator comprises one or more of Irgacure 127, irgacure 1173, irgacure 2959, benzophenone, irgacure 2022, (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide TP 0.
Preferably, the molecular weight of the hydrophilic compound is not less than 200000, and the hydrophilic compound comprises one or more of hyaluronic acid, polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol and polyacrylate.
Preferably, the molecular weight of the stabilizer is 600-2000, and the stabilizer comprises one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitol monostearate and polyoxyethylene sorbitan palmitate.
Preferably, the first solvent is one or more of water, methanol and ethanol, and the second solvent is one or more of water, methanol and ethanol.
In a second aspect, the present invention provides a method for preparing a solution of a hydrophilic coating according to any one of the first aspects, the method comprising:
under the condition of avoiding light, adding the prepolymer into a first solvent for ultrasonic dispersion, then adding a first cross-linking agent, and stirring at room temperature for a first period of time to obtain a first mixed solution;
Under the condition of avoiding light, dissolving a first photoinitiator in the first solvent, adding the first photoinitiator into the first mixed solution, and stirring at room temperature for a second period of time to obtain a bonding layer solution;
Adding a hydrophilic compound into a second solvent under the condition of avoiding light, stirring for a third time period at room temperature, adding a second crosslinking agent which is the same as the first crosslinking agent, uniformly mixing, and adding a stabilizer, uniformly mixing to obtain a second mixed solution;
And under the condition of avoiding light, dissolving a second photoinitiator in the second solvent, adding the second photoinitiator into the second mixed solution, and stirring at room temperature for a fourth period of time to obtain a lubricating layer solution, thereby obtaining a hydrophilic coating solution comprising a bonding layer solution and the lubricating layer solution.
Preferably, the ultrasonic dispersion time is 10min-90min, the first time is 1 hour-3 hours, the second time is 0.5 hour-2 hours, the third time is 1 hour-5 hours, and the fourth time is 0.5 hour-2 hours.
In a third aspect, the present invention provides the use of a hydrophilic coating according to any of the first aspects described above, which can be applied in a to-be-lubricated object prepared from polyurethane PU, thermoplastic polyurethane TPU, polyether amide Pebax, nylon PA, polyvinyl chloride PVC, and silicone materials, as well as on the surface of an irregular catheter, on the surface of a guidewire, on the surface of a catheter with an inner diameter of 0.012 inches to 0.096 inches.
The hydrophilic coating comprises a bonding layer and a lubricating layer, wherein the bonding layer is adhered to the surface of an object to be lubricated through polymerization of a prepolymer, bonding firmness between the hydrophilic coating and the object to be lubricated is improved, a second cross-linking agent of the lubricating layer is identical to a first cross-linking agent, so that the second cross-linking agent can be stably cross-linked with the bonding layer, bonding firmness between the lubricating layer and the bonding layer is guaranteed, and the hydrophilic compound is present, so that the lubricating layer has hydrophilicity, and the object to be lubricated with the hydrophilic coating can have a good lubricating effect when being used in a working environment.
Drawings
FIG. 1 is a flow chart of a method for preparing a solution of a hydrophilic coating according to an embodiment of the present invention;
FIG. 2 is a chart showing the test of the friction coefficient of the catheter according to example 1 of the present invention;
FIG. 3 is a chart showing the test of the friction coefficient of the catheter according to example 2 of the present invention;
fig. 4 is a chart showing the friction coefficient test of the catheter according to comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The technical scheme of the invention is further described in detail through the drawings and the embodiments.
Embodiments of the present invention provide a hydrophilic coating that may specifically include a bonding layer and a lubricating layer, with a coefficient of friction of no greater than 0.04.
The composition of the bonding layer can specifically comprise 5% -12% of prepolymer, 0.3% -2.5% of first cross-linking agent, 0.05% -0.8% of first photoinitiator and 85% -94% of first solvent. Preferably comprising 7% -9% of prepolymer, 0.5% -2.2% of first cross-linking agent, 0.2% -0.5% of first photoinitiator and 88% -91% of first solvent.
The molecular weight of the prepolymer is 1000-50000 and can comprise one or more of polyester acrylate, unsaturated polyester, polyurethane acrylate, epoxy acrylate, polyether acrylate, polyene mercaptan system and water-based acrylate.
The first crosslinking agent has a molecular weight of 100-2000 and may include one or more of polyethylene glycol diacrylate, diethylenetriamine, and ethylene glycol dimethacrylate.
The first photoinitiator may include one or more of Irgacure 127, irgacure 1173, irgacure 2959, benzophenone, irgacure 2022, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide TP 0.
The first solvent may be one or more of water, methanol, ethanol.
The bonding layer is used as a bottom layer of the hydrophilic coating and is generally contacted with the surface of the object to be lubricated, when ultraviolet light is irradiated, the prepolymer can be polymerized under the action of the first photoinitiator and the first crosslinking agent to generate a polymer with viscosity, so that the polymer is bonded on the surface of the object to be lubricated, and the connection firmness of the hydrophilic coating and the object to be lubricated is improved.
The lubricating layer comprises 2% -7% of hydrophilic compound, 1% -5% of second cross-linking agent, 0% -0.3% of stabilizing agent, 0.05% -0.8% of second photoinitiator and 88% -96% of second solvent. Preferably comprising 4% -6% of a hydrophilic compound, 1% -4% of a second cross-linking agent, 0% -0.1% of a stabilizing agent, 0.1% -0.5% of a second photoinitiator and 90% -95% of a second solvent.
The hydrophilic compound has a molecular weight of 200000 or more selected from hyaluronic acid, polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol, and polyacrylate. The addition of the hydrophilic compound renders the lubricating layer hydrophilic.
The second crosslinking agent has a molecular weight of 100-2000 and may include one or more of polyethylene glycol diacrylate, diethylenetriamine, and ethylene glycol dimethacrylate. The second crosslinking agent is the same as the first crosslinking agent.
The molecular weight of the stabilizer is 600-2000, and can comprise one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitol monostearate and polyoxyethylene sorbitan palmitate.
The second photoinitiator may include one or more of Irgacure 127, irgacure 1173, irgacure 2959, benzophenone, irgacure 2022, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide TP 0.
The second solvent may be one or more of water, methanol, ethanol.
The lubricating layer mainly plays a lubricating role because of hydrophilicity, and is generally used as a surface layer to cover the bonding layer, and the second cross-linking agent is the same as the first cross-linking agent, so that stable cross-linking can be performed between the lubricating layer and the bonding layer under the irradiation of ultraviolet light, and the firmness of the hydrophilic coating is ensured.
In summary, the hydrophilic coating provided by the embodiment of the invention comprises the bonding layer and the lubricating layer, wherein the bonding layer is adhered to the surface of an object to be lubricated through polymerization of the prepolymer, so that the bonding firmness between the hydrophilic coating and the object to be lubricated is improved, the second cross-linking agent of the lubricating layer is the same as the first cross-linking agent, so that the second cross-linking agent can be stably cross-linked with the bonding layer, the bonding firmness between the lubricating layer and the bonding layer is ensured, and the hydrophilic compound is present, so that the lubricating layer has hydrophilicity, and the hydrophilic coating can have a good lubricating effect when the object to be lubricated with the hydrophilic coating is used in a working environment.
The invention also provides a preparation method of the solution of the hydrophilic coating, which mainly comprises the steps as shown in figure 1:
it should be noted that the materials of the hydrophilic coating involved in the following steps are all the materials described above, and will not be described in detail herein.
Step 110, adding the prepolymer into a first solvent for ultrasonic dispersion under the light-shielding condition, adding a first cross-linking agent, and stirring at room temperature for a first period of time to obtain a first mixed solution;
in particular, the time of the ultrasonic dispersion may be 10min to 90min, preferably 30min, and the first time period may be 1 hour to 3 hours, preferably 2 hours. Stirring may be accomplished by mechanical stirring or magnetic stirring.
Step 120, under the condition of avoiding light, dissolving a first photoinitiator in a first solvent, adding the first photoinitiator into the first mixed solution, and stirring the mixture at room temperature for a second period of time to obtain a bonding layer solution;
In particular, the second time period may be from 0.5 hours to 2 hours, preferably 1 hour. The first photoinitiator is dissolved in the first solvent independently and then mixed with the first mixed solution, so that the dissolution time of the first photoinitiator can be reduced, and the configuration time of the solution of the whole hydrophilic coating is saved. The binding layer solution needs to be preserved in the dark. When the hydrophilic coating is required to be coated, the bonding layer solution is firstly used as base solution to be coated on the surface of the object to be lubricated, and the prepolymer is polymerized to be adhered to the surface of the object to be lubricated, so that the firmness of the hydrophilic coating is improved.
130, Adding a hydrophilic compound into a second solvent under the light-shielding condition, stirring for a third time period at room temperature, adding a second crosslinking agent which is the same as the first crosslinking agent, uniformly mixing, and adding a stabilizer, uniformly mixing to obtain a second mixed solution;
In particular, the third period of time may be from 1 hour to 5 hours, preferably 3 hours.
And 140, dissolving a second photoinitiator in a second solvent under the light-shielding condition, adding the second photoinitiator into the second mixed solution, and stirring at room temperature for a fourth period of time to obtain a lubricating layer solution, thereby obtaining a hydrophilic coating solution comprising a bonding layer solution and the lubricating layer solution.
Specifically, the fourth time period may be 0.5 hours to 2 hours, preferably 1 hour. The lubricating layer solution needs to be preserved in the dark. When the hydrophilic coating is required to be coated, the lubricating layer solution is used as the surface liquid to be coated on the surface of the bonding layer, and the second cross-linking agent is cross-linked with the first cross-linking agent, so that the firmness of the hydrophilic coating is further improved. The coating time is shortened. The hydrophilic compound makes the hydrophilic coating hydrophilic, and has good lubricating effect when contacting with hydrophilic substances.
According to the preparation method of the solution of the hydrophilic coating, provided by the embodiment of the invention, the solution of the hydrophilic coating is obtained by respectively preparing the solution of the bonding layer and the solution of the lubricating layer, when the solution is required to be used, the solution of the bonding layer is firstly used as a base solution to be coated on the surface of an object to be lubricated, and the prepolymer is polymerized to be adhered with the surface of the object to be lubricated, so that the firmness of the hydrophilic coating is improved. The lubricating layer solution is used as surface liquid to be coated on the surface of the bonding layer, and the second cross-linking agent is cross-linked with the first cross-linking agent, so that the firmness of the hydrophilic coating is further improved. The hydrophilic compound makes the hydrophilic coating hydrophilic, and has good lubricating effect when contacting with hydrophilic substances. The preparation method can be realized only under the condition of light shielding at room temperature, is simple and quick to operate, greatly shortens the coating time and improves the coating efficiency.
The hydrophilic coating provided by the embodiment of the invention can be applied to substances to be lubricated prepared from Polyurethane (PU), thermoplastic Polyurethane (TPU), polyether amide (Pebax), nylon (PA), polyvinyl chloride (PVC) and silica gel materials. The method can also be applied to the surface of irregular catheters such as balloon catheters, the surface of guide wires and the surface of catheters with inner diameters of 0.012-0.096 inches.
The method of using the hydrophilic coating will be described below using the catheter as an example of the object to be lubricated.
Firstly, the distal end of the catheter is sealed by adopting a mode of plugging a silica gel plug or sealing a heat shrinkage tube.
And immersing the catheter in the solution of the bonding layer for 2-20 s at the speed of 10-30 mm/s, then lifting the catheter at the speed of 5-15 mm/s, and irradiating the catheter with ultraviolet light for 20-150 s after the catheter is completely lifted, so that the prepolymer is crosslinked under the action of the ultraviolet light and is bonded on the surface of the catheter, thus obtaining the catheter bonded with the bonding layer.
Then, immersing the catheter with the bonding layer in the lubricating layer solution at a speed of 10mm/s-30mm/s for 2s-20s, then carrying out lifting at a speed of 5mm/s-15mm/s, and carrying out ultraviolet irradiation for 50s-300s after the catheter is completely lifted, so as to obtain the catheter coated with the hydrophilic coating.
In order to better understand the technical scheme provided by the invention, the following specific processes for preparing the hydrophilic coating by applying the method provided by the embodiment of the invention and the properties of the prepared hydrophilic coating are respectively described in a plurality of specific examples.
Example 1
In the first step, 25g of polyurethane acrylate was added to 300mL of ethanol under a dark condition, and subjected to ultrasonic dispersion for 30min, and then 5g of polyethylene glycol diacrylate (molecular weight: 308) was slowly added thereto, followed by magnetically stirring for 2 hours, to obtain a first mixed solution.
And secondly, 1g of Irgacure 2959 is dissolved in 60mL of ethanol under the light-shielding condition, and is added into the first mixed solution, magnetically stirred for 1 hour, and the binding layer solution is obtained and then stored in a light-shielding condition. The tie layer solution included 7.94% urethane acrylate, 1.59% polyethylene glycol diacrylate, 0.32% Irgacure 2959, and 90.16% ethanol.
Thirdly, under the condition of avoiding light, 300mL of ethanol is magnetically stirred at normal temperature, then 15g of polyvinylpyrrolidone (with molecular weight of 360000) is slowly added into the mixture, the mixture is stirred for 3 hours at normal temperature, then 7g of polyethylene glycol diacrylate is added into the mixture, the stirring is continued for 0.5 hour, and then 0.5g of polyoxyethylene sorbitan monooleate is dissolved into the mixture, so as to obtain a second mixed solution.
And fourthly, dissolving 0.4g of Irgacure 2959 in 60mL of ethanol under the light-proof condition, adding the solution into the second mixed solution, magnetically stirring the solution for 1 hour, and preserving the solution in the light-proof condition after obtaining the lubricating layer solution. The lubricating layer solution included 4.89% polyvinylpyrrolidone, 2.28% polyethylene glycol diacrylate, 0.18% polyoxyethylene sorbitan monooleate, 0.13% Irgacure 2959, and 92.54% ethanol.
Thereafter, a catheter having an inner diameter of 0.072 inch and a surface containing TPU and Pebax was coated with the solution of the hydrophilic coating prepared as described above, and a friction coefficient test was performed.
First, the distal end of the catheter was closed with a silicone plug and the outer surface thereof was wiped with ethanol.
And immersing the catheter in the solution of the bonding layer for 5s at 15mm/s, then lifting the catheter at a speed of 10mm/s, and irradiating ultraviolet light for 50s after the catheter is completely lifted, so that polyurethane acrylic ester is crosslinked under the action of ultraviolet light and is bonded on the surface of the catheter, thereby obtaining the catheter bonded with the bonding layer.
Then, the catheter bonded with the bonding layer was immersed in the lubricating layer solution at a speed of 15mm/s for 5 seconds, then pulled at a speed of 10mm/s, and after the catheter was completely pulled, irradiated with ultraviolet light for 60 seconds, to obtain a catheter coated with a hydrophilic coating.
Finally, the catheter coated with the hydrophilic coating was immersed in water for 30s using a full-automatic friction tester with a clamping force of 300g and a speed of 10mm/s, and tested 40 times.
Example 2
In the first step, 25g of polyurethane acrylate is added into 300mL of ethanol under the condition of avoiding light, ultrasonic dispersion is carried out for 30min, then 4g of polyethylene glycol diacrylate (with the molecular weight of 700) is slowly added into the mixture, and magnetic stirring is carried out for 2 hours, thus obtaining a first mixed solution.
In the second step, 0.8g of Irgacure 2959 is dissolved in 60mL of ethanol under the light-proof condition, and added into the first mixed solution, magnetically stirred for 1 hour, and the binding layer solution is obtained and stored in a light-proof condition. The tie layer solution included 7.97% urethane acrylate, 1.28% polyethylene glycol diacrylate, 0.25% Irgacure 2959, and 90.5% ethanol.
Thirdly, under the condition of avoiding light, 300mL of ethanol is magnetically stirred at normal temperature, then 15g of polyvinylpyrrolidone (with molecular weight of 360000) is slowly added into the mixture, the mixture is stirred for 3 hours at normal temperature, then 5g of polyethylene glycol diacrylate is added into the mixture, and the mixture is continuously stirred for 0.5 hour, so as to obtain a second mixed solution.
And fourthly, dissolving 0.3g of Irgacure 2959 in 60mL of ethanol under the light-proof condition, adding the solution into the second mixed solution, magnetically stirring the solution for 1 hour, and preserving the solution in the light-proof condition after obtaining the lubricating layer solution. The lubricating layer solution included 4.93% polyvinylpyrrolidone, 1.64% polyethylene glycol diacrylate, 0.1% Irgacure 2959, and 93.33% ethanol.
The test procedure was as in example 1.
Example 3
In the first step, 15.17g of polyester acrylate was added to 300mL of methanol under a dark condition, and the mixture was ultrasonically dispersed for 10 minutes, and then 1.52g of diethylenetriamine (molecular weight 103) was slowly added thereto, and magnetically stirred for 1 hour, to obtain a first mixed solution.
In the second step, 1.52g of Irgacure 127 was dissolved in 60mL of methanol under a dark condition, and added to the first mixed solution, magnetically stirred for 0.5 hour, to obtain a solution of the binding layer, and then stored under a dark condition. The tie layer solution included 5% polyester acrylate, 0.5% diethylenetriamine, 0.5% Irgacure 127, and 94% methanol.
Thirdly, 300mL of ethanol is magnetically stirred under the condition of light shielding at normal temperature, then 5.92g of hyaluronic acid (with molecular weight of 1000000) is slowly added into the mixture, the mixture is stirred for 1 hour at normal temperature, then 2.96g of diethylenetriamine is added into the mixture, the stirring is continued for 0.5 hour, and then 0.59g of polyoxyethylene sorbitol monostearate is dissolved into the mixture, so as to obtain a second mixed solution.
Fourth, 2.37g of Irgacure 2022 was dissolved in 60mL of ethanol under a dark condition, and added to the second mixed solution, magnetically stirred for 0.5 hour, to obtain a lubricating layer solution, and then stored under a dark condition. The lubricating layer solution included 2% hyaluronic acid, 1% diethylenetriamine, 0.2% polyethylene oxide sorbitol mono-stearate, 0.8% Irgacure 2022 and 96% ethanol.
Example 4
In the first step, 50.82g of epoxy acrylate was added to 300mL of water under a dark condition, and subjected to ultrasonic dispersion for 90min, and then 9.32g of polyethylene glycol diacrylate (molecular weight: 2000) was slowly added thereto, followed by magnetic stirring for 3 hours, to obtain a first mixed solution.
In the second step, 3.39g of Irgacure 1173 is dissolved in 60mL of water under the condition of avoiding light, and added into the first mixed solution, magnetically stirred for 2 hours, and then the binding layer solution is obtained and stored in a dark place. The bond coat solution included 12% epoxy acrylate, 2.2% polyethylene glycol diacrylate, 0.8% Irgacure 1173, and 85% water.
Thirdly, 300mL of water is magnetically stirred at normal temperature under the condition of avoiding light, then 28.64g of polyacrylamide (with the molecular weight of 6000000) is slowly added into the water, the water is stirred for 5 hours at normal temperature, then 18.41g of polyethylene glycol diacrylate is added into the water, and the stirring is continued for 0.5 hour, thus obtaining a second mixed solution.
And fourthly, under the light-proof condition, 2.05g of Irgacure 2959 is dissolved in 60mL of water, and is added into the second mixed solution, magnetically stirred for 2 hours, and the lubricating layer solution is obtained and then stored in a light-proof condition. The lubricating layer solution comprises 7% of polyacrylamide, 4.5% of polyethylene glycol diacrylate, 0.5% of Irgacure 2959 and 88% of water.
Example 5
In the first step, 22.02g of polyether acrylate was added to 300mL of ethanol under a dark condition, and the mixture was subjected to ultrasonic dispersion for 60 minutes, and then 7.86g of ethylene glycol dimethacrylate (molecular weight: 198) was slowly added thereto, followed by magnetically stirring for 2.5 hours, to obtain a first mixed solution.
And secondly, dissolving 0.63g of TPO in 60mL of ethanol under the light-shielding condition, adding the TPO into the first mixed solution, magnetically stirring the TPO for 0.8 hour to obtain a bonding layer solution, and preserving the bonding layer solution in the light-shielding condition. The tie layer solution included 7% polyether acrylate, 2.5% ethylene glycol dimethacrylate, 0.2% TPO and 90.3% ethanol.
Thirdly, 300mL of ethanol is magnetically stirred at normal temperature under the condition of avoiding light, then 12.56g of polyacrylate (with molecular weight of 500000) is slowly added into the mixture, the mixture is stirred for 4 hours at normal temperature, then 1.49g of ethylene glycol dimethacrylate is added into the mixture, the stirring is continued for 0.5 hour, and then 0.75g of polyoxyethylene sorbitan palmitate is dissolved into the mixture, so as to obtain a second mixed solution.
Fourthly, 0.15g of TPO is dissolved in 60mL of ethanol under the light-proof condition, and is added into the second mixed solution, magnetically stirred for 0.8 hour, and the lubricating layer solution is obtained and stored in a light-proof condition. The lubricating layer solution included 4.2% polyacrylate, 0.5% ethylene glycol dimethacrylate, 0.25% polyoxyethylene sorbitan palmitate, 0.05% TPO and 95% ethanol.
Example 6
In the first step, 28.31g of aqueous acrylic ester was added to 300mL of methanol under a dark condition, and the mixture was subjected to ultrasonic dispersion for 40 minutes, and then 0.94g of polyethylene glycol diacrylate (molecular weight: 308) was slowly added thereto, followed by magnetically stirring for 2 hours, to obtain a first mixed solution.
And secondly, dissolving 0.16g of benzophenone in 60mL of methanol under the light-shielding condition, adding the solution into the first mixed solution, magnetically stirring the solution for 1 hour, and storing the solution in the light-shielding condition after obtaining a bonding layer solution. The bonding layer solution comprises 9% of aqueous acrylic ester, 0.3% of polyethylene glycol diacrylate, 0.05% of benzophenone and 90.65% of methanol.
Thirdly, under the condition of avoiding light, 300mL of water is magnetically stirred at normal temperature, then 24g of polyvinyl alcohol (with molecular weight of 200000) is slowly added into the water, stirring is carried out at normal temperature for 3 hours, then 14.8g of polyethylene glycol diacrylate is added into the water, stirring is continued for 0.5 hour, and then 0.4g of polyethylene oxide sorbitol monocardant is dissolved into the water, so as to obtain a second mixed solution.
And fourthly, dissolving 0.8g of benzophenone in 60mL of water under the light-shielding condition, adding the solution into the second mixed solution, magnetically stirring the solution for 1 hour, and preserving the solution in the light-shielding condition after obtaining the lubricating layer solution. The lubricating layer solution comprises 6% of polyvinyl alcohol, 3.7% of polyethylene glycol diacrylate, 0.1% of polyethylene oxide sorbitol mono-hard acid ester, 0.2% of diphenyl ketone and 90% of water.
Comparative example 1
The test was performed using a fully automatic friction tester, and a catheter with an inner diameter of 0.072 inch and a surface containing TPU and Pebax, which was not coated with a hydrophilic coating, was immersed in water for 30 seconds, and the catheter was tested using a clamping force of 300g and a speed of 10 mm/s.
As shown in fig. 2 and 3, the maximum friction coefficient of the catheters in the examples 1 and 2 of the present invention is not more than 0.04, the calculated maximum friction force is not more than 12g, and after 40 times of testing, the friction coefficient value is stable, and the hydrophilic coating is not raised, which means that the hydrophilic coating is not fallen off after 40 times of friction, and the firmness is very good.
As shown in fig. 4, the catheter of comparative example 1 has not been subjected to 40 tests, and its maximum friction coefficient has been greater than 1.3, indicating poor surface lubricity.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (10)

1. A hydrophilic coating, wherein the hydrophilic coating comprises a bonding layer and a lubricating layer;
The composition of the bonding layer comprises 5% -12% of prepolymer, 0.3% -2.5% of first cross-linking agent, 0.05% -0.8% of first photoinitiator and 85% -94% of first solvent;
The lubricating layer is covered on the bonding layer, and the lubricating layer comprises 2% -7% of hydrophilic compound, 1% -5% of second cross-linking agent, 0% -0.3% of stabilizing agent, 0.05% -0.8% of second photoinitiator and 88% -96% of second solvent, wherein the first cross-linking agent and the second cross-linking agent are the same.
2. The hydrophilic coating of claim 1 wherein the prepolymer has a molecular weight of 1000 to 50000 and comprises one or more of polyester acrylates, unsaturated polyesters, polyurethane acrylates, epoxy acrylates, polyether acrylates, polythiol systems, and aqueous acrylates.
3. The hydrophilic coating of claim 1 wherein the first cross-linking agent has a molecular weight of 100-2000 and comprises one or more of polyethylene glycol diacrylate, diethylenetriamine, and ethylene glycol dimethacrylate, and wherein the second cross-linking agent has a molecular weight of 100-2000 and comprises one or more of polyethylene glycol diacrylate, diethylenetriamine, and ethylene glycol dimethacrylate.
4. The hydrophilic coating of claim 1 wherein the first photoinitiator comprises one or more of Irgacure 127, irgacure 1173, irgacure 2959, benzophenone, irgacure 2022, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide TP0 and the second photoinitiator comprises one or more of Irgacure 127, irgacure 1173, irgacure 2959, benzophenone, irgacure 2022, (2, 4, 6-trimethylbenzoyl) diphenylphosphine oxide TP 0.
5. The hydrophilic coating according to claim 1, wherein the hydrophilic compound has a molecular weight of not less than 200000 and comprises one or more of hyaluronic acid, polyvinylpyrrolidone, polyacrylamide, polyvinyl alcohol, and polyacrylate.
6. The hydrophilic coating of claim 1 wherein the stabilizer has a molecular weight of 600 to 2000 and comprises one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitol monostearate, and polyoxyethylene sorbitan palmitate.
7. The hydrophilic coating of claim 1 wherein the first solvent is one or more of water, methanol, and ethanol and the second solvent is one or more of water, methanol, and ethanol.
8. A method for preparing a solution of a hydrophilic coating according to any one of claims 1 to 7, characterized in that the method comprises:
under the condition of avoiding light, adding the prepolymer into a first solvent for ultrasonic dispersion, then adding a first cross-linking agent, and stirring at room temperature for a first period of time to obtain a first mixed solution;
Under the condition of avoiding light, dissolving a first photoinitiator in the first solvent, adding the first photoinitiator into the first mixed solution, and stirring at room temperature for a second period of time to obtain a bonding layer solution;
Adding a hydrophilic compound into a second solvent under the condition of avoiding light, stirring for a third time period at room temperature, adding a second crosslinking agent which is the same as the first crosslinking agent, uniformly mixing, and adding a stabilizer, uniformly mixing to obtain a second mixed solution;
And under the condition of avoiding light, dissolving a second photoinitiator in the second solvent, adding the second photoinitiator into the second mixed solution, and stirring at room temperature for a fourth period of time to obtain a lubricating layer solution, thereby obtaining a hydrophilic coating solution comprising a bonding layer solution and the lubricating layer solution.
9. The method of claim 8, wherein the ultrasonic dispersion is performed for a period of 10min to 90min, the first period of time is 1 hour to 3 hours, the second period of time is 0.5 hour to 2 hours, the third period of time is 1 hour to 5 hours, and the fourth period of time is 0.5 hour to 2 hours.
10. Use of a hydrophilic coating according to any one of claims 1-7, wherein the hydrophilic coating is applicable in articles to be lubricated prepared with polyurethane PU, thermoplastic polyurethane TPU, polyether amide Pebax, nylon PA, polyvinyl chloride PVC and silicone materials, as well as on irregular catheters, on guide wires, on catheters with an inner diameter of 0.012 inches-0.096 inches.
CN202510012083.4A 2025-01-06 2025-01-06 A hydrophilic coating and its preparation method and application Pending CN119405912A (en)

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