Special cleaning endoscope cap for gastroscope and preparation method thereof

Abstract

The invention provides a cleaning endoscope cap special for a gastroscope and a preparation method of the cleaning endoscope cap, and belongs to the technical field of endoscope caps. A modified coating is uniformly sprayed on the surface of the cleaning endoscope cap special for the gastroscope, heating pre-curing and ultraviolet lamp cross-linking curing are performed to form a coating, the cleaning endoscope cap special for the gastroscope is prepared, and the modified coating is prepared by mixing polydopamine and tannic acid modified carbon nano tube deposited silicon dioxide microspheres with sulfonated bisphenol A type polyether-ether-ketone for reaction. The water-based dispersion liquid is prepared under the action of a surfactant and a silane coupling agent. The surface of the prepared cleaning endoscope cap special for the gastroscope is coated with a modified coating, so that the prepared cleaning endoscope cap special for the gastroscope has good antistatic property, anti-pollution property, anti-fog property, hydrophilicity, antibacterial property and anti-sagging property, meanwhile, has good tolerance to a gastric acid environment, and has wide application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of endoscope caps, and in particular to a special cleaning endoscope cap for gastroscopes and a preparation method thereof. Background Art

[0002] A medical clean endoscope cap, also known as an endoscope tip cap, is a medical device used to protect the tip of an endoscope and maintain an appropriate endoscopic field of view. It is commonly used in digestive endoscopy and procedures such as EMR (endoscopic mucosal resection), ESD (endoscopic submucosal dissection), and POEM (peroral endoscopic myotomy). It is typically made of polymer materials such as thermoplastic polyurethane (TPU), sterilized with ethylene oxide, and is disposable. The product's principle is to use a dedicated medical coating to prevent the effects of blood, mist, and mucus on doctors during endoscopic (arthroscopic, laparoscopic, etc.) procedures, thereby improving surgical quality. This product must ensure an unobstructed field of view during surgery, improve surgical efficiency, shorten surgical time, and protect the endoscope lens from infection.

[0003] However, the coatings on the endoscope caps currently on the market lack good hydrophilicity, anti-fog, anti-fouling, anti-dripping, anti-static, and antibacterial properties. Furthermore, the gastroscope-specific clean endoscope caps also need to have good acid resistance to ensure they are not easily deformed in acidic conditions to ensure normal function. Summary of the Invention

[0004] The purpose of the present invention is to propose a special clean endoscope cap for gastroscope and a preparation method thereof, and a modified coating is sprayed on the surface so that the prepared special clean endoscope cap for gastroscope has good antistatic, anti-fouling, anti-fog, hydrophilic and antibacterial properties, good anti-sagging properties, and at the same time, has good tolerance to gastric acid environment, and has broad application prospects.

[0005] The technical solution of the present invention is achieved as follows:

[0006] The present invention provides a preparation method of a special clean endoscope cap for gastroscopes. The modified coating is uniformly sprayed on the surface of the special clean endoscope cap for gastroscopes, pre-cured by heating, and cross-linked and cured by ultraviolet light to form a coating, so as to prepare the special clean endoscope cap for gastroscopes. The modified coating is an aqueous dispersion prepared by a mixed reaction of carbon nanotube-deposited silica microspheres modified with polydopamine and tannic acid and sulfonated bisphenol A type polyetheretherketone under the action of a surfactant and a silane coupling agent.

[0007] As a further improvement of the present invention, the preparation method of the modified coating is as follows:

[0008] S1. Preparation of organic resin microspheres: Formaldehyde and melamine were added to water, polyvinyl alcohol and citric acid were added under heating conditions, the reaction was stirred and insulated, centrifuged, washed, and dried to obtain organic resin microspheres;

[0009] S2. Preparation of silica @ organic resin microspheres: Dissolve alkyl orthosilicate in ethanol, add organic resin microspheres, add concentrated hydrochloric acid and water, stir the reaction, centrifuge, wash, and dry to obtain silica @ organic resin microspheres;

[0010] S3. In situ deposition of carbon nanotubes: Silica@organic resin microspheres were immersed in an iron salt solution, centrifuged, and heated under inert gas to deposit carbon nanotubes. The solution was cooled to room temperature to produce antistatic silica microspheres.

[0011] S4. Preparation of modified microspheres: Antistatic silica microspheres were added to a Tris-HCl solution, tannic acid was added, the mixture was heated with stirring, centrifuged, washed, and dried. The product was added to a Tris-HCl solution, dopamine hydrochloride was added, the mixture was heated with stirring, centrifuged, washed, and dried to obtain modified microspheres.

[0012] S5. Preparation of bisphenol A polyetheretherketone: Bisphenol A monomer, 4,4'-difluorobenzophenone, carbonate, and toluene were added to dimethyl sulfoxide and stirred at room temperature to form a salt. Under an inert gas atmosphere, the reaction was heated and stirred, and the mixture was added to water, filtered, washed, dried, and pulverized to obtain bisphenol A polyetheretherketone.

[0013] S6. Preparation of sulfonated polyetheretherketone: bisphenol A polyetheretherketone was mixed with concentrated sulfuric acid, filtered, washed, and dried to obtain sulfonated bisphenol A polyetheretherketone;

[0014] S7. Preparation of modified coating: dissolve sulfonated bisphenol A type polyetheretherketone in chloroform, add modified microspheres and silane coupling agent, stir and mix evenly to obtain an organic phase; add surfactant into water to obtain an aqueous phase; mix the aqueous phase and the organic phase evenly, treat with a colloid mill, reduce pressure and heat to remove chloroform, cool to room temperature, add leveling agent and thickener, sieve to obtain a modified coating.

[0015] As a further improvement of the present invention, the mass ratio of formaldehyde, melamine, polyvinyl alcohol and citric acid in step S1 is 1-3:1-3:0.3-0.7:0.1-0.3, the temperature of the heating condition is 75-85°C, and the time of the heat preservation and stirring reaction is 10-20 minutes.

[0016] As a further improvement of the present invention, the alkyl orthosilicate in step S2 is methyl orthosilicate or ethyl orthosilicate, the mass ratio of the alkyl orthosilicate, ethanol, organic resin microspheres, concentrated hydrochloric acid and water is 8-10:100-120:5-8:7-10:3-5, and the stirring reaction time is 10-15 hours.

[0017] As a further improvement of the present invention, the iron salt content in the iron salt solution in step S3 is 1-3wt%, and the iron salt is ferric chloride, ferric sulfate or ferric nitrate. The heating conditions are to raise the temperature to 850-950°C at a rate of 10-20°C / min and keep the reaction warm for 50-70min.

[0018] As a further improvement of the present invention, the pH value of the Tris-HCl solution in step S4 is 8.5-9.5, the mass ratio of the antistatic silica microspheres, tannic acid and dopamine hydrochloride is 10:3-4:4-6, and the temperature of the heating and stirring reaction is 40-50° C. and the time is 3-5 hours.

[0019] As a further improvement of the present invention, in step S5, the molar ratio of bisphenol A monomer, 4,4'-difluorobenzophenone, and toluene is 1:1:2-4, the amount of carbonate added is 3-5 wt% of the mass of 4,4'-difluorobenzophenone, and the carbonate is sodium carbonate or potassium carbonate. The salt-forming reaction time is 1-3 hours, and the temperature of the heating and stirring reaction is 190-210° C. for 4-6 hours.

[0020] As a further improvement of the present invention, the solid-liquid ratio of bisphenol A type polyether ether ketone and concentrated sulfuric acid in step S6 is 1:10-20 g / mL, and the mixing reaction time is 12-18 hours; the thickener in step S7 is a polyacrylate thickening rheological agent HV-30, the leveling agent is N-methyl pyrrolidone, the mass ratio of the sulfonated bisphenol A type polyether ether ketone, modified microspheres, silane coupling agent, surfactant, thickener and leveling agent is 40-50:15-20:5-8:8-10:2-4:1-3, the silane coupling agent is KH560, the surfactant is at least one of N-acyl glutamate, sodium N-acyl glutamate, cocoyl arginine ethyl ester salt, and N-acyl glutamate diester salt, the colloid mill treatment time is 1-3 hours, and the mesh size of the sieving is 40-80 mesh.

[0021] As a further improvement of the present invention, the spraying amount is 2-4 mL / cm 3 The pressure of the spray gun is 25-35 MPa, the heating pre-curing condition is to keep the temperature at 110-130°C for 10-20 minutes, and the UV curing time is 10-20 minutes.

[0022] The present invention further protects a special cleaning endoscope cap for gastroscopes prepared by the above-mentioned preparation method.

[0023] The present invention has the following beneficial effects:

[0024] The present invention first prepares an organic resin microsphere, the main component of which is melamine formaldehyde resin, and the surface is fixed with a silica shell layer, and then the rough surface is loaded with Fe 3+ During the heating and calcining process, melamine formaldehyde resin is pyrolyzed into CO and NH3 gas, which has reducing properties and can convert Fe 3+ The coating is reduced to elemental Fe atoms, which then act as catalysts to catalyze the in-situ chemical vapor deposition of CO to grow carbon nanotubes, thereby producing antistatic silica microspheres. The carbon nanotubes have excellent antistatic properties, greatly improving the static dissipation of the coating surface and achieving excellent antistatic properties. Furthermore, the coating is less susceptible to staining, significantly improving its anti-pollution properties.

[0025] Tannic acid and polydopamine were distributed on the surface of the prepared antistatic silica microspheres, which greatly improved the antibacterial and adhesion properties of the modified microspheres, and further improved the adhesion between the coating and the organic material of the gastroscope-specific cleaning endoscope cap. At the same time, the coating also has good antibacterial properties.

[0026] In addition, since modified microspheres are added to the coating of the present invention to form a micro-nano structure, the sol-gel anti-fog coating formed by the combination of hydrophilic groups and modified microspheres can not only maintain hydrophilicity but also form a strong chemical bond with the organic and inorganic substrates, making the coating resistant to scrubbing, water immersion, and solvents, thereby greatly improving the anti-fog durability of the coating.

[0027] Polyetheretherketone polymers without special functional groups are non-hydrophilic. Therefore, to prepare a polymer emulsion, the polymer solid particles must be suspended in water. By using a surfactant, the surface tension is reduced so that the polyetheretherketone polymer can be evenly dispersed in the emulsion to form a coating.

[0028] The present invention prepares a bisphenol A polyetheretherketone (PEEK) polymer, which is then reacted with concentrated sulfuric acid for sulfonation, attaching sulfonate groups to aromatic rings in the PEEK to produce sulfonated PEEK. After sulfonation, a layer of strongly acidic sulfonic acid groups forms on the surface of the PEEK. These sulfonic acid groups can interact with acids to a certain extent, preventing acid from corroding the material. The sulfonation reaction also changes the molecular structure of the PEEK, making it more stable and thus improving its acid resistance.

[0029] The carbonyl group structure and methyl groups of sulfonated polyetheretherketone (SPEK) serve as crosslinking points. These groups can undergo crosslinking reactions under high temperatures or UV irradiation, improving the material's usability. This flexible structure allows for excellent processing properties. Furthermore, post-processing crosslinking and curing further enhances the material's acid and solvent resistance, making it more adaptable to the highly acidic environment of gastric acid.

[0030] The surfactant used in the present invention has an amino group and can react and couple with the epoxy group of the silane coupling agent, thereby reducing the surface energy of the coating, having a self-cleaning effect, and effectively preventing problems such as fogging and hanging. At the same time, the silane coupling agent can couple the modified microspheres with the polymer, thereby greatly improving the compatibility of the modified microspheres. On the other hand, the silane coupling agent can also undergo a ring-opening reaction with the polyurethane material used for cleaning endoscope caps specifically for gastroscopes, thereby further improving the adhesion of the coating. In addition, the leveling agent added to the modified coating of the present invention is N-methylpyrrolidone (NMP), which has a good leveling effect and rarely causes sagging and orange peel phenomena.

[0031] The surface of the clean endoscope cap for gastroscopes prepared by the present invention is sprayed with a modified coating, so that the clean endoscope cap for gastroscopes prepared has good antistatic, anti-fouling, anti-fog, hydrophilic and antibacterial properties, good anti-sagging properties, and at the same time, has good tolerance to gastric acid environment, and has broad application prospects. DETAILED DESCRIPTION

[0032] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0033] Example 1

[0034] This embodiment provides a gastroscope-specific clean endoscope cap, on the surface of which the modified coating is evenly sprayed, and the spraying amount is 2mL / cm 3 The pressure of the spray gun is 25 MPa, the coating is formed by heat preservation and curing at 110°C for 10 minutes, and cross-linking and curing with an ultraviolet lamp for 10 minutes to obtain a special clean endoscope cap for gastroscope.

[0035] The preparation method of the modified coating is as follows:

[0036] S1. Preparation of organic resin microspheres: 1 g formaldehyde and 1 g melamine were added to 120 mL of water, heated to 75°C, 0.3 g polyvinyl alcohol and 0.1 g citric acid were added, and the mixture was stirred and reacted for 10 min. The mixture was centrifuged, washed, and dried to obtain organic resin microspheres.

[0037] S2. Preparation of silica @ organic resin microspheres: 8 g of methyl orthosilicate was dissolved in 100 g of ethanol, 5 g of organic resin microspheres were added, 7 g of concentrated hydrochloric acid and 3 g of water were added, the reaction was stirred for 10 h, centrifuged, washed, and dried to obtain silica @ organic resin microspheres;

[0038] S3. In situ deposition of carbon nanotubes: 10 g of silica@organic resin microspheres were immersed in 100 mL of a 1 wt% iron salt solution for 12 h, centrifuged, and heated to 850°C under nitrogen at a rate of 10°C / min for 50 min to deposit carbon nanotubes. The temperature was then cooled to room temperature to produce antistatic silica microspheres.

[0039] S4. Preparation of modified microspheres: 10 g of antistatic silica microspheres were added to 200 mL of Tris-HCl solution (pH 8.5), 3 g of tannic acid was added, and the mixture was heated to 40°C with stirring for 3 h. The mixture was centrifuged, washed, and dried. The resulting mixture was then added to 200 mL of Tris-HCl solution (pH 8.5), 4 g of dopamine hydrochloride was added, and the mixture was heated to 40°C with stirring for 3 h. The mixture was centrifuged, washed, and dried to produce modified microspheres.

[0040] S5. Preparation of bisphenol A polyetheretherketone: 0.2 mol of bisphenol A monomer, 0.2 mol of 4,4'-difluorobenzophenone, sodium carbonate, and 0.4 mol of toluene were added to 500 mL of dimethyl sulfoxide (DMSO), where the amount of sodium carbonate added was 3 wt % of the mass of 4,4'-difluorobenzophenone. The mixture was stirred at room temperature for 1 hour to form a salt. Under nitrogen protection, the temperature was raised to 190°C and stirred for 4 hours. The mixture was then added to an equal volume of water, filtered, washed, dried, and pulverized to produce bisphenol A polyetheretherketone.

[0041] S6. Preparation of sulfonated polyetheretherketone: 10 g of bisphenol A polyetheretherketone was mixed with 100 mL of concentrated sulfuric acid and reacted for 12 h, filtered, washed, and dried to obtain sulfonated bisphenol A polyetheretherketone;

[0042] S7. Preparation of modified coating: Dissolve 40 g of sulfonated bisphenol A type polyetheretherketone in 200 mL of chloroform, add 15 g of modified microspheres and 5 g of silane coupling agent KH560, and stir and mix for 20 minutes to obtain an organic phase; add 8 g of N-acyl glutamate diester salt to 200 mL of water to obtain an aqueous phase; mix the aqueous phase and the organic phase for 20 minutes, treat with a colloid mill for 1 hour, reduce pressure and heat to remove chloroform, cool to room temperature, add 1 g of N-methylpyrrolidone and 2 g of polyacrylate thickening rheological agent HV-30, and pass through a 40-mesh sieve to obtain a modified coating.

[0043] Example 2

[0044] This embodiment provides a gastroscope-specific cleaning endoscope cap, on the surface of which the modified coating is evenly sprayed, and the spraying amount is 4mL / cm 3 The pressure of the spray gun is 35 MPa, the coating is formed by heat preservation and curing at 130°C for 20 minutes, and cross-linking and curing with an ultraviolet lamp for 20 minutes to obtain a special clean endoscope cap for gastroscope.

[0045] The preparation method of the modified coating is as follows:

[0046] S1. Preparation of organic resin microspheres: 3 g of formaldehyde and 3 g of melamine were added to 120 mL of water, heated to 85°C, 0.7 g of polyvinyl alcohol and 0.3 g of citric acid were added, and the mixture was stirred and reacted for 20 min. The mixture was centrifuged, washed, and dried to obtain organic resin microspheres.

[0047] S2. Preparation of silica @ organic resin microspheres: 10 g of ethyl orthosilicate was dissolved in 120 g of ethanol, 8 g of organic resin microspheres were added, 10 g of concentrated hydrochloric acid and 5 g of water were added, and the reaction was stirred for 15 h, centrifuged, washed, and dried to obtain silica @ organic resin microspheres;

[0048] S3. In situ deposition of carbon nanotubes: 10 g of silica@organic resin microspheres were immersed in 100 mL of a 3 wt% iron salt solution for 12 h, centrifuged, and heated to 950°C under nitrogen at a rate of 20°C / min for 70 min to deposit carbon nanotubes. The temperature was then cooled to room temperature to produce antistatic silica microspheres.

[0049] S4. Preparation of modified microspheres: 10 g of antistatic silica microspheres were added to 200 mL of Tris-HCl solution (pH 9.5), 4 g of tannic acid was added, and the mixture was heated to 50°C with stirring for 5 h. The mixture was centrifuged, washed, and dried. The resulting mixture was then added to 200 mL of Tris-HCl solution (pH 9.5), 6 g of dopamine hydrochloride was added, and the mixture was heated to 50°C with stirring for 5 h. The mixture was centrifuged, washed, and dried to produce modified microspheres.

[0050] S5. Preparation of bisphenol A polyetheretherketone: 0.2 mol of bisphenol A monomer, 0.2 mol of 4,4'-difluorobenzophenone, potassium carbonate, and 0.8 mol of toluene were added to 500 mL of dimethyl sulfoxide (DMSO), where the amount of potassium carbonate added was 5 wt % of the mass of 4,4'-difluorobenzophenone. The mixture was stirred at room temperature for 3 h to form a salt. Under nitrogen, the temperature was raised to 210°C and stirred for 6 h. The mixture was then added to an equal volume of water, filtered, washed, dried, and pulverized to produce bisphenol A polyetheretherketone.

[0051] S6. Preparation of sulfonated polyetheretherketone: 10 g of bisphenol A polyetheretherketone was mixed with 200 mL of concentrated sulfuric acid and reacted for 18 h, filtered, washed, and dried to obtain sulfonated bisphenol A polyetheretherketone;

[0052] S7. Preparation of modified coating: 50 g of sulfonated bisphenol A type polyetheretherketone was dissolved in 200 mL of chloroform, 20 g of modified microspheres and 8 g of silane coupling agent KH560 were added, and the mixture was stirred for 20 min to obtain an organic phase; 10 g of cocoyl arginine ethyl ester was added to 200 mL of water to obtain an aqueous phase; the aqueous phase and the organic phase were mixed for 20 min, and the mixture was colloid milled for 3 h. The chloroform was removed by heating under reduced pressure, and the mixture was cooled to room temperature. 3 g of N-methylpyrrolidone and 4 g of polyacrylate thickening rheological agent HV-30 were added, and the mixture was passed through an 80-mesh sieve to obtain a modified coating.

[0053] Example 3

[0054] This embodiment provides a gastroscope-specific cleaning endoscope cap, on the surface of which the modified coating is evenly sprayed, and the spraying amount is 3mL / cm 3 The pressure of the spray gun is 30 MPa, the coating is formed by heat preservation and curing at 120°C for 15 minutes, and cross-linking and curing with an ultraviolet lamp for 15 minutes to obtain a special clean endoscope cap for gastroscope.

[0055] The preparation method of the modified coating is as follows:

[0056] S1. Preparation of organic resin microspheres: 2 g of formaldehyde and 2 g of melamine were added to 120 mL of water, heated to 80°C, 0.5 g of polyvinyl alcohol and 0.2 g of citric acid were added, and the mixture was stirred and reacted for 15 min. The mixture was centrifuged, washed, and dried to obtain organic resin microspheres.

[0057] S2. Preparation of silica @ organic resin microspheres: 9 g of ethyl orthosilicate was dissolved in 110 g of ethanol, 6 g of organic resin microspheres were added, 8 g of concentrated hydrochloric acid and 4 g of water were added, and the reaction was stirred for 12 h, centrifuged, washed, and dried to obtain silica @ organic resin microspheres;

[0058] S3. In situ deposition of carbon nanotubes: 10 g of silica@organic resin microspheres were immersed in 100 mL of a 2 wt% iron salt solution for 12 h, centrifuged, and heated to 900°C under nitrogen at a rate of 15°C / min for 60 min to deposit carbon nanotubes. The temperature was then cooled to room temperature to produce antistatic silica microspheres.

[0059] S4. Preparation of modified microspheres: 10 g of antistatic silica microspheres were added to 200 mL of Tris-HCl solution (pH 9), 3.5 g of tannic acid was added, and the mixture was heated to 45°C with stirring for 4 h. The mixture was centrifuged, washed, and dried. The resulting mixture was then added to 200 mL of Tris-HCl solution (pH 9), 5 g of dopamine hydrochloride was added, the mixture was heated to 45°C with stirring for 4 h, centrifuged, washed, and dried to produce modified microspheres.

[0060] S5. Preparation of bisphenol A polyetheretherketone: 0.2 mol of bisphenol A monomer, 0.2 mol of 4,4'-difluorobenzophenone, potassium carbonate, and 0.6 mol of toluene were added to 500 mL of dimethyl sulfoxide (DMSO), where the amount of potassium carbonate added was 4 wt % of the mass of 4,4'-difluorobenzophenone. The mixture was stirred at room temperature for 2 h to form a salt. Under nitrogen, the temperature was raised to 200°C and stirred for 5 h. The mixture was then added to an equal volume of water, filtered, washed, dried, and pulverized to produce bisphenol A polyetheretherketone.

[0061] S6. Preparation of sulfonated polyetheretherketone: 10 g of bisphenol A polyetheretherketone was mixed with 150 mL of concentrated sulfuric acid and reacted for 15 h, filtered, washed, and dried to obtain sulfonated bisphenol A polyetheretherketone;

[0062] S7. Preparation of modified coating: Dissolve 45 g of sulfonated bisphenol A type polyetheretherketone in 200 mL of chloroform, add 17 g of modified microspheres and 6 g of silane coupling agent KH560, and stir and mix for 20 minutes to obtain an organic phase; add 9 g of sodium N-acyl glutamate to 200 mL of water to obtain an aqueous phase; mix the aqueous phase and the organic phase for 20 minutes, treat with a colloid mill for 2 hours, reduce pressure and heat to remove chloroform, cool to room temperature, add 2 g of N-methylpyrrolidone and 3 g of polyacrylate thickening rheological agent HV-30, and pass through a 60-mesh sieve to obtain a modified coating.

[0063] Comparative Example 1

[0064] Compared with embodiment 3, the difference is that step S3 is not performed.

[0065] The details are as follows:

[0066] S1. Preparation of organic resin microspheres: 2 g of formaldehyde and 2 g of melamine were added to 120 mL of water, heated to 80°C, 0.5 g of polyvinyl alcohol and 0.2 g of citric acid were added, and the mixture was stirred and reacted for 15 min. The mixture was centrifuged, washed, and dried to obtain organic resin microspheres.

[0067] S2. Preparation of silica @ organic resin microspheres: 9 g of ethyl orthosilicate was dissolved in 110 g of ethanol, 6 g of organic resin microspheres were added, 8 g of concentrated hydrochloric acid and 4 g of water were added, and the reaction was stirred for 12 h, centrifuged, washed, and dried to obtain silica @ organic resin microspheres;

[0068] S3. Preparation of modified microspheres: 10 g of silica@organic resin microspheres were added to 200 mL of Tris-HCl solution (pH 9), 3.5 g of tannic acid was added, and the mixture was heated to 45°C with stirring for 4 h. The mixture was centrifuged, washed, and dried. The product was then added to 200 mL of Tris-HCl solution (pH 9), 5 g of dopamine hydrochloride was added, and the mixture was heated to 45°C with stirring for 4 h. The mixture was centrifuged, washed, and dried to obtain modified microspheres.

[0069] S4. Preparation of bisphenol A polyetheretherketone: 0.2 mol of bisphenol A monomer, 0.2 mol of 4,4'-difluorobenzophenone, potassium carbonate, and 0.6 mol of toluene were added to 500 mL of dimethyl sulfoxide (DMSO), where the amount of potassium carbonate added was 4 wt % of the mass of 4,4'-difluorobenzophenone. The mixture was stirred at room temperature for 2 h to form a salt. Under nitrogen, the temperature was raised to 200°C and stirred for 5 h. The mixture was then added to an equal volume of water, filtered, washed, dried, and pulverized to produce bisphenol A polyetheretherketone.

[0070] S5. Preparation of sulfonated polyetheretherketone: 10 g of bisphenol A polyetheretherketone was mixed with 150 mL of concentrated sulfuric acid and reacted for 15 h, filtered, washed, and dried to obtain sulfonated bisphenol A polyetheretherketone;

[0071] S6. Preparation of modified coating: 45 g of sulfonated bisphenol A type polyetheretherketone was dissolved in 200 mL of chloroform, 17 g of modified microspheres and 6 g of silane coupling agent KH560 were added, and the mixture was stirred for 20 min to obtain an organic phase; 9 g of sodium N-acyl glutamate was added to 200 mL of water to obtain an aqueous phase; the aqueous phase and the organic phase were mixed for 20 min, and the mixture was colloid milled for 2 h. The chloroform was removed by heating under reduced pressure, and the mixture was cooled to room temperature. 2 g of N-methylpyrrolidone and 3 g of polyacrylate thickening rheological agent HV-30 were added, and the mixture was passed through a 60-mesh sieve to obtain a modified coating.

[0072] Comparative Example 2

[0073] Compared with Example 3, the difference is that tannic acid is not added in step S4.

[0074] The details are as follows:

[0075] S4. Preparation of modified microspheres: 10 g of antistatic silica microspheres were added to 200 mL of Tris-HCl solution with a pH of 9, 5 g of dopamine hydrochloride was added, and the mixture was heated to 45°C and stirred for 4 h. The mixture was centrifuged, washed, and dried to obtain modified microspheres.

[0076] Comparative Example 3

[0077] Compared with Example 3, the difference is that dopamine hydrochloride is not added in step S4.

[0078] The details are as follows:

[0079] S4. Preparation of modified microspheres: 10 g of antistatic silica microspheres were added to 200 mL of Tris-HCl solution with a pH of 9, 3.5 g of tannic acid was added, and the mixture was heated to 45°C and stirred for 4 h. The mixture was centrifuged, washed, and dried to obtain modified microspheres.

[0080] Comparative Example 4

[0081] Compared with embodiment 3, the difference is that step S4 is not performed.

[0082] The details are as follows:

[0083] S1. Preparation of organic resin microspheres: 2 g of formaldehyde and 2 g of melamine were added to 120 mL of water, heated to 80°C, 0.5 g of polyvinyl alcohol and 0.2 g of citric acid were added, and the mixture was stirred and reacted for 15 min. The mixture was centrifuged, washed, and dried to obtain organic resin microspheres.

[0084] S2. Preparation of silica @ organic resin microspheres: 9 g of ethyl orthosilicate was dissolved in 110 g of ethanol, 6 g of organic resin microspheres were added, 8 g of concentrated hydrochloric acid and 4 g of water were added, and the reaction was stirred for 12 h, centrifuged, washed, and dried to obtain silica @ organic resin microspheres;

[0085] S3. In situ deposition of carbon nanotubes: 10 g of silica@organic resin microspheres were immersed in 100 mL of a 2 wt% iron salt solution for 12 h, centrifuged, and heated to 900°C under nitrogen at a rate of 15°C / min for 60 min to deposit carbon nanotubes. The temperature was then cooled to room temperature to produce antistatic silica microspheres.

[0086] S3. Preparation of bisphenol A polyetheretherketone: 0.2 mol of bisphenol A monomer, 0.2 mol of 4,4'-difluorobenzophenone, potassium carbonate, and 0.6 mol of toluene were added to 500 mL of dimethyl sulfoxide (DMSO), where the amount of potassium carbonate added was 4 wt % of the mass of 4,4'-difluorobenzophenone. The mixture was stirred at room temperature for 2 h to form a salt. Under nitrogen, the temperature was raised to 200°C and stirred for 5 h. The mixture was then added to an equal volume of water, filtered, washed, dried, and pulverized to obtain bisphenol A polyetheretherketone.

[0087] S5. Preparation of sulfonated polyetheretherketone: 10 g of bisphenol A polyetheretherketone was mixed with 150 mL of concentrated sulfuric acid and reacted for 15 h, filtered, washed, and dried to obtain sulfonated bisphenol A polyetheretherketone;

[0088] S6. Preparation of modified coating: 45 g of sulfonated bisphenol A type polyetheretherketone was dissolved in 200 mL of chloroform, 17 g of antistatic silica microspheres and 6 g of silane coupling agent KH560 were added, and the mixture was stirred for 20 min to obtain an organic phase; 9 g of sodium N-acyl glutamate was added to 200 mL of water to obtain an aqueous phase; the aqueous phase and the organic phase were mixed for 20 min, and the mixture was colloid milled for 2 h. The chloroform was removed by heating under reduced pressure, and the mixture was cooled to room temperature. 2 g of N-methylpyrrolidone and 3 g of polyacrylate thickening rheological agent HV-30 were added, and the mixture was passed through a 60-mesh sieve to obtain a modified coating.

[0089] Comparative Example 5

[0090] Compared with embodiment 3, the difference is that step S6 is not performed.

[0091] The details are as follows:

[0092] S1. Preparation of organic resin microspheres: 2 g of formaldehyde and 2 g of melamine were added to 120 mL of water, heated to 80°C, 0.5 g of polyvinyl alcohol and 0.2 g of citric acid were added, and the mixture was stirred and reacted for 15 min. The mixture was centrifuged, washed, and dried to obtain organic resin microspheres.

[0093] S2. Preparation of silica @ organic resin microspheres: 9 g of ethyl orthosilicate was dissolved in 110 g of ethanol, 6 g of organic resin microspheres were added, 8 g of concentrated hydrochloric acid and 4 g of water were added, and the reaction was stirred for 12 h, centrifuged, washed, and dried to obtain silica @ organic resin microspheres;

[0094] S3. In situ deposition of carbon nanotubes: 10 g of silica@organic resin microspheres were immersed in 100 mL of a 2 wt% iron salt solution for 12 h, centrifuged, and heated to 900°C under nitrogen at a rate of 15°C / min for 60 min to deposit carbon nanotubes. The temperature was then cooled to room temperature to produce antistatic silica microspheres.

[0095] S4. Preparation of modified microspheres: 10 g of antistatic silica microspheres were added to 200 mL of Tris-HCl solution (pH 9), 3.5 g of tannic acid was added, and the mixture was heated to 45°C with stirring for 4 h. The mixture was centrifuged, washed, and dried. The resulting mixture was then added to 200 mL of Tris-HCl solution (pH 9), 5 g of dopamine hydrochloride was added, the mixture was heated to 45°C with stirring for 4 h, centrifuged, washed, and dried to produce modified microspheres.

[0096] S5. Preparation of bisphenol A polyetheretherketone: 0.2 mol of bisphenol A monomer, 0.2 mol of 4,4'-difluorobenzophenone, potassium carbonate, and 0.6 mol of toluene were added to 500 mL of dimethyl sulfoxide (DMSO), where the amount of potassium carbonate added was 4 wt % of the mass of 4,4'-difluorobenzophenone. The mixture was stirred at room temperature for 2 h to form a salt. Under nitrogen, the temperature was raised to 200°C and stirred for 5 h. The mixture was then added to an equal volume of water, filtered, washed, dried, and pulverized to produce bisphenol A polyetheretherketone.

[0097] S6. Preparation of modified coating: 45 g of bisphenol A type polyetheretherketone was dissolved in 200 mL of chloroform, 17 g of modified microspheres and 6 g of silane coupling agent KH560 were added, and the mixture was stirred for 20 min to obtain an organic phase; 9 g of sodium N-acyl glutamate was added to 200 mL of water to obtain an aqueous phase; the aqueous phase and the organic phase were mixed for 20 min, and the mixture was colloid milled for 2 h. The chloroform was removed by heating under reduced pressure, and the mixture was cooled to room temperature. 2 g of N-methylpyrrolidone and 3 g of polyacrylate thickening rheological agent HV-30 were added, and the mixture was passed through a 60-mesh sieve to obtain a modified coating.

[0098] Comparative Example 6

[0099] Compared with Example 3, the difference is that the silane coupling agent KH560 is not added in step S7.

[0100] The details are as follows:

[0101] S7. Preparation of modified coating: Dissolve 45 g of sulfonated bisphenol A type polyetheretherketone in 200 mL of chloroform, add 17 g of modified microspheres, and stir for 20 minutes to obtain an organic phase; add 9 g of sodium N-acyl glutamate to 200 mL of water to obtain an aqueous phase; mix the aqueous phase and the organic phase for 20 minutes, treat with a colloid mill for 2 hours, reduce pressure and increase temperature to remove chloroform, cool to room temperature, add 2 g of N-methylpyrrolidone and 3 g of polyacrylate thickening rheological agent HV-30, and pass through a 60-mesh sieve to obtain a modified coating.

[0102] Comparative Example 7

[0103] Compared with Example 3, the difference is that in step S7, sodium N-acyl glutamate is replaced by sodium lauryl sulfate of equal mass.

[0104] The details are as follows:

[0105] S7. Preparation of modified coating: Dissolve 45 g of sulfonated bisphenol A type polyetheretherketone in 200 mL of chloroform, add 17 g of modified microspheres and 6 g of silane coupling agent KH560, and stir and mix for 20 minutes to obtain an organic phase; add 9 g of sodium lauryl sulfate to 200 mL of water to obtain an aqueous phase; mix the aqueous phase and the organic phase for 20 minutes, treat with a colloid mill for 2 hours, reduce pressure and heat to remove chloroform, cool to room temperature, add 2 g of N-methylpyrrolidone and 3 g of polyacrylate thickening rheological agent HV-30, and pass through a 60-mesh sieve to obtain a modified coating.

[0106] Test Example 1

[0107] The surface coatings of the gastroscope-specific clean endoscope caps prepared in Examples 1-3 and Comparative Examples 1-7 were tested. The antibacterial rate test used Gram-negative bacteria Escherichia coli (ATCC 25922), and the results are shown in Table 1.

[0108] Table 1

[0109]

[0110]

[0111] As can be seen from the above table, the surface coatings of the clean endoscope caps for gastroscopes prepared in Examples 1-3 of the present invention have good adhesion, flexibility, stain resistance, self-cleaning properties, antibacterial properties and impact resistance.

[0112] Test Example 2

[0113] The surface coatings of the gastroscope-specific clean endoscope caps prepared in Examples 1-3 of the present invention and Comparative Examples 1-7 were subjected to an average light transmittance test under visible light of 400-700 nm. The results are shown in Table 2.

[0114] Table 2

[0115] Group Average light transmittance (%) Example 1 91.5 Example 2 91.9 Example 3 92.2 Comparative Example 1 90.5 Comparative Example 2 87.4 Comparative Example 3 85.7 Comparative Example 4 83.2 Comparative Example 5 88.9 Comparative Example 6 86.4 Comparative Example 7 82.6

[0116] It can be seen from the above table that the surface coatings of the medical clean endoscope caps prepared in Examples 1-3 of the present invention have good anti-reflection effects.

[0117] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a gastroscope-specific cleaning endoscope cap, characterized in that: A modified coating is evenly sprayed on the surface of a special clean endoscope cap for gastroscopes, pre-cured by heating, and cross-linked and cured by ultraviolet light to form a coating, thereby preparing a special clean endoscope cap for gastroscopes. The modified coating is an aqueous dispersion prepared by a mixed reaction of carbon nanotube-deposited silica microspheres modified with polydopamine and tannic acid and sulfonated bisphenol A type polyetheretherketone under the action of a surfactant and a silane coupling agent.

2. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 1, characterized in that: The preparation method of the modified coating is as follows: S1. Preparation of organic resin microspheres: Formaldehyde and melamine were added to water, polyvinyl alcohol and citric acid were added under heating conditions, the reaction was stirred and insulated, centrifuged, washed, and dried to obtain organic resin microspheres; S2. Preparation of silica @ organic resin microspheres: Dissolve alkyl orthosilicate in ethanol, add organic resin microspheres, add concentrated hydrochloric acid and water, stir the reaction, centrifuge, wash, and dry to obtain silica @ organic resin microspheres; S3. In situ deposition of carbon nanotubes: Silica@organic resin microspheres were immersed in an iron salt solution, centrifuged, and heated under inert gas to deposit carbon nanotubes. The solution was cooled to room temperature to produce antistatic silica microspheres. S4. Preparation of modified microspheres: Antistatic silica microspheres were added to a Tris-HCl solution, tannic acid was added, the mixture was heated with stirring, centrifuged, washed, and dried. The product was added to a Tris-HCl solution, dopamine hydrochloride was added, the mixture was heated with stirring, centrifuged, washed, and dried to obtain modified microspheres. S5. Preparation of bisphenol A polyetheretherketone: Bisphenol A monomer, 4,4'-difluorobenzophenone, carbonate, and toluene were added to dimethyl sulfoxide and stirred at room temperature to form a salt. Under an inert gas atmosphere, the reaction was heated and stirred, and the mixture was added to water, filtered, washed, dried, and pulverized to obtain bisphenol A polyetheretherketone. S6. Preparation of sulfonated polyetheretherketone: bisphenol A polyetheretherketone was mixed with concentrated sulfuric acid, filtered, washed, and dried to obtain sulfonated bisphenol A polyetheretherketone; S7. Preparation of modified coating: dissolve sulfonated bisphenol A type polyetheretherketone in chloroform, add modified microspheres and silane coupling agent, stir and mix evenly to obtain an organic phase; add surfactant into water to obtain an aqueous phase; mix the aqueous phase and the organic phase evenly, treat with a colloid mill, reduce pressure and heat to remove chloroform, cool to room temperature, add leveling agent and thickener, sieve to obtain a modified coating.

3. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 2, characterized in that: In step S1, the mass ratio of formaldehyde, melamine, polyvinyl alcohol and citric acid is 1-3:1-3:0.3-0.7:0.1-0.3, the heating temperature is 75-85° C., and the heat preservation and stirring reaction time is 10-20 minutes.

4. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 2, characterized in that: In step S2, the alkyl orthosilicate is methyl orthosilicate or ethyl orthosilicate, the mass ratio of the alkyl orthosilicate, ethanol, organic resin microspheres, concentrated hydrochloric acid and water is 8-10:100-120:5-8:7-10:3-5, and the stirring reaction time is 10-15 hours.

5. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 2, characterized in that: The iron salt content in the iron salt solution in step S3 is 1-3wt%, and the iron salt is ferric chloride, ferric sulfate or ferric nitrate. The heating conditions are to increase the temperature to 850-950°C at a rate of 10-20°C / min and keep the reaction warm for 50-70min.

6. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 2, characterized in that: The pH value of the Tris-HCl solution in step S4 is 8.5-9.5, the mass ratio of the antistatic silica microspheres, tannic acid and dopamine hydrochloride is 10:3-4:4-6, the temperature of the heating and stirring reaction is 40-50° C., and the time is 3-5 hours.

7. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 2, characterized in that: In step S5, the molar ratio of bisphenol A monomer, 4,4'-difluorobenzophenone, and toluene is 1:1:2-4. The amount of carbonate added is 3-5 wt% of the mass of 4,4'-difluorobenzophenone. The carbonate is sodium carbonate or potassium carbonate. The salt-forming reaction time is 1-3 hours. The temperature of the heating and stirring reaction is 190-210° C. for 4-6 hours.

8. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 2, characterized in that: In step S6, the solid-liquid ratio of bisphenol A polyetheretherketone to concentrated sulfuric acid is 1:10-20 g / mL, and the mixing reaction time is 12-18 hours. In step S7, the thickener is a polyacrylate thickening rheological agent HV-30, the leveling agent is N-methylpyrrolidone, the mass ratio of the sulfonated bisphenol A polyetheretherketone, modified microspheres, silane coupling agent, surfactant, thickener and leveling agent is 40-50:15-20:5-8:8-10:2-4:1-3, the silane coupling agent is KH560, the surfactant is at least one of N-acyl glutamic acid, sodium N-acyl glutamate, cocoyl arginine ethyl ester salt, and N-acyl glutamate diester salt, the colloid mill treatment time is 1-3 hours, and the mesh size of the sieving is 40-80 mesh.

9. The method for preparing a gastroscope-specific cleaning endoscope cap according to claim 1, characterized in that: The spraying amount is 2-4 mL / cm 3 The pressure of the spray gun is 25-35 MPa, the heating pre-curing condition is to keep the temperature at 110-130°C for 10-20 minutes, and the UV curing time is 10-20 minutes.

10. A special clean endoscope cap for gastroscope made by the preparation method according to any one of claims 1 to 9.

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