A manufacturing method of a coated nano-silver antibacterial polyurethane lens

Abstract

The present invention relates to a manufacturing method of a coated nano-silver antibacterial polyurethane lens, which is characterized in that the specific steps are as follows: The inner and outer surfaces of the substrate of the resin lens are subjected to organosiliconization. The specific method is to immerse the resin lens in an organosilicon solution, and after the organosilicon adheres to the inner and outer surfaces of the resin lens, it can be cured in an oven. In this application, a nano-silver loaded titanium dioxide composite powder with good dispersibility is obtained by a light irradiation method. Nano-silver has a higher antibacterial effect. The loading material titanium dioxide itself has antibacterial function, and at the same time, the refractive index is 2.76 - 2.55, and it is used in the lens coating process for the first time as a high refractive index material.

Description

Technical Field

[0001] The present invention relates to the technical field of lenses, and specifically, to a manufacturing method of a coated nano-silver antibacterial polyurethane lens. Background Art

[0002] Antibacterial materials refer to a new type of materials that have the function of killing or inhibiting microorganisms by themselves. The main component in antibacterial materials is an antibacterial agent, which is a chemical component highly sensitive to certain bacteria, molds and other microorganisms. A very small amount of antibacterial agent added to ordinary materials can make antibacterial materials. Inorganic antibacterial materials mainly utilize the antibacterial properties of metals such as silver, copper, and zinc. The silver, copper, zinc and other metals (or their ions) are fixed on the surface or pore channels of porous materials such as zeolites and silica gels by physical adsorption or ion exchange methods, and then added to products to obtain antibacterial materials. Inorganic antibacterial agents can be divided into two categories: oxide semiconductor photoactivated antibacterial and heavy metal oxide sterilization. They both have broad-spectrum antibacterial properties, are safe to use, and can maintain good antibacterial effects for a long time. However, the sterilization efficiency of semiconductor oxides is relatively low, and ultraviolet light must be used for catalysis during use; although heavy metal oxides have significant antibacterial effects, they are expensive, most of them are toxic to the human body, the scope of use and the amount of use are limited, and the discoloration problem of antibacterial agents such as silver ions in plastics is serious. Therefore, more in-depth research is still needed on inorganic antibacterial materials in aspects such as improving antibacterial ability, expanding application fields, and studying the mechanism of antibacterial properties. Since Fujishima and Honda in Japan reported the phenomenon of photocatalytic water electrolysis on a TiO2 electrode in 1972, the research on semiconductor photocatalysis has attracted extensive attention from scientists in the fields of international chemistry, physics, and materials science. After years of in-depth research, scientists have found that semiconductor photocatalytic materials have broad-spectrum antibacterial properties. Under the irradiation of ultraviolet light, they have good inhibitory and killing effects on various common pathogenic bacteria: they can decompose organic pollutants such as COx, Sox waste gases, chlorides, and organophosphorus through photocatalytic oxidation to achieve harmlessness.

[0003] Nano silver-loaded inorganic antibacterial material is a composite material of silver and inorganic nano-carriers. It is obtained by loading silver on nano-carriers by physical adsorption, ion exchange and other methods by utilizing the large specific surface area and high surface activity of nano-carriers. Titanium dioxide has the effect of photo-activated antibacterial. After being doped with metal ions or metal oxides, its activation efficiency can be improved and its antibacterial activity can be enhanced. At the same time, silver ions themselves have a good antibacterial effect. Therefore, in this patent, nano silver doped titanium dioxide is used to prepare a composite antibacterial powder. Silver nanoparticles have a large specific surface area due to the quantum effect. According to the Young-Laplace equation, the larger the surface area, the greater the degree of dissociation of silver, and the greater the concentration of silver ions in the solution, thereby achieving the purpose of improving the biochemical activity and sterilization of silver-based nano antibacterial materials. According to scientific research results, silver nanoparticles have strong photocatalytic ability. By activating oxygen in water and air, hydroxyl free radicals and negative oxygen ions are generated, so that they can obtain photocatalytic sterilization ability, which makes their antibacterial performance far greater than that of traditional silver ion bactericides. Nanoparticles adhere to the surface of cell membranes and penetrate into bacteria. Nanosilver interacts with sulfur-containing proteins in bacterial membranes in cells. When silver nanoparticles enter bacterial cells, they form a small molecular weight region in the center of the bacteria, and the bacteria group forms a cluster. The particles attack the respiratory chain, cell division and ultimately cell death. In bacterial cells, the nanoparticles release silver ions, thereby increasing their bactericidal activity. Due to the large specific surface area and extremely high surface activity of the nanoparticle carrier, the antibacterial agent can fully contact with the bacteria, and the amount of antibacterial agent used can be reduced. Therefore, silver-based nano antibacterial agents have greatly improved in many aspects such as long-lasting antibacterial properties, broad spectrum, high temperature resistance, no drug resistance, not easy to decompose, safety and hygiene, and high efficiency. Its antibacterial performance is better than that of traditional antibacterial agents and can be widely used in antibacterial treatment of textiles, plastics, coatings, water treatment, ceramics, etc.

[0004] This application provides a manufacturing method of a coated nano - silver antibacterial polyurethane lens. First, prepare nano - silver - loaded titanium dioxide powder. Configure titanium dioxide sol by mixing anhydrous ethanol, methanol, and acetic acid evenly and dropping tetrabutyl titanate into the above - mentioned solution drop by drop to obtain titanium dioxide sol. First, prepare an aqueous silver nitrate solution by dissolving polyvinylpyrrolidone in water to prepare an aqueous solution and then adding silver nitrate to obtain a silver nitrate solution. The concentration of silver nitrate is 0.001 - 1 mol / L. Then, configure silver nitrate - titanium dioxide sol by dropping the silver nitrate solution into the titanium dioxide sol drop by drop to obtain silver nitrate - titanium dioxide sol. After stirring the silver nitrate - titanium dioxide sol at room temperature, use the method of light irradiation to reduce silver nitrate to silver nanoparticles, thereby obtaining nano - silver - titanium dioxide sol. Finally, dry the nano - silver - titanium dioxide sol to obtain nano - silver - doped titanium dioxide. Subsequently, coat the nano - silver - doped titanium dioxide on the surface of the lens. The coating structure is 7 layers, including 7 layers from the inside to the outside. The first layer is a low - refractive - index film, the second layer is a high - refractive - index film, the third layer is a low - refractive - index film, the fourth layer is a high - refractive - index film, the fifth layer is a low - refractive - index film, the sixth layer is a nano - silver - doped titanium dioxide layer, and the seventh layer is a fluoride. The film - layer structures on both the upper and lower surfaces of the lens are 7 layers. The thicknesses of the coating film layers are as follows: the first layer is silicon dioxide with a thickness of 90 nm; the second layer is zirconium dioxide with a thickness of 15 nm; the third layer is silicon dioxide with a thickness of 45 nm; the fourth layer is zirconium dioxide with a thickness of 35 nm; the fifth layer is silicon dioxide with a thickness of 17 nm; the sixth layer is a nano - silver - doped titanium dioxide layer with a thickness of 35 nm; the seventh layer is a fluoride with a thickness of 12 nm. The reflectivity of the vacuum film is 0.3 - 1.2%. Before coating, the lens needs to be hardened. The steps are as follows: First, silicone - coat the inner and outer surfaces of the resin lens. The specific method is to immerse the resin lens in a silicone solution, and after the silicone adheres to the inner and outer surfaces of the resin lens, cure it in an oven. The vacuum degree of the vacuum coating method is less than or equal to 3.0×10 - 3 Pa, and the coating temperature is greater than 40°C. The composition of polyurethane is poly - thiol and isocyanate respectively. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a manufacturing method of a coated nano - silver antibacterial polyurethane lens. This application first proposes to apply nano - silver - titanium dioxide sol to the lens technology field by the method of coating film, which is prepared by the light irradiation method, rather than the traditional heating method.

[0006] The purpose of the present invention is achieved by the following technical solutions:

[0007] A manufacturing method of a coated nano - silver antibacterial polyurethane lens,

[0008] Siliconize the inner and outer surfaces of the substrate of the resin lens. Specifically, immerse the resin lens in the silicone solution. After the silicone adheres to the inner and outer surfaces of the resin lens, it can be cured in an oven. Specifically, first clean the polyurethane lens substrate with a lens cleaning machine, and then immerse it in a silicone composite titanium dioxide sol with a refractive index of 1.67 by dipping. After slowly taking it out of the sol, dry it on the surface in an oven at 80 °C. After surface drying, cure it in an oven at 120 °C for two hours. Then, deposit different refractive index materials on both sides of the hardened polyurethane lens of the resin lens by vacuum coating. From the inside to the outside, it includes a seven-layer structure, namely, the first layer is a low refractive index film, the second layer is a high refractive index film, the third layer is a low refractive index film, the fourth layer is a high refractive index film, the fifth layer is a low refractive index film, the sixth layer is an antibacterial film layer, and the seventh layer is a fluoride.

[0009] The conditions for coating are that the vacuum degree is less than or equal to 3.0×10-3 Pa, and the coating temperature is higher than 40 °C.

[0010] The film layer structures on the upper and lower surfaces of the substrate of the lens are both seven-layer structures.

[0011] Specifically, the preferred seven-layer structure is as follows: the first layer is silica with a thickness of 90 nm; the second layer is zirconia with a thickness of 15 nm; the third layer is silica with a thickness of 45 nm; the fourth layer is zirconia with a thickness of 35 nm; the fifth layer is silica with a thickness of 17 nm; the sixth layer is a nano-silver doped titanium dioxide layer with a thickness of 35 nm; the seventh layer is a fluoride with a thickness of 12 nm.

[0012] For nano-silver doped titanium dioxide, the mass percentage of its raw material components is:

[0013]

[0014] The preparation method of nano-silver doped titanium dioxide, the specific steps are as follows: it is obtained by irradiating the nano-silver titanium dioxide sol with an irradiation wavelength of 280 nm to 450 nm for 0.5 to 12 hours; among them, the nano-silver titanium dioxide sol is prepared by configuring a titanium dioxide sol, mixing anhydrous ethanol, methanol and acetic acid evenly, and dropping tetrabutyl titanate into the above solution drop by drop to obtain a titanium dioxide sol. Then prepare an aqueous silver nitrate solution, dissolve polyvinylpyrrolidone in water to prepare an aqueous solution, and then add silver nitrate to obtain a silver nitrate solution; the concentration of silver nitrate is 0.001 to 1 mol / L; configure a silver nitrate titanium dioxide sol, and drop the silver nitrate solution into the titanium dioxide sol drop by drop to obtain a nano-silver titanium dioxide sol; finally, irradiate the nano-silver titanium dioxide sol to obtain nano-silver doped titanium dioxide.

[0015] The substrate of the polyurethane lens is obtained by thermosetting polymerization of isocyanate and polythiol. The polythiol includes polythioether thiol and polyester thiol, and the polythioether thiol and polyester thiol are one or more combinations of 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,5-bis(mercaptomethyl)-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithioundecane, trimethylolpropane tris(3-mercaptopropionate), trimethylolethane tris(2-mercaptoacetate), pentaerythritol tetra(2-mercaptoacetate) and pentaerythritol tetra(3-mercaptopropionate), bis(2-hydroxyethyl) sulfide, 1,2-bis(2-hydroxyethylmercapto)ethane, bis(2-hydroxyethyl) disulfide and 1,4-dithiane-2,5-diol. The polyisocyanate is one or more combinations of 1,3-bis(isocyanatomethyl)benzene (m-xylylene diisocyanate, m-XDI), 1,4-bis(isocyanatomethyl)benzene (p-xylylene diisocyanate, p-XDI), 1,3-bis(2-isocyanatopropan-2-yl)benzene (m-tetramethylxylylene diisocyanate, m-TMXDI), 1,4-bis(2-isocyanatopropan-2-yl)benzene (p-tetramethylxylylene diisocyanate, p-TMXDI), 1,3-bis(isocyanatomethyl)-4-methylbenzene, 1,3-bis(isocyanatomethyl)-4-ethylbenzene, 1,3-bis(isocyanatomethyl)-5-methylbenzene, 1,3-bis(isocyanatomethyl)-4,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,5-dimethylbenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetramethylbenzene, 1,3-bis(isocyanatomethyl)-5-tert-butylbenzene, 1,3-bis(isocyanatomethyl)-4-chlorobenzene, 1,3-bis(isocyanatomethyl)-4,5-dichlorobenzene, 1,3-bis(isocyanatomethyl)-2,4,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrachlorobenzene, 1,4-bis(isocyanatomethyl)-2,3,5,6-tetrabromobenzene, 1,4-bis(2-isocyanatoethyl)benzene, 1,4-bis(isocyanatomethyl)naphthalene. The auxiliaries generally used in the polymerization of polythiol and isocyanate include catalysts, mold release agents, colorants, antioxidants and light absorbers, etc.First, add all the auxiliaries to the isocyanate and stir to dissolve. After complete dissolution, add the polythiol while stirring; and the ratio of polythiol to polyisocyanate is based on the molar ratio of functional group NCO / SH of 0.8:1 to 1.2:1. After vacuum degassing, pour the raw materials into a glass mold, and place the polyurethane raw materials in a specific curing furnace according to the curing procedure for curing. After complete curing, cool down to 80 degrees, and obtain the substrate of the polyurethane lens after demolding and cleaning; the curing procedure is as follows.

[0016]

[0017] At 80 °C, remove the mold to obtain the substrate of the polyurethane lens.

[0018] Compared with the prior art, the positive effects of the present invention are:

[0019] In this application, a nano-silver loaded titanium dioxide composite powder with good dispersibility is obtained by the light irradiation method. Nano-silver has a higher antibacterial effect. The loading material titanium dioxide itself has antibacterial function, and at the same time, the refractive index is 2.76 - 2.55, which is used for the first time in the lens coating process as a high refractive index material. Specific embodiments

[0020] The following provides specific embodiments of a manufacturing method of a coated nano-silver antibacterial polyurethane lens of the present invention.

[0021] Example 1

[0022] Mix 10 grams of anhydrous ethanol, 10 grams of methanol and grams of acetic acid evenly, and drop 10 grams of tetrabutyl titanate into the above solution drop by drop to obtain titanium dioxide sol. Dissolve 10 grams of polyvinylpyrrolidone in 10 grams of water to prepare an aqueous solution, and then add 1 gram of silver nitrate to obtain a silver nitrate solution. Drop 20 grams of the silver nitrate solution into the titanium dioxide sol drop by drop to obtain a silver nitrate - titanium dioxide sol; irradiate the prepared silver nitrate - titanium dioxide sol under the light in the wavelength range of 365 nm - 380 nm for 1 hour until the color of the solution finally changes from colorless to yellow, that is, the nano-silver loaded titanium dioxide sol is prepared. Subsequently, dry the nano-silver loaded titanium dioxide sol to obtain nano-silver doped titanium dioxide. For the surface-cured polyurethane lens hardening film, then use the vacuum coating method to deposit different refractive index materials on both sides of the resin lens hardening film, including seven layers from the inside to the outside, the first layer is a low refractive index film, the second layer is a high refractive index film, the third layer is a low refractive index film, the fourth layer is a high refractive index film, the fifth layer is a low refractive index film, the sixth layer is an antibacterial film layer, and the seventh layer is a fluoride. The coating conditions are that the vacuum degree is less than or equal to 3.0×10 -3Pa, the coating temperature is 50 °C. Specifically, the first layer is silicon dioxide with a thickness of 90 nm; the second layer is zirconium dioxide with a thickness of 15 nm; the third layer is silicon dioxide with a thickness of 45 nm; the fourth layer is zirconium dioxide with a thickness of 35 nm; the fifth layer is silicon dioxide with a thickness of 17 nm; the sixth layer is a nano-silver doped titanium dioxide layer with a thickness of 35 nm; the seventh layer is fluoride with a thickness of 12 nm.

[0023] Through antibacterial experiments, it was found that the antibacterial rate against Escherichia coli was 99.1%; the antibacterial rate against Staphylococcus aureus was 99.4%; the antibacterial rate against Candida albicans was 99.2%. From the above experimental data, it can be seen that the antibacterial functional polyurethane lens prepared by the present invention has a broad-spectrum and high-efficiency antibacterial effect.

[0024] Example 2

[0025] Mix 10 grams of absolute ethanol, 10 grams of methanol and grams of acetic acid evenly, and drop 10 grams of tetrabutyl titanate into the above solution drop by drop to obtain titanium dioxide sol. Dissolve 10 grams of polyvinylpyrrolidone in 10 grams of water to prepare an aqueous solution, and then add 1.5 grams of silver nitrate to obtain a silver nitrate solution. Drop 20 grams of the silver nitrate solution into the titanium dioxide sol drop by drop to obtain a silver nitrate-titanium dioxide sol; irradiate the prepared silver nitrate-titanium dioxide sol with light in the wavelength range of 365 nm to 380 nm for 1 hour until the color of the solution finally changes from colorless to yellow, that is, nano-silver loaded titanium dioxide sol is prepared. Subsequently, the nano-silver titanium dioxide sol is dried to obtain nano-silver doped titanium dioxide. The surface-cured polyurethane lens hardening film is then deposited with different refractive index materials on both sides of the resin lens hardening film by vacuum coating, including seven layers from the inside to the outside, the first layer is a low refractive index film, the second layer is a high refractive index film, the third layer is a low refractive index film, the fourth layer is a high refractive index film, the fifth layer is a low refractive index film, the sixth layer is an antibacterial film layer, and the seventh layer is fluoride. The coating conditions are a vacuum degree less than or equal to 3.0×10 -3 Pa, the coating temperature is 60 °C. Specifically, the first layer is silicon dioxide with a thickness of 90 nm; the second layer is zirconium dioxide with a thickness of 15 nm; the third layer is silicon dioxide with a thickness of 45 nm; the fourth layer is zirconium dioxide with a thickness of 35 nm; the fifth layer is silicon dioxide with a thickness of 17 nm; the sixth layer is a nano-silver doped titanium dioxide layer with a thickness of 35 nm; the seventh layer is fluoride with a thickness of 12 nm.

[0026] Through antibacterial experiments, it was found that the antibacterial rate against Escherichia coli was 99.2%; the antibacterial rate against Staphylococcus aureus was 99.1%; the antibacterial rate against Candida albicans was 99.5%. From the above experimental data, it can be seen that the antibacterial functional polyurethane lens prepared by the present invention has a broad-spectrum and high-efficiency antibacterial effect.

[0027] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as within the protection scope of the present invention.

Claims

1. A manufacturing method of a coated nano - silver antibacterial polyurethane lens, characterized in that, The specific steps are as follows: Siliconize the inner and outer surfaces of the substrate of the resin lens. The specific method is to immerse the resin lens in the silicone solution, and after the silicone adheres to the inner and outer surfaces of the resin lens, it can be cured in an oven. Specifically, first clean the polyurethane lens substrate with a lens cleaning machine, then immerse it in a silicone composite titanium dioxide sol with a refractive index of 1.67 by the immersion method. After slowly taking it out of the sol, perform surface drying in an oven at 80 °C, and then cure it in an oven at 120 °C for two hours. The hardened polyurethane lens with a cured surface is then deposited with different refractive index materials on both sides of the hard coating of the resin lens by vacuum coating, including seven-layer structures from the inside to the outside. The first layer is a low refractive index film, the second layer is a high refractive index film, the third layer is a low refractive index film, the fourth layer is a high refractive index film, the fifth layer is a low refractive index film, the sixth layer is an antibacterial film layer, and the seventh layer is a fluoride. The seven-layer structure is as follows: the first layer is silicon dioxide with a thickness of 90 nm; the second layer is zirconium dioxide with a thickness of 15 nm; the third layer is silicon dioxide with a thickness of 45 nm; the fourth layer is zirconium dioxide with a thickness of 35 nm; the fifth layer is silicon dioxide with a thickness of 17 nm; the sixth layer is a titanium dioxide layer doped with silver nanoparticles with a thickness of 35 nm; the seventh layer is a fluoride with a thickness of 12 nm. For titanium dioxide doped with silver nanoparticles, the mass percentages of its raw material components are as follows: Ethanol 1 - 10% Methanol 6 - 30% Acetic acid 5 - 30% Tetrabutyl titanate 5 - 35% Silver nitrate 1 - 10% Polyvinylpyrrolidone 2 - 20% Water the balance.

2. The manufacturing method of a coated nano-silver antibacterial polyurethane lens according to claim 1, characterized in that, The conditions for coating are that the vacuum degree is less than or equal to 3.0×10-3 Pa, and the coating temperature is greater than 40 °C.

3. The manufacturing method of a coated nano-silver antibacterial polyurethane lens according to claim 1, characterized in that, The film layer structures on the upper and lower surfaces of the substrate of the lens are both seven-layer structures.

4. The manufacturing method of a coated nano-silver antibacterial polyurethane lens according to claim 1, characterized in that, Silver-loaded titanium dioxide nanoparticles are obtained by irradiating a silver-titanium dioxide sol with an irradiation wavelength of 280 nm - 450 nm for 0.5 - 12 hours. Among them, the silver-titanium dioxide sol is prepared by preparing a titanium dioxide sol, mixing anhydrous ethanol, methanol, and acetic acid evenly, and dropping tetrabutyl titanate into the above solution drop by drop to obtain a titanium dioxide sol; then preparing an aqueous silver nitrate solution, dissolving polyvinylpyrrolidone in water to prepare an aqueous solution, and then adding silver nitrate to obtain a silver nitrate solution; the concentration of silver nitrate is 0.001 - 1 mol / L; preparing a silver nitrate-titanium dioxide sol, and adding the silver nitrate solution drop by drop to the titanium dioxide sol to obtain a silver-titanium dioxide sol; finally irradiating the silver-titanium dioxide sol to obtain titanium dioxide doped with silver nanoparticles.

5. The manufacturing method of a coated nano-silver antibacterial polyurethane lens according to claim 1, characterized in that, The substrate of the polyurethane lens is obtained by thermally curing and polymerizing isocyanate and polythiol, where the polythiol includes polythioether thiol and polyester thiol.

6. The manufacturing method of a coated nano-silver antibacterial polyurethane lens according to claim 1, characterized in that, Preparation of the substrate of the polyurethane lens: First, add all the additives to the isocyanate and stir to dissolve. After complete dissolution, add the polythiol while stirring; and the ratio of polythiol to polyisocyanate is based on the molar ratio of functional groups NCO / SH of 0.8:1 to 1.2:

1. After vacuum degassing, pour the raw materials into a glass mold, and place the polyurethane raw materials in a curing furnace according to the curing procedure for curing. After complete curing, cool down to 80 degrees, demold and clean to obtain the substrate of the polyurethane lens; the curing procedure is as follows: 25°C - 35°C for 0.5 h - 3 h 35°C - 41°C for 2 h - 5 h 41°C - 57°C for 2 h - 5 h 57°C - 81°C for 3 h - 5 h 81°C - 96°C for 2 h - 5 h 96°C - 130°C for 2 h - 5 h 130°C - 130°C for 2 h - 5 h 130°C - 80°C for 2 h - 5 h 80°C - 80°C for 0.5 h - 3 h At 80°C, remove the mold to obtain the substrate of the polyurethane lens.

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