阅读说明：本技术 一种抗菌润滑涂层及其制备方法和应用 (Antibacterial lubricating coating and preparation method and application thereof ) 是由 杜学敏 刘美金 王芳 于 2021-07-08 设计创作，主要内容包括：本申请提供了一种抗菌润滑涂层,该抗菌润滑涂层包括铁电材料基层和设置在铁电材料基层一侧表面的润滑层,铁电材料基层包括铁电材料。该抗菌润滑涂层不仅可以降低医疗器械表面的摩擦系数提高润滑性能,并且具有良好的抗菌效果和生物相容性,将其应用在医疗器械中可以使医疗器械具有持久的润滑效果和稳定的抗菌性能。本申请还提供了该抗菌润滑涂层的制备方法和一种医疗器械。(The application provides an antibacterial lubricating coating which comprises a ferroelectric material base layer and a lubricating layer arranged on one side surface of the ferroelectric material base layer, wherein the ferroelectric material base layer comprises a ferroelectric material. The antibacterial lubricating coating not only can reduce the friction coefficient of the surface of the medical instrument and improve the lubricating property, but also has good antibacterial effect and biocompatibility, and when the antibacterial lubricating coating is applied to the medical instrument, the medical instrument can have a durable lubricating effect and stable antibacterial property. The application also provides a preparation method of the antibacterial lubricating coating and a medical appliance.)

1. An antibacterial lubricating coating, characterized in that the antibacterial lubricating coating comprises a ferroelectric material base layer and a lubricating layer arranged on one side surface of the ferroelectric material base layer, wherein the ferroelectric material base layer comprises a ferroelectric material.

2. The antimicrobial lubricating coating of claim 1, wherein the ferroelectric material comprises one or more of a ferroelectric polymer and an inorganic ferroelectric material.

3. The antimicrobial lubricating coating of claim 2, wherein the ferroelectric polymer comprises one or more of polyvinylidene fluoride and copolymers thereof, polytetrafluoroethylene, odd numbered carbon nylon, polyacrylonitrile, polyimide, polyvinylidenedicyanide, polyurea, polyphenylcyanoether, polyvinyl chloride, polyvinyl acetate, or polypropylene.

4. The antimicrobial lubricating coating of claim 2, wherein the inorganic ferroelectric material comprises one or more of a bismuth layered perovskite structured ferroelectric, a tungsten bronze type ferroelectric, and a perovskite type organometallic halide ferroelectric.

5. The antimicrobial lubricating coating of any one of claims 1-4, wherein the ferroelectric-material base layer further comprises a photo-thermal material; the mass ratio of the ferroelectric material to the photothermal material is greater than or equal to 2.33.

6. The antimicrobial lubricating coating of any one of claims 1-5, wherein the ferroelectric base layer has a thickness of 100nm to 1 mm.

7. The antimicrobial lubricious coating of any one of claims 1 to 6 wherein the lubricious coating comprises one or more of vegetable oil, glycol, perfluoropolyether, mineral oil, glycerol, paraffin, polyurethane, acrylic polyurethane, fluoro oil, vegetable seed oil, n-decanol, motor oil, kerosene, oleic acid, methyl oleate, ethyl oleate, ferrofluid, thermotropic liquid crystals, ionic liquids, iodoacetic acid, mannitol, eicosapentaenoic acid, algin, alginic acid, mucopolysaccharide, hyaluronic acid, collagen, elastin, allantoin, glucuronic acid, glycolic acid, collagen, mushroom fluid, emodin, and silicone oil.

8. The antimicrobial lubricating coating of any one of claims 1-7, wherein the lubricating layer has a static contact angle to water of from 50 ° to 110 °; the dynamic contact angle of the lubricating layer to water is 0-10 degrees.

9. A method for preparing an antibacterial lubricating coating is characterized by comprising the following steps:

providing a matrix, mixing a ferroelectric material with a solvent to obtain a mixed solution, and coating the mixed solution on the surface of the matrix to obtain the matrix with the ferroelectric material base layer;

carrying out polarization treatment on the matrix with the ferroelectric material base layer;

and infiltrating a lubricant on the surface of the ferroelectric material base layer to form a lubricating layer, thus obtaining the antibacterial lubricating coating.

10. A medical device comprising a medical device body and the antimicrobial lubricious coating of any of claims 1-9 disposed on a surface of the medical device body.

Technical Field

The application relates to the field of antibacterial lubricating coatings, in particular to an antibacterial lubricating coating and a preparation method and application thereof.

Background

When the medical appliance is implanted into a human body, on one hand, the medical appliance can rub with human tissues to cause pain and increase the risk of damage of a blood vessel wall, and on the other hand, bacteria are easily adhered to the surface of the medical appliance and proliferate to form a biological membrane, so that wound infection of a patient is caused, and the treatment difficulty is increased. Therefore, there is a need for improvement of the existing medical devices to improve the antibacterial property and the lubricating property of the medical devices so that the medical devices can have a durable lubricating effect and a stable antibacterial property.

Disclosure of Invention

In order to solve the problems, the application provides an antibacterial lubricating coating which not only can reduce the friction coefficient of the surface of a medical instrument and improve the lubricating property, but also has good antibacterial effect and biocompatibility, and can enable the medical instrument to have a lasting lubricating effect and stable antibacterial property when being applied to the medical instrument.

Specifically, the present application provides, in a first aspect, an antibacterial lubricating coating including a ferroelectric material base layer including a ferroelectric material and a lubricating layer provided on a surface of the ferroelectric material base layer.

In the application, the ferroelectric material base layer can generate electric charges on the surface of the antibacterial lubricating coating after being polarized, so that bacteria are inhibited from being adhered to the surface of the coating, and the ferroelectric material base layer can also generate transient electric charges under the stimulation of light or heat, so that active oxygen is generated to kill the bacteria on the surface of the coating; the lubricating layer has low interfacial tension, can reduce the adhesion of cells and bacteria, thereby inhibiting the growth of the bacteria, and can also improve the biocompatibility of the coating and reduce the stimulation of medical appliances to human bodies.

Optionally, the ferroelectric material comprises one or more of a ferroelectric polymer and an inorganic ferroelectric material.

Optionally, the ferroelectric polymer includes one or more of polyvinylidene fluoride and its copolymer, polytetrafluoroethylene, nylon with odd number of carbon atoms, polyacrylonitrile, polyimide, polyvinylidene cyanide, polyurea, polyphenylcyano ether, polyvinyl chloride, polyvinyl acetate, or polypropylene.

Optionally, the polyvinylidene fluoride copolymer comprises polyvinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride-tetrafluoroethylene copolymer, polyvinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene copolymer and polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene copolymer.

Optionally, the inorganic ferroelectric material includes one or more of a bismuth layered perovskite structure ferroelectric, a tungsten bronze type ferroelectric, and a perovskite type organic metal halide ferroelectric.

Optionally, the inorganic ferroelectric material includes one or more of lead titanate, barium titanate, potassium niobate, lithium tantalate, bismuth titanate, bismuth ferrite, potassium dihydrogen phosphate, ammonium triglycolate sulfate, and rhodinate.

Optionally, the ferroelectric material base layer further comprises a photo-thermal material.

Optionally, the photo-thermal material includes one or more of gold nano-material, palladium nano-material, carbon nano-tube, graphene, carbon black, black phosphorus, copper sulfide, indocyanine green, polyaniline and strontium ruthenate.

Optionally, the gold nanomaterial comprises one or more of a gold nanorod, a gold nanoshell, a gold nanocage and a hollow gold nanosphere, and the palladium nanomaterial comprises one or more of a palladium nanosheet, palladium @ silver and palladium @ silicon dioxide.

Optionally, a mass ratio of the ferroelectric material to the photo-thermal material is greater than or equal to 2.33.

Optionally, the thickness of the ferroelectric material base layer is 100nm-1 mm.

Optionally, the lubricating layer comprises one or more of vegetable oil, glycol, perfluoropolyether, mineral oil, glycerol, paraffin, polyurethane, acrylic polyurethane, fluoro oil, vegetable seed oil, n-decanol, motor lubricating oil, kerosene, oleic acid, methyl oleate, ethyl oleate, ferrofluid, thermotropic liquid crystal, ionic liquid, iodoacetic acid, mannitol, eicosapentaenoic acid, algin, alginic acid, mucopolysaccharide, hyaluronic acid, collagen, elastin, allantoin, glucuronic acid, glycolic acid, collagen, mushroom fluid, emodin, and silicone oil.

Optionally, the lubricating layer has a thickness of 1nm to 100 μm.

Optionally, the lubricating layer has a static contact angle to water of 50 ° to 110 °.

Optionally, the dynamic contact angle of the lubricating layer to water is 0 ° to 10 °.

Optionally, the thickness of the antibacterial lubricating coating is 101nm-1100 μm.

In a second aspect, the present application provides a method for preparing an antibacterial lubricating coating, comprising:

providing a matrix, mixing a ferroelectric material with a solvent to obtain a mixed solution, and coating the mixed solution on the surface of the matrix to obtain the matrix with the ferroelectric material base layer;

carrying out polarization treatment on the matrix with the ferroelectric material base layer;

and infiltrating a lubricant on the surface of the ferroelectric material base layer to form a lubricating layer, thus obtaining the antibacterial lubricating coating.

Optionally, the coating includes any one of spray coating, dip coating, drop coating, spin coating, or printing.

Optionally, the solvent comprises one or more of dimethyl sulfoxide, N-dimethylformamide acetone, trimethyl phosphate, N-dimethylformamide, N-dimethylacetamide, propylene glycol, N-methylpyrrolidone, tetrahydrofuran, tetramethylurea, hexamethylphosphoric acid amide, and hexafluoroisopropanol.

Optionally, the mass concentration of the ferroelectric material in the mixed solution is 1-50%.

Optionally, the polarization treatment comprises one or more of applied force, electricity, magnetism or irradiation.

In a third aspect, the present application provides a medical device comprising a medical device body and an antimicrobial lubricious coating disposed on a surface of the medical device body.

Optionally, the medical device comprises one or more of an instrument, device, utensil or material that is applied directly to the body.

Optionally, some or all of the components of the medical device are disposed within the subject or enter the subject during use. The medical apparatus includes a medical apparatus for detection and a medical apparatus for treatment.

Optionally, the medical device comprises any one of a contact lens, an implantable catheter, a stent, an artificial joint, an orthopedic staple, a urinary catheter, an intravaginal or digestive tract device (stomach tube, sigmoidoscope, colonoscope, gastroscope), an endotracheal tube, a bronchoscope, a denture, an orthodontic appliance, an intrauterine device, a burn tissue dressing, an oral dressing, a therapeutic device, a laparoscope, an arthroscope, a dental filling material, an artificial muscle bond, an artificial larynx and a subperiosteal implant.

Optionally, the medical device is made of gold, silver, platinum, palladium, aluminum, copper, steel, tantalum, magnesium, nickel, chromium, iron, nickel-titanium alloy, cobalt-chromium alloy, high nitrogen nickel-free stainless steel, cobalt-chromium-molybdenum alloy, gallium arsenide, titanium, hydroxyapatite, tricalcium phosphate, polylactic acid, carbon fiber, polyglycolic acid, polylactic acid-glycolic acid copolymer, poly epsilon- (caprolactone), polyanhydride, polyorthoester, polyvinyl alcohol, polyethylene glycol, polyurethane, polyacrylic acid, poly-N-isopropylacrylamide, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide), polytetrafluoroethylene, polycarbonate, polyurethane, nitrocellulose, polystyrene, polyethylene terephthalate, polydimethylsiloxane, polyacrylonitrile-butadiene-styrene, polyetheretherketone, silicon oxide, polyethylene glycol, polyacrylonitrile-butadiene-styrene, polyetheretherketone, silicon oxide, or mixtures thereof, At least one material of titanium oxide, aluminum oxide, zirconium oxide, niobium oxide, organic silicon, silicon rubber and glass.

Optionally, the method for sterilizing the medical device comprises applying one or more of an external force or a thermal stimulus to the medical device; the external force comprises one or more of pressure, tension, deflection force and ultrasonic wave; the thermal stimulus comprises one or more of heat and light.

The medical instrument that this application third aspect provided has good structural stability and biocompatibility, and the antibiotic lubricated coating on its surface has improved medical instrument's lubricating property, reduces the damage to human tissue when medical instrument implants to greatly reduced medical instrument use in-process wound infection's risk, higher security has.

Drawings

FIG. 1 is a schematic structural view of an antimicrobial lubricating coating provided in accordance with an embodiment of the present application;

fig. 2 is a scanning electron microscope image of the ferroelectric material base layer provided in example 1 of the present application.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

During the use of the medical device, bacteria easily invade from the entrance of the device and are adsorbed on the outer wall of the medical device by van der waals force to cause infection, so the antibacterial property of the medical device is of great significance, but the existing medical device has low antibacterial capability. In addition, the surface lubricating property of the existing medical apparatus is poor, and the human tissue is easy to damage. In order to obtain the medical instrument with good antibacterial performance and lubricating performance, the application provides the antibacterial lubricating coating which has strong antibacterial performance and good lubricating performance and biocompatibility, and the safety of the medical instrument can be greatly improved by applying the antibacterial lubricating coating to the surface of the medical instrument.

Referring to fig. 1, fig. 1 is a schematic structural diagram of an antibacterial lubricating coating according to an embodiment of the present application, wherein the antibacterial lubricating coating includes a ferroelectric material base layer 10 and a lubricating layer 20 disposed on a surface of the ferroelectric material base layer 10. In the embodiment of the application, the ferroelectric material base layer comprises a ferroelectric material, dipoles in the material after the ferroelectric material is polarized are orderly arranged, and charges are generated on the surface of the antibacterial lubricating coating, so that the adhesion of bacteria is inhibited, and the coating has a good antibacterial effect. In the embodiment of the present application, the means for polarizing the ferroelectric material substrate includes one or more of external force, electricity, magnetism, or irradiation. In the embodiments of the present application, the piezoelectric coefficient d of the ferroelectric material base layer₃₃Greater than or equal to 10 pC/N. Piezoelectric coefficient d of base layer of ferroelectric material₃₃Specifically, but not limited to, 10pC/N, 15pC/N, 20pC/N, 25pC/N, 30pC/N or 50 pC/N. In the application, the larger the piezoelectric coefficient of the ferroelectric material base layer is, the better the antibacterial performance of the antibacterial lubricating coating is, and the more stable sterilization performance is realized. In the embodiment of the present application, the piezoelectric coefficient of the ferroelectric material base layer after polarization treatment is higher than the piezoelectric coefficient without polarization treatment under the same condition.

In an embodiment of the present application, the ferroelectric material includes one or more of a ferroelectric polymer and an inorganic ferroelectric material. In the embodiment of the present application, the ferroelectric polymer includes one or more of polyvinylidene fluoride and its copolymer, polytetrafluoroethylene, nylon with odd number of carbon atoms, polyacrylonitrile, polyimide, polyvinylidene cyanide, polyurea, polyphenylcyano ether, polyvinyl chloride, polyvinyl acetate, polypropylene or ferroelectric liquid crystal. In some embodiments of the present application, the polyvinylidene fluoride and copolymers thereof include one or more of polyvinylidene fluoride-trifluoroethylene copolymer, polyvinylidene fluoride-tetrafluoroethylene copolymer, polyvinylidene fluoride-trifluoroethylene-chlorotrifluoroethylene copolymer, and polyvinylidene fluoride-trifluoroethylene-chlorofluoroethylene copolymer. In some embodiments of the present application, the ferroelectric material comprises nylon having an odd number of carbon atoms.

In an embodiment of the present application, the inorganic ferroelectric material includes one or more of a bismuth layered perovskite structure ferroelectric, a tungsten bronze type ferroelectric, and a perovskite type organic metal halide ferroelectric. In some embodiments of the present application, the inorganic ferroelectric material comprises one or more of lead titanate, barium titanate, potassium niobate, lithium tantalate, bismuth titanate, bismuth ferrite, potassium dihydrogen phosphate, ammonium triglycinate sulfate, and a salt of rosette. In the embodiment of the present application, the particle size of the inorganic ferroelectric material is 1nm to 100 μm. The particle size of the inorganic ferroelectric material may specifically be, but not limited to, 1nm, 10nm, 50nm, 100nm, 500nm, 1 μm, 10 μm or 100 μm.

In some embodiments of the present application, the ferroelectric material based layer further comprises a photo-thermal material. The photo-thermal material is added in the ferroelectric material base layer, so that the antibacterial lubricating coating can generate an electric signal under illumination, and the sterilization effect is realized. In the embodiment of the present application, the photothermal material has a photothermal conversion ratio of 1% to 90%. In an embodiment of the present application, the photo-thermal material includes one or more of gold nanomaterial, palladium nanomaterial, carbon nanotube, graphene, carbon black, black phosphorus, copper sulfide, indocyanine green, polyaniline, and strontium ruthenate. In some embodiments of the present application, the gold nanomaterials comprise one or more of gold nanorods, gold nanoshells, gold nanocages, and hollow gold nanospheres. In some embodiments of the present application, the palladium nanomaterial comprises one or more of palladium nanoplate, palladium @ silver, and palladium @ silica, wherein palladium @ silver represents a silver-coated palladium core-shell nanomaterial and palladium @ silica represents a silica-coated palladium core-shell nanomaterial. In the present application, when the ferroelectric material base layer includes the photo-thermal material, the mass ratio of the ferroelectric material to the photo-thermal material is 100:0 to 70:30 (excluding 100: 0). The mass ratio of the ferroelectric material to the photothermal material may specifically be, but not limited to, 100:1, 95:5, 90:10, 80:20, 75:25, or 70: 30. Within the mass ratio range, the photo-thermal material and the ferroelectric material can realize good cooperation, and the light can be effectively converted into electric signals, so that stable and good sterilization effect is realized.

In the embodiment of the application, the thickness of the ferroelectric material base layer is 100nm-1 mm. In some embodiments of the present application, the ferroelectric material base layer has a thickness of 100nm to 100 μm. The thickness of the ferroelectric material base layer may specifically, but not exclusively, be 100nm, 300nm, 500nm, 1 μm, 10 μm, 100 μm or 1 mm.

The research of the application finds that the lubricating layer and the ferroelectric material base layer have a good synergistic effect, so that the antibacterial lubricating coating has good antibacterial performance, specifically, the lubricating layer can reduce the adhesion of water molecules and biomolecules on the antibacterial lubricating coating, so that the breeding of bacteria on the surface of the coating is inhibited, the coating has good antibacterial performance, meanwhile, the polarized ferroelectric material can generate charges on the surface of the antibacterial lubricating coating to reduce the adhesion of the bacteria on the surface of the antibacterial lubricating coating, and in addition, the ferroelectric material can also generate transient charges under external stimulation to further generate active oxygen to kill the bacteria. And the lubricating layer can also improve the biocompatibility and the lubricating property of the antibacterial lubricating coating, so that the coating can effectively improve the safety of medical instruments.

In an embodiment of the present application, the lubricant layer includes one or more of vegetable oil, glycol, mineral oil, glycerol, perfluoropolyether, paraffin, polyurethane, acrylic polyurethane, fluoro oil, vegetable seed oil, n-decanol, motor lubricant, kerosene, oleic acid, methyl oleate, ethyl oleate, ferrofluid, thermotropic liquid crystal, ionic liquid, iodoacetic acid, mannitol, eicosapentaenoic acid, algin, alginic acid, mucopolysaccharide, hyaluronic acid, collagen, elastin, allantoin, glucuronic acid, glycolic acid, collagen, mushroom fluid, emodin, and silicone oil. The material has good affinity with the ferroelectric material base layer, and can form a stable antibacterial lubricating coating. In the embodiment of the present application, the thickness of the lubricating layer is 1nm to 100. mu.m. The thickness of the lubricating layer may specifically be, but not limited to, 1nm, 5nm, 10nm, 100nm, 500nm, 1 μm, 10 μm, 20 μm or 50 μm.

In the embodiment of the present application, the static contact angle of the antibacterial lubricating coating to water is 50 ° to 110 °, and the static contact angle of the antibacterial lubricating coating to water may specifically be, but not limited to, 50 °, 60 °, 70 °, 80 °, 90 °, 100 °, or 110 °. In the embodiment of the application, the dynamic contact angle of the antibacterial lubricating coating to water is 0-10 degrees. The dynamic contact angle of the antimicrobial lubricious coating to water may specifically be, but is not limited to, 0 °, 3 °, 5 °, 7 °, or 10 °. A higher dynamic contact angle of the antimicrobial lubricious coating to water indicates a less adherent coating to bacteria. In the embodiment of the application, the thickness of the antibacterial lubricating coating is 101nm-1100 mu m. The thickness of the antimicrobial lubricating coating may specifically, but not exclusively, be 101nm, 200nm, 300nm, 500nm, 800nm, 1000nm or 1100 nm.

The application also provides a medical instrument, and the surface of the medical instrument is provided with the antibacterial lubricating coating. In the embodiment of the application, the medical apparatus includes instruments, equipment, appliances and materials directly applied to human body, and some or all parts of the medical apparatus are arranged in the body of the subject or enter the body of the subject when being applied. In some embodiments of the present application, the medical device comprises one or more of a contact lens, an implantable catheter, a stent, an artificial joint, an orthopedic staple, a urinary catheter, an intravaginal or digestive tract device (gastric tube, sigmoidoscope, colonoscope, gastroscope), an endotracheal tube, a bronchoscope, a denture, an orthodontic appliance, an intrauterine device, a burn tissue dressing, an oral dressing, a therapeutic device, a laparoscope, an arthroscope, a dental filling material, an artificial muscle tendon, an artificial larynx, and a subperiosteal implant.

In some embodiments of the present application, the medical device is made of gold, silver, platinum, palladium, aluminum, copper, steel, tantalum, magnesium, nickel, chromium, iron, nickel-titanium alloy, cobalt-chromium alloy, high nitrogen nickel-free stainless steel, cobalt-chromium-molybdenum alloy, gallium arsenide, titanium, hydroxyapatite, tricalcium phosphate, polylactic acid, carbon fiber, polyglycolic acid, polylactic acid-glycolic acid copolymer, poly-epsilon- (caprolactone), polyanhydride, polyorthoester, polyvinyl alcohol, polyethylene glycol, polyurethane, polyacrylic acid, poly-N-isopropylacrylamide, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide), polytetrafluoroethylene, polycarbonate, polyurethane, nitrocellulose, polystyrene, polyethylene terephthalate, polydimethylsiloxane, polyacrylonitrile-butadiene-styrene, polyetheretherketone, polyethylene glycol, polyethylene, at least one material of silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, niobium oxide, organic silicon, silicon rubber and glass.

In some embodiments of the present application, a method of sterilizing a medical device includes applying one or more of an external force or a thermal stimulus to the medical device, wherein the external force includes one or more of pressure, tension, deflection, and ultrasound, and the thermal stimulus includes one or more of heat and light. In the present application, external force or thermal stimulation is applied to the medical device to generate electric charges on the surface of the medical device, thereby inhibiting adhesion of bacteria and simultaneously generating active oxygen to kill bacteria on the surface of the device. In the embodiment of the application, after external force or thermal stimulation is applied to the medical apparatus, the open-circuit voltage of the antibacterial lubricating coating is 1mV-500V, and the short-circuit current of the antibacterial lubricating coating is 1nA-100mA/cm². Under the open circuit voltage and the short circuit current, bacteria can be effectively killed.

In some embodiments of the present application, the external force applied to the medical device comprises one or more of a compressive force, a tensile force, and a flexural force, the external force value ranging from 1Pa to 1000kPa when the antimicrobial lubricious coating comprises a ferroelectric polymer; when the antibacterial lubricating coating comprises an inorganic ferroelectric material, the external force value is 1Pa-1000 MPa. In some embodiments of the present application, the external force applied to the medical device is ultrasound, the frequency of the ultrasound is 20kHz-200MHz, and the power density of the ultrasound is 1W/cm²-1kW/cm². In some embodiments of the present application, the medical device is heated to sterilize, wherein the heating temperature is 20 ℃ to 40 ℃. In some embodiments of the present application, the medical device is irradiated with light to sterilize, wherein the wavelength of the light is 100nm to 4000nm, and the power density of the light is 1mW/cm²-5000mW/cm²。

The antibacterial lubricating coating provided by the application can effectively reduce the friction between the medical instrument and human tissues, improve the biocompatibility of the medical instrument and reduce the adhesion of bacteria on the surface of the medical instrument; and the antibacterial lubricating coating can generate active oxygen under external force or thermal stimulation so as to kill bacteria on the surface of the medical appliance and realize stable sterilization performance.

The application also provides a preparation method of the antibacterial lubricating coating, which comprises the following steps:

step 100: providing a matrix, mixing a ferroelectric material with a solvent, and coating the mixed solution on the surface of the matrix to obtain the matrix with the ferroelectric material base layer;

step 200: carrying out polarization treatment on the matrix with the ferroelectric material base layer;

step 300: and infiltrating the lubricant on the surface of the ferroelectric material base layer to form a lubricating layer to obtain the antibacterial lubricating coating.

In step 100, the ferroelectric material includes one or more of a ferroelectric polymer and an inorganic ferroelectric material. In the embodiment of the present application, the solvent includes one or more of dimethyl sulfoxide, N-dimethylformamide acetone, trimethyl phosphate, N-dimethylformamide, N-dimethylacetamide, propylene glycol, N-methylpyrrolidone, tetrahydrofuran, tetramethylurea, hexamethylphosphoric acid amide, and hexafluoroisopropanol, and the use of the above solvent is advantageous for forming a uniform ferroelectric layer. In the embodiment of the present application, the mass concentration of the ferroelectric material in the mixed solution is 1% to 50%. The mass concentration of the ferroelectric material may specifically but not exclusively be 1%, 5%, 10%, 20%, 30%, 40% or 50%. In the embodiment of the present application, the application of the mixed solution to the surface of the substrate may be one or more of spraying, dipping, dropping, spin coating, or printing.

In step 200, the substrate with the base layer of ferroelectric material is subjected to a polarization treatment by one or more of applied force, electricity, magnetism, or irradiation. In some embodiments of the present application, polarization is achieved by high voltage corona.

In step 300, the lubricant is applied to the surface of the base layer of ferroelectric material by coating or dipping. In some embodiments of the present application, a lubricant layer is formed on the surface of the ferroelectric material base layer by a spraying method, and an antibacterial lubricant coating is obtained. In some embodiments of the present application, a lubricant layer is formed on the surface of the ferroelectric material base layer by using a soaking method, and an antibacterial lubricant coating is obtained. In some embodiments of the present application, when the lubricant infiltrates the surface of the ferroelectric material base layer, a part of the lubricant infiltrates the ferroelectric material base layer, so as to form an infiltrated layer structure in the ferroelectric material base layer, which is beneficial to improving the lubricating performance of the antibacterial lubricating coating, and makes the lubricating effect more durable. In some embodiments of the present application, the provided substrate is a medical device body, and the antibacterial lubricating coating is formed on the surface of the medical device body by the above preparation method, so as to obtain the medical device with good antibacterial performance.

The preparation method of the antibacterial lubricating coating is simple to operate, controllable in process and suitable for industrial production.

The following further describes embodiments of the present application in terms of a number of examples.

Example 1

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

dissolving polyvinylidene fluoride in dimethyl sulfoxide to obtain a polyvinylidene fluoride solution with the mass percent of 10%, coating 5mL of the polyvinylidene fluoride solution on the surface of the laparoscope made of zirconia by a dripping method, and drying at 80 ℃ for 12h to obtain the laparoscope with the polyvinylidene fluoride coating. Performing corona polarization on the laparoscope by adopting 26kV high voltage, wherein the polarized laparoscope has a piezoelectric coefficient d of the laparoscope with a polyvinylidene fluoride coating₃₃18pC/N and a surface potential of 60V. And soaking the polarized laparoscope with the polyvinylidene fluoride coating in silicone oil for silicone oil infusion to obtain the laparoscope with the antibacterial lubricating coating after the silicone oil infusion, namely obtaining the antibacterial lubricating coating.

Example 2

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

dissolving polyvinylidene fluoride-trifluoroethylene copolymer (PVDF-TrFE) in N, N-dimethylformamide to obtain 10% PVDF-TrFE solution, coating 5ml VDF-TrFE solution on the surface of a gastroscope made of polyether-ether-ketone by a spraying method, and drying at 80 ℃ for 12 h. Performing corona polarization on the gastroscope by adopting 26kV high voltage, and obtaining the gastroscope piezoelectric coefficient d with the PVDF-TrFE coating after polarization₃₃30pC/N and a surface potential of 60V. And soaking the polarized gastroscope with the PVDF-TrFE coating in molten paraffin for paraffin perfusion to obtain the gastroscope with the antibacterial lubricating coating after the paraffin is perfused, thus obtaining the antibacterial lubricating coating.

Example 3

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

dissolving polyimide in N, N-dimethylformamide to obtain a polyimide solution with the mass percent of 10%, coating 5mL of the polyimide solution on the surface of a gastroscope made of polyether-ether-ketone by a dip coating method, and drying at 80 ℃ for 12 h. Performing corona polarization on the gastroscope by adopting 26kV high voltage, and obtaining the gastroscope piezoelectric coefficient d with a polyimide coating after polarization₃₃Is 27 pC/N. And (3) carrying out mannitol perfusion on the gastroscope with the polyimide coating, and obtaining the gastroscope with the antibacterial lubricating coating after the mannitol perfusion, namely obtaining the antibacterial lubricating coating.

Example 4

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

dissolving polyvinyl acetate in N, N-dimethylformamide to obtain 10% polyvinyl acetate solution, coating 5mL of polyvinyl acetate solution on the surface of a gastroscope made of polylactic acid by a spin coating method, and drying at 80 ℃ for 12 h. Performing corona polarization on the gastroscope by adopting 26kV high voltage, and obtaining the gastroscope piezoelectric coefficient d with a polyvinyl acetate coating after polarization₃₃Is 26 pC/N. And (3) alginic acid perfusion is carried out on the gastroscope with the polyvinyl acetate coating, and the gastroscope with the antibacterial lubricating coating is obtained after the perfusion, namely the antibacterial lubricating coating is obtained.

Example 5

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

barium titanate particles with the particle size of 100nm are dispersed in dimethyl sulfoxide through ultrasonic dispersion, and polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) copolymer is added to obtain a mixed solution, wherein the mass percent of barium titanate in the mixed solution is 1%, and the mass percent of PVDF-TrFE in the mixed solution is 10%. 5mL of the mixed solution is coated on the surface of the artificial muscle bond made of titanium by a spin coating method, and dried for 12 hours at 80 ℃. Adopting 26kV high voltage to carry out corona polarization on the artificial muscle bond, and having the piezoelectric coefficient d of the artificial muscle bond with the ferroelectric material base layer after polarization₃₃Is 24 pC/N. Mineral oil is dripped into artificial muscle bond with ferroelectric material base layer for mineral oil irrigationAnd (5) injecting and pouring to obtain the artificial muscle bond with the antibacterial lubricating coating, namely the antibacterial lubricating coating.

Example 6

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

ultrasonically dispersing barium titanate particles with the particle size of 100nm in dimethyl sulfoxide, and adding polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) copolymer to obtain a mixed solution, wherein the mass percent of barium titanate in the mixed solution is 1%, and the mass percent of PVDF-TrFE in the mixed solution is 10%. 5mL of the mixed solution is coated on the surface of a catheter made of polyether-ether-ketone by a spraying method, and dried for 12 hours at 80 ℃. Carrying out corona polarization on the catheter by adopting 26kV high voltage, and obtaining the catheter voltage coefficient d with the ferroelectric material base layer after polarization₃₃Is 24 pC/N. And (3) carrying out vegetable oil perfusion on the catheter with the ferroelectric material base layer, and obtaining the catheter with the antibacterial lubricating coating after perfusion, namely obtaining the antibacterial lubricating coating.

Example 7

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

ultrasonically dispersing barium titanate particles with the particle size of 100nm in dimethyl sulfoxide, and adding polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) copolymer to obtain a mixed solution, wherein the mass percent of barium titanate in the mixed solution is 1%, and the mass percent of PVDF-TrFE in the mixed solution is 10%. 5mL of the mixed solution is coated on the surface of a colonoscope made of zirconia by a dripping method and dried for 12 hours at 80 ℃. Colonoscope piezoelectric coefficient d with ferroelectric material base layer after polarization by adopting 26kV high voltage to carry out corona polarization on the colonoscope₃₃Is 24 pC/N. And performing allantoin perfusion on the colonoscope with the ferroelectric material base layer, and obtaining the colonoscope with the antibacterial lubricating coating after perfusion, namely obtaining the antibacterial lubricating coating.

Example 8

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

ultrasonically dispersing lithium tantalite particles with the particle size of 100nm in dimethyl sulfoxide, and adding polyacrylonitrile to obtain a mixed solution, wherein the mass percent of lithium tantalite in the mixed solution is 1%, and the mass percent of polyacrylonitrile isThe mass percentage is 10%. 5mL of the mixed solution is coated on the surface of a colonoscope made of polylactic acid by a dripping method, and dried for 12h at 80 ℃. Colonoscope piezoelectric coefficient d with ferroelectric material base layer after polarization by adopting 26kV high voltage to carry out corona polarization on the colonoscope₃₃Is 23 pC/N. And (3) performing emodin perfusion on the colonoscope with the ferroelectric material base layer to obtain the colonoscope with the antibacterial lubricating coating after perfusion, namely obtaining the antibacterial lubricating coating.

Example 9

An antibacterial lubricating coating and a preparation method thereof, comprising the following steps:

ultrasonically dispersing monopotassium phosphate particles with the particle size of 150nm in dimethyl sulfoxide, and adding polyurea to obtain a mixed solution, wherein the mass percent of monopotassium phosphate in the mixed solution is 1%, and the mass percent of polyurea is 10%. 5mL of the mixed solution is coated on the surface of a colonoscope made of tricalcium phosphate by a dripping method, and the colonoscope is dried for 12 hours at 80 ℃. Colonoscope piezoelectric coefficient d with ferroelectric material base layer after polarization by adopting 26kV high voltage to carry out corona polarization on the colonoscope₃₃Is 25 pC/N. And (3) performing glucuronic acid perfusion on the colonoscope with the ferroelectric material base layer, and obtaining the colonoscope with the antibacterial lubricating coating after the glucuronic acid perfusion, namely obtaining the antibacterial lubricating coating.

Effects of the embodiment

In order to verify the performance of the antibacterial lubricating coating prepared by the application, the application also provides an effect embodiment.

1) The appearance of the laparoscope (before polarization treatment) with the polyvinylidene fluoride coating in example 1 is characterized by using a scanning electron microscope, please refer to fig. 2, and fig. 2 is a scanning electron microscope image of the ferroelectric material substrate provided in example 1 of the present application. It can be seen from fig. 2 that the pvdf forms a uniform ferroelectric material base layer on the surface of the laparoscope.

2) The wetting properties of the antimicrobial lubricating coatings of examples 1-9 were tested and the results are shown in Table 1.

TABLE 1 wetting Performance of the antimicrobial lubricating coatings of examples 1-9

As can be seen from Table 1, the antibacterial lubricating coating has poor wettability to water, so that the adhesion of water molecules and biomolecules to the antibacterial lubricating coating can be effectively reduced, the breeding of bacteria on the surface of the coating is inhibited, and the coating has good antibacterial performance.

3) The antimicrobial lubricating coatings of examples 1-9 were tested for antimicrobial performance as follows: coli (E.coli) was inoculated into 10mL Erlenmeyer flask containing Tryptone Soy Broth (TSB), cultured in a constant temperature shaker for 12h (37 ℃ C. with a shaking rate of 200r/min), and diluted to 1X 10 by Mach turbidimetry⁶CFU/mL of bacterial suspension. Samples of 10X 10mm size were placed in 12-well plates, and 1mL of the bacterial TSB suspension obtained above was added thereto, respectively, and cultured in an incubator at 37 ℃ for 48 hours. After incubation, the samples were removed and gently washed with 0.9% NaCl solution to the coated surface, transferred to a new 12-well plate, and then incubated for 15min with 1ml of LTSB medium and appropriate amount of SYTO 9/PI stain.

The sample is placed in 10 mL0.9% NaCl solution for ultrasonic cleaning for 10min (200W, 40kHz), bacteria adhered to the surface of the sample are promoted to be dispersed in the NaCl solution, then 100 mu L of the sample is used for observing the growth condition of the bacteria by a plate coating method, the experimental results are repeated for at least 3 times, and the bacteriostasis rate of each sample is obtained after the average value is taken.

In the application, the antibacterial performance test of each group of examples is provided with a control group, specifically, the control group 1 is an unpolarized medical apparatus with a ferroelectric material base layer and is named as sample 1; control 2 was an unpolarized medical device having a ferroelectric base layer and a lubricating layer, designated sample 2; control 3 was a polarized medical device with a ferroelectric based layer, designated sample 3; the experimental group for the antimicrobial performance test was a medical device with an antimicrobial lubricious coating, designated sample 4. Taking example 1 as an example, sample 1 of example 1 was an unpolarized laparoscope with a polyvinylidene fluoride coating, sample 2 was an unpolarized laparoscope with a polyvinylidene fluoride coating and a silicone oil lubricating layer, sample 3 was a polarized laparoscope with a polyvinylidene fluoride coating, and sample 4 was a laparoscope with an antibacterial lubricating coating. The specific test results are shown in table 2, and table 2 is the results of the bacteriostatic ratio of the antibacterial lubricating coatings and the control groups of examples 1-9.

TABLE 2 results of bacteriostasis rates of the antimicrobial lubricating coatings of examples 1-9 and their control groups

As can be seen from Table 2, the antibacterial lubricating coating has good antibacterial performance, and compared with a sample which is not polarized, the antibacterial lubricating coating has greatly improved bacteriostasis rate after being polarized. The antibacterial lubricating coating can be applied to medical instruments, so that the safety of the medical instruments can be effectively improved.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.