WO2022116005A1 - 一种二氧化钛杀菌消毒膜 - Google Patents

一种二氧化钛杀菌消毒膜 Download PDF

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WO2022116005A1
WO2022116005A1 PCT/CN2020/133152 CN2020133152W WO2022116005A1 WO 2022116005 A1 WO2022116005 A1 WO 2022116005A1 CN 2020133152 W CN2020133152 W CN 2020133152W WO 2022116005 A1 WO2022116005 A1 WO 2022116005A1
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titanium dioxide
sterilization
solution
disinfection
liquid
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PCT/CN2020/133152
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English (en)
French (fr)
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赵志伟
周晓林
王航波
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莱恩创科（北京）科技有限公司
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Priority to PCT/CN2020/133152 priority Critical patent/WO2022116005A1/zh
Publication of WO2022116005A1 publication Critical patent/WO2022116005A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

  • the invention relates to the field of titanium dioxide materials, in particular to a titanium dioxide sterilization and disinfection film.
  • Touch-type electronic devices are widely used in life, such as mobile phones, tablet computers, information inquiry machines in public places, touch-type educational equipment, etc. When people use them, sweat, saliva and oil on their faces will adhere to the On the screen, this provides favorable conditions for the production and persistence of viruses and bacteria. If you just use a mobile phone, then rub your eyes or touch food with your hands, you will bring viruses and bacteria on the mobile phone into your body, so that the mobile phone becomes a transmission medium for viruses and bacteria. In addition to personal items such as mobile phones, touch-screen information inquiry machines, teaching equipment, self-checkout equipment, self-service scales and other equipment in public places have a common feature of cross-use by multiple people, which makes the spread of viruses and bacteria more serious.
  • Ultraviolet rays are harmful rays, and direct exposure to ultraviolet rays has an impact on human health and cannot be used in a human environment; not only that, ultraviolet rays will accelerate the aging of some materials, and also affect the equipment itself. Therefore, the use of alcohol and ultraviolet disinfection and sterilization have certain limitations, and cannot be effectively carried out in time and anywhere.
  • antibacterial glass In addition to the application of alcohol and ultraviolet disinfection, there is also a plan to apply antibacterial glass on the screen.
  • the main application of antibacterial ions such as silver and copper is to replace other metal ions on the glass surface under certain conditions, so that the antibacterial metal ions can be planted Into the glass matrix, it has antibacterial properties.
  • Chinese patent, application number CN202010334218.6, name of invention a preparation method of antibacterial glass and antibacterial glass.
  • the invention mainly introduces antibacterial silver ions into the glass surface to make the glass have antibacterial properties.
  • the inventor found that none of the prior art considers the method of applying the light source of the screen itself to perform active sterilization and disinfection.
  • the traditional method uses silver ions for sterilization, which mainly relies on the release of silver ions.
  • the process of sterilization and disinfection is uncontrollable and has low efficiency; at the same time, silver ions will age and change color after long-term use, which will affect the display effect.
  • Using the light source of the screen itself for active disinfection can not only overcome the problem of discoloration of the screen, but also improve the efficiency of sterilization and disinfection, and prolong the duration of the beneficial effect of sterilization and disinfection.
  • the inventor also found that in the scheme of using the screen's own light source to carry out sterilization and disinfection, the titanium dioxide material can be attached to the screen by means of coating or filming, effectively reducing the screen.
  • the portion of the emitted light that is blue light. While achieving disinfection and sterilization, it can also reduce the harm to the human body caused by the blue light of the screen.
  • Blue light mainly refers to light with relatively high energy wavelengths between 400nm-480nm, especially blue light with wavelengths below 450nm, which has high energy and can cause some ophthalmic diseases after entering the eyes, and also cause other negative effects on human health. , is harmful blue light; while blue light above 450nm has the effect of adjusting biological rhythm, but is beneficial to the human body. Corresponding requirements are also put forward in the national standard "GB/T 38120-2019 Technical Requirements for Light Health and Light Safety Application of Blue Light Protective Films". The inventor proposes a method for screen disinfection and sterilization, which realizes the precise elimination of harmful blue light, and uses the eliminated harmful blue light as an energy source for disinfection and sterilization, while allowing beneficial blue light to pass through.
  • the inventor found that when a titanium dioxide sterilization and disinfection film is applied to the screen, since the screen has a light source, it can emit light by itself, and the titanium dioxide can use the light emitted by the screen to perform a photocatalytic reaction.
  • the sterilization and disinfection film contains titanium dioxide material, and the titanium dioxide material is doped, which can efficiently utilize the harmful blue light emitted by the screen to produce a photocatalytic reaction, solve the problem of germs on the screen of electronic equipment, and can also consume and utilize harmful blue light emitted by electronic equipment.
  • the doped titanium dioxide material can solve the two problems of sterilization and anti-blue light at the same time.
  • the titanium dioxide material is doped with nitrogen or cobalt.
  • the titanium dioxide doping method is to synthesize doped titanium dioxide by hydrolyzing titanium alkoxide, and coat the doped titanium dioxide material on the surface of the desired material by coating or coating.
  • Nitrogen-doped or metal-doped titanium dioxide can increase the wavelength of titanium dioxide to absorb light waves, more effectively use the light source of the screen, and improve the photocatalytic efficiency and disinfection and sterilization capabilities. Not only that, the doped titanium dioxide can also effectively utilize the blue light emitted by the electronic screen, thereby reducing the harm of blue light to the human body.
  • the doped titanium dioxide material of the present invention is also suitable for surface treatment of glass, ceramics, metals, plastics and electronic equipment.
  • Figure 3 shows the DRS light absorption spectrum of Example 3.
  • FIG. 4 Schematic diagram of screen structure
  • 101 is a carrier
  • 102 is a titanium dioxide coating
  • a titanium dioxide sterilization and disinfection film is applied, and nitrogen-doped titanium dioxide material is produced by introducing nitrogen elements in the titanium dioxide preparation process, and the doping is doped by coating or coating.
  • the titanium dioxide material is coated to the desired material surface.
  • the method of introducing nitrogen element can be high temperature roasting method, hydrolysis precipitation method, organic precursor pyrolysis method, sol-gel method and so on.
  • the high-temperature roasting method refers to calcining titanium dioxide or other titanium-containing compounds in air or nitrogen-containing atmosphere.
  • the gas used is usually NH 3 , N 2 or a mixture of NH 3 and Ar.
  • doped TiO 2 with different properties can be prepared.
  • the hydrolysis precipitation method is to directly hydrolyze the titanium salt in a nitrogen-containing aqueous solution or hydrolyze the titanium salt and then react with a nitrogen-containing substance to obtain nitrogen-doped titanium dioxide.
  • the organic precursor pyrolysis method uses titanium salts to react with nitrogen-containing organic substances to obtain organic precursors containing Ti-N bonds, and then calcined in different temperatures and atmospheres to obtain doped TiO 2 .
  • the sol-gel method hydrolyzes titanium alkoxide or titanium inorganic salt, and then polymerizes and gels the solute to obtain titanium dioxide.
  • a titanium dioxide sterilization and disinfection film is applied, and by introducing metal elements such as Fe, Cr, Co, Mo and the like into the titanium dioxide preparation process, the electronic structure can be changed by mixing into the titanium dioxide. , thereby broadening the spectral response range of titanium dioxide, and coating the doped titanium dioxide material on the surface of the desired material by coating or coating.
  • This embodiment provides a preferred method for preparing a titanium dioxide sterilizing and disinfecting film.
  • a titanium dioxide coating with an efficient anti-blue light function can be manufactured.
  • the titanium dioxide sterilization and disinfection film uses the test method in GB/T38120-2019 to achieve a blue light absorption rate of 65-80% for a wavelength of 400-450nm, and a blue light absorption rate for a wavelength of 450nm-500nm less than 30%.
  • the light energy including harmful blue light
  • the titanium dioxide is excited to produce an active disinfection and sterilization effect.
  • the solvent described in the preparation method of the present invention is one or a combination of ethanol, ethylene glycol, isopropanol, and isopropylene glycol.
  • the inhibitor is one or a combination of nitric acid, hydrochloric acid, sulfuric acid, glacial acetic acid, acetylacetone, diethanolamine, and triethanolamine.
  • the sol E is used for the preparation of titanium dioxide sterilization and disinfection film.
  • Adhering methods such as pulling and dipping, spraying, rolling, magnetron sputtering, vapor deposition, etc. can be used to attach the active ingredient in the sol E to the desired surface to obtain a titanium dioxide sterilization and disinfection film, and the surface can be Surfaces of screens, lamps, and other light-emitting components.
  • the thickness of titanium dioxide sterilization and disinfection film is 100-500nm.
  • This embodiment provides a preferred method for preparing a titanium dioxide sterilization and disinfection film, which is to synthesize nitrogen-doped titanium dioxide by hydrolyzing titanium alkoxide, and coat the doped titanium dioxide material on the surface of the desired material by coating or coating. Preparation of titanium dioxide sterilization and disinfection film.
  • the specific preparation method includes the following steps:
  • the sol E was used for the preparation of antibacterial and anti-blue light layers.
  • the mass percentage concentration of the hydrofluoric acid in the present invention is 35% to 45%.
  • the mass percentage concentration of the nitric acid in the present invention is 60% to 80%.
  • the solvent described in the preparation method of the present invention is one or a combination of ethanol, ethylene glycol, isopropanol, and isopropylene glycol.
  • the inhibitor is one or a combination of nitric acid, hydrochloric acid, sulfuric acid, glacial acetic acid, acetylacetone, diethanolamine, and triethanolamine.
  • the mode of adding the C' solution to the B' solution in the step (4) is the mode of dropwise addition.
  • the sol E' is used for the preparation of cobalt-doped titanium dioxide sterilization and disinfection film.
  • Adhering methods such as pulling and dipping, spraying, rolling coating, magnetron sputtering, vapor deposition, etc. can be used to attach the active ingredients in the sol E' to the desired surface to obtain a titanium dioxide sterilization and disinfection film.
  • the surface can be It is the surface of screens, electronic equipment, tiles, etc.
  • the titanium dioxide sterilization and disinfection film prepared by the method in this example, and the test method in GB/T 38120-2019 has a blue light absorption rate of 400-450nm wavelength greater than 60%-80%, and a blue light absorption rate of 450nm-500nm wavelength. less than 30%.
  • the titanium dioxide sterilization and disinfection film prepared by the method of this embodiment can consume the harmful blue light generated by the screen, and at the same time use the harmful blue light as the light source of the photocatalytic reaction to stimulate the titanium dioxide to produce the effect of sterilization. In addition, it does not affect the display effect.
  • the technical solution of an embodiment of the present invention relates to a method for modifying titanium dioxide with fluorosilane, and the titanium dioxide sterilization and disinfection film obtained by using the fluorosilane-modified titanium dioxide has oleophobic and hydrophobic properties, which can reduce the grease of fingerprints Persistence on the screen, and reduces the chance of transmission through contact, thereby further improving the ability to fight pathogenic bacteria.
  • a titanium dioxide sol solution is synthesized and prepared by hydrolyzing titanium alkoxide; and then fluorine-modified alkylsilane is grafted on the surface of titanium dioxide to obtain a fluorosilane-modified titanium dioxide material.
  • the specific preparation method includes the following steps:
  • the sol E or E' is used for the preparation of antibacterial and anti-blue light layers.
  • fluorine-modified alkylsilane the structural formula is R f -(CH 2 ) n -Si(OR 1 ) 3 , wherein, R 1 is methyl or ethyl, and R f is C m F 2m+1 or C 6 F 5 , 0 ⁇ n ⁇ 3, 1 ⁇ m ⁇ 13, n and m are integers;
  • the mass percentage concentration of the hydrofluoric acid in the present invention is 35% to 45%.
  • the mass percentage concentration of the nitric acid in the present invention is 60% to 80%.
  • the solvent described in the preparation method of the present invention is one or a combination of ethanol, ethylene glycol, isopropanol, and isopropylene glycol.
  • Described inhibitor is one in nitric acid, hydrochloric acid, sulfuric acid, glacial acetic acid, acetylacetone, diethanolamine, triethanolamine or its combination.
  • step (4) the mode of adding the C solution to the B solution or adding the C' solution to the B' solution is the mode of dropwise addition.
  • the mass percentage concentration of the hydrofluoric acid in this embodiment is 35%-45%.
  • the mass percentage concentration of the hydrofluoric acid in this embodiment is 35%-45%.
  • the mass percentage concentration of the hydrofluoric acid in this embodiment is 35%-45%.
  • step (6) Aging the solution obtained in step (5) at a constant temperature of 25° C. for 24 h to obtain a sol E, that is, the preparation of the nitrogen-doped TiO 2 impregnation solution is completed.
  • step (5) The solution obtained in step (5) is aged at a constant temperature of 30° C. for 48 hours, and the obtained sol E, namely, the preparation of the cobalt-doped TiO 2 impregnation solution is completed.
  • the mass percentage concentration of the hydrofluoric acid in this embodiment is 35%-45%.
  • the steps for preparing the titanium dioxide sterilization and disinfection film are as follows, and the material used for the attachment of titanium dioxide is called a carrier, and the carrier can be glass, plexiglass and other materials:
  • the carrier is soaked in acetone solution with a mass fraction of 10-20% for 1-2 hours to remove organic impurities on its surface, and after soaking, it is taken out and rinsed with distilled water.
  • the cleaned carrier is etched with hydrofluoric acid with a mass fraction of 10-20% for 1-2 hours.
  • the purpose of etching is to make the surface of the carrier have a certain roughness, which is beneficial to increase the loading and loading of titanium dioxide. firmness;
  • the carrier is taken out, rinsed with distilled water, and placed in an ultrasonic cleaner.
  • the cleaning temperature is set to 50-60° C.
  • the frequency is 50 kHz
  • the cleaning is performed for 30-60 minutes.
  • the carrier is moved into a constant temperature blast drying oven to be dried at 80-100° C. for 3-6 hours, and then used to support the doped titanium dioxide after cooling.
  • the attachment method is to attach the doped titanium dioxide to the surface of the carrier by pulling and dipping, and put the prepared sol containing titanium dioxide into the liquid tank; insert the carrier vertically into the customized card basket, and place the card The basket is immersed in the liquid tank until the liquid is completely submerged in the carrier, and the immersion time is 3-10 minutes.
  • the titanium dioxide sol is a nitrogen-doped or cobalt-doped titanium dioxide sol.
  • the calcination conditions of step (6) are, when the carrier is glass, calcination at 400-600° C. for 20-40 minutes.
  • the calcination condition in step 6 is to heat up from room temperature to 95 to 105°C at 4 to 6°C/min, then to 195 to 205°C at 6 to 8°C/min, and to keep at 195 to 205°C for 10 minutes. ⁇ 15min; then raise the temperature to 395°C ⁇ 405°C at 8 ⁇ 9°C/min, keep at 395°C ⁇ 405°C for 10 ⁇ 15min; then raise the temperature to 495°C ⁇ 505°C at 8 ⁇ 9°C/min; ⁇ 6°C/min to raise the temperature to 600 ⁇ 800°C, and keep the temperature for 30 ⁇ 40min.
  • the thickness of the titanium dioxide sterilization and disinfection film prepared by applying this example is 200 nm, and the titanium dioxide sterilization and disinfection film contains siloxane bonds after heat treatment, which can make the titanium dioxide firmly connect with the glass.
  • the crystal structure of the heat-treated titanium dioxide is anatase type.
  • the cleaned carrier is etched with hydrofluoric acid with a mass fraction of 10% for 2 hours, and the purpose of the etching is to make the surface of the carrier have a certain roughness, which is beneficial to increase the loading capacity and loading firmness of titanium dioxide;
  • the carrier is taken out, rinsed with distilled water, and placed in an ultrasonic cleaner.
  • the cleaning temperature is set to 60° C.
  • the frequency is 50 kHz
  • the cleaning is performed for 40 minutes.
  • the carrier was moved into a constant temperature blast drying oven and dried at 90 °C for 4 h, and then used to attach doped titanium dioxide after cooling.
  • the attachment method is to attach the doped titanium dioxide to the surface of the carrier by pulling and dipping, and put the prepared dipping solution into the liquid tank; insert the carrier vertically into the customized card basket, and immerse the card basket in the In the liquid tank, until the liquid is completely immersed in the carrier, the immersion time is 5 minutes.
  • the immersion solution uses a sol prepared by a nitrogen-doped or cobalt-doped titanium dioxide preparation scheme.
  • the calcination conditions are as follows: from room temperature at 5°C/min to 100°C, then at 8°C/min to 200°C, and holding at 200°C for 15min; then at 10°C/min to 400°C, at 400°C. The temperature was maintained for 15 min; then the temperature was increased to 500 °C at 8 °C/min; then the temperature was increased to 600 °C at 5 °C/min, and the temperature was maintained for 30 min.
  • the thickness of the titanium dioxide sterilization and disinfection film prepared by applying this example is 130 nm.
  • the doped titanium dioxide coating contains chromium oxide, zinc sulfide, zirconium oxide or their combination. Conductive particles composed of materials, these fine particles make the doped titanium dioxide coating with antistatic properties.
  • the average particle size of the conductive particles is 0.01-1 ⁇ m. This is because if the average particle diameter of the fine particles is less than 0.01 ⁇ m, the surface energy of the conductive particles is large, and agglomeration of a plurality of particles is likely to occur, thereby reducing the light transmittance. However, if the average particle size of the conductive particles is larger than 1 ⁇ m, with the increase of the particle size, the light scattering will be enhanced, and the light transmittance of the coating will also be reduced.
  • the average particle diameter of the preferred fine particles is 0.05 to 0.15 ⁇ m, and more preferably 0.05 to 0.1 ⁇ m.
  • the thickness of the titanium dioxide sterilization and disinfection film containing conductive particles is 400nm.
  • etching and coating methods can be used on the surface of the screen glass to increase its roughness and have an anti-glare effect.
  • the glass surface is treated with a corrosive chemical solution, so that the glass surface is corroded to form an uneven microstructure and has the effect of scattering light. Since this method overlaps with the chemical agent used in the doped titanium dioxide coating step, it can be combined with the doped titanium dioxide coating step, so that the glass carrier can not only have the functions of anti-blue light and sterilization, but also have the function of anti-glare.
  • the process steps and formula of the microstructure formed by etching the surface of the carrier are as follows: first, coat a layer of paraffin on the glass product, draw matrix dots on the surface of the paraffin, expose the glass part to be etched, and immerse the glass product in the prepared etching solution for 15 minutes, and finally wash the etching solution and paraffin to obtain an etched cellophane product.
  • the formula of the etching solution is: 3%-6% hydrochloric acid, 0.5%-3% hydrofluoric acid, 0.03%-0.1% pickling corrosion inhibitor.
  • a preferred formulation of the etching solution is: 4%-5% hydrochloric acid, 1% hydrofluoric acid, 0.05% pickling corrosion inhibitor.
  • the thickness of the titanium dioxide sterilization and disinfection film with anti-glare function is 300nm.
  • the present invention relates to a method for sterilizing and disinfecting a screen.
  • the power of the light source can be increased to enhance the sterilization effect.
  • the power of the light source can be increased, and the sterilization effect can be enhanced by using the unmanned time.
  • the power of the light source can be increased to enhance the sterilization effect.
  • the DRS test was carried out on the samples prepared by the methods of Implementation 1, Example 2 and Example 3 to investigate the influence of the doping amount of nitrogen element on the absorption wavelength of the samples.
  • the characterization results are shown in Figure 1, Figure 2, and Figure 3 , the band gap of pure titanium dioxide is 3.2eV, so its maximum absorption wavelength is 538nm, and it can be seen from Figure 1 that the maximum absorption wavelength of Example 1 is about 400nm, and the DRS corresponding to the samples of Example 2 and Example 3
  • the spectrograms are shown in Figure 2 and Figure 3, and the maximum absorption wavelengths of Example 2 and Example 3 are 435 nm and 457 nm, respectively.
  • Nitrogen-doped TiO2 has undergone a significant red shift compared to pure TiO2. The results of DRS show that doping nitrogen can effectively increase the absorption wavelength of TiO2 and red-shift to the direction of visible light.

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Abstract

一种二氧化钛杀菌消毒膜，将其应用于屏幕上，由于屏幕具有光源，可以自发光，二氧化钛可以利用屏幕发出的光进行光催化反应。该杀菌消毒膜的含有二氧化钛材料，二氧化钛材料经过掺杂，可以高效利用屏幕发射出的有害蓝光发生光催化反应，解决电子设备屏幕的病菌问题，同时还可以消耗并利用电子设备发出的有害蓝光。经过掺杂的二氧化钛材料可以同时解决消毒杀菌和防蓝光的两个问题。

Description

一种二氧化钛杀菌消毒膜 技术领域
本发明涉及二氧化钛材料领域，具体涉及一种二氧化钛杀菌消毒膜。
背景技术
触摸式电子设备在生活中应用广泛，比如生活中使用的手机、平板电脑、公众场所的信息查询机、触摸式教育设备等，人们在使用的时候，脸上的汗液、唾液、油脂会附着在屏幕上，这就为病毒和细菌的产生和存留提供了有利条件。如果刚使用过手机，接着就用手揉擦眼睛或者接触食物，就会将手机上的病毒和细菌带入体内，这样手机就成为了病毒和细菌的传播媒介。除了手机等个人物品外，公共场所的触屏式信息查询机、教学设备、自助结账设备、自助称量器等设备，它们的共有特点就是多人交叉使用，致使病毒和细菌的传播更严重。
对于触摸式电子设备屏幕的病毒和细菌问题，目前最常用的方法是通过酒精和紫外线进行消毒灭菌处理，但是酒精和紫外都有其固有的缺点。酒精消毒的使用频次是有限的，使得交叉感染难以避免。另外，酒精作为易燃液体加之其低沸点特性，易产生安全隐患，其次酒精在使用过程中也可渗入触摸屏的电路元件中，如果这种高精密仪器不具备防水功能则会造成不可逆的损害。紫外线属于有害光线，直接暴露在紫外线对人体健康有影响，不能在有人的环境下使用；不仅如此，紫外线会加速一些材料的老化，对设备本身也有影响。因此使用酒精和紫外消毒灭菌均有一定的局限性，不能及时随地有效进行。
除了应用酒精、紫外线消毒之外，还有在屏幕上应用抗菌玻璃的方案，目前主要是应用如银、铜等抗菌性离子，在一定条件下在玻璃表面置换其它金属离子，让抗菌金属离子植入玻璃基体，使其具有抗菌性能。如中国专利，申请号CN202010334218.6，发明名称：一种抗菌玻璃的制备方法及抗菌玻璃。该发明主要将抗菌的银离子引入玻璃表面使玻璃具有抗菌性能。但由于引入了银离子，银离子容易氧化变色而失效，抗菌效果降低并且影响显示效果；表层的银离子还会缓慢释放，使用后期浓度降低，无法达到长效抗菌等问题。同时使用银离子，还带来了成本较高的问题。因此屏幕不适合使用银离子作为抗菌材料。
发明内容
问题描述与发明简介
在实现本发明的一个实施例的过程中，发明人发现现有技术都没有考虑应用屏幕本身的光源进行主动杀菌消毒的方法。传统方法采用银离子杀菌，主要依赖银离子的释放，杀菌消毒的过程不可控而且效率较低；同时银离子在长期使用后会老化变色，会影响显示效果。应用屏幕本身的光源进行主动消毒，不但可以克服屏幕变色的问题，还可以提高杀菌消毒的效率，并且延长杀菌消毒有益效果持续的时间。在实现本发明的一个实施例的过程中，发明人还发现，在使用屏幕自带光源开展杀菌消毒的方案中，可以通过镀膜或涂膜的手段，将二氧化钛材料附着在屏幕上，有效降低屏幕所发射光线中蓝光的部分。在实现消毒杀菌的同时，还可以实现降低屏幕蓝光的对人体的危害。
蓝光主要指波长处于400nm-480nm之间具有相对较高能量的光线，尤其是波长在450nm以下的蓝光，其能量较高，进入眼睛内后会导致一些眼科疾病，同时对人体健康造成其他负 面影响，是有害的蓝光；而450nm以上的蓝光具有调整生物节律的作用，反而对人体是有益的。在国标“GB/T 38120-2019蓝光防护膜的光健康与光安全应用技术要求”中也提出了相对应的要求。发明人提出了一种屏幕消毒杀菌的方法，实现了精准消除有害蓝光，并利用消除的有害蓝光作为消毒杀菌的能源；同时允许有益蓝光通过。
在实现本发明的一个实施例的过程中，发明人发现在将一种二氧化钛杀菌消毒膜应用于屏幕上，由于屏幕具有光源，可以自发光，二氧化钛可以利用屏幕发出的光进行光催化反应。该杀菌消毒膜的含有二氧化钛材料，二氧化钛材料经过掺杂，可以高效利用屏幕发射出的有害蓝光发生光催化反应，解决电子设备屏幕的病菌问题，同时还可以消耗并利用电子设备发出的有害蓝光。经过掺杂的二氧化钛材料可以同时解决消毒杀菌和防蓝光的两个问题。
本发明的一个实施例涉及的技术方案中，二氧化钛材料经过了氮掺杂或钴掺杂。所述二氧化钛的掺杂方法是通过水解钛醇盐合成制备掺杂的二氧化钛，通过镀膜或涂膜的方法将掺杂的二氧化钛材料镀层至所需的材料表面。
氮掺杂或金属掺杂的二氧化钛可以提升二氧化钛吸收光波的波长，更有效的利用屏幕的光源，提升光催化效率与消毒杀菌的能力。不仅如此，掺杂的二氧化钛还可以有效利用电子屏幕发射出的蓝光，从而降低蓝光对人体的危害。
再一方面，基于相同的思路，本发明掺杂的二氧化钛材料，还适合应用于玻璃、陶瓷、金属、塑料及电子设备等的表面处理。
附图说明
图1实施例一DRS光吸收谱图。
图2实施例二DRS光吸收谱图。
图3实施例三的DRS光吸收谱图。
图4屏幕结构示意图
其中，101为载体，102为二氧化钛镀层。
具体实施方式
基础方案1
本发明的一个实施例涉及的技术方案中，应用了一种二氧化钛杀菌消毒膜，通过在二氧化钛制备过程中引入氮元素的方式制作氮掺杂的二氧化钛材料，通过镀膜或涂膜的方法将掺杂的二氧化钛材料镀层至所需的材料表面。
引入氮元素的方法可以是高温焙烧法、水解沉淀法、有机前驱体热解法、溶胶－凝胶法等。高温焙烧法是指将二氧化钛或其他含钛化合物在空气或含氮气氛中煅烧，所用气体通常为NH 3、N 2或者NH 3和Ar混合气等，通过调节焙烧过程中的温度、气氛、时间等条件可制备不同性质的掺杂TiO 2。水解沉淀法是使用钛盐直接在含氮的水溶液中水解或钛盐水解后再与含氮的物质反应，从而制得掺杂氮的二氧化钛。有机前驱体热解法是用钛盐与含氮有机物 反应，得到含有Ti-N键的有机前驱体，然后在不同的温度和气氛中煅烧，得到掺杂TiO 2。溶胶－凝胶法是将钛醇盐或者钛的无机盐水解，然后使溶质聚合凝胶化，得到二氧化钛。
基础方案2
本发明的一个实施例涉及的技术方案中，应用了一种二氧化钛杀菌消毒膜，通过在二氧化钛制备过程中引入Fe、Cr、Co、Mo等金属元素，掺入到二氧化钛杀中能够改变其电子结构，从而拓宽二氧化钛杀光谱响应范围，通过镀膜或涂膜的方法将掺杂的二氧化钛材料镀层至所需的材料表面。
优选方案1
本实施例提供了一种优选的二氧化钛杀菌消毒膜制备方法，通过对于氮掺杂的方法的控制，可以实现制造出具有高效防蓝光功能的二氧化钛镀层。该二氧化钛杀菌消毒膜应用GB/T38120-2019中的测试方法，可以实现对400-450nm波长的蓝光吸收率为65-80％，对450nm-500nm波长的蓝光吸收率小于30％。同时利用这些光能(包括有害蓝光)作为光催化反应的光源，激发二氧化钛产生主动的消毒杀菌效果。
本发明实现优化的氮掺杂的一个实施例包含如下步骤：
(1)将钛醇盐加入溶剂中搅拌混合得到A液；按质量比钛醇盐∶溶剂＝1∶2～8。
(2)向A液中加入尿素作为掺杂的氮源，并持续混合至尿素完全溶解后形成B液。
(3)将水、溶剂、抑制剂搅拌混合得到C液；按质量比水∶溶剂∶抑制剂＝1～5∶4～18∶0.5～2。
(4)在30～60℃温度下，将C液加入到B液后，调节pH值为1～3，搅拌反应1～6h，制得呈透明的D液。
(6)将D液在20～40℃下恒温陈化12～72h，得到溶胶E，即完成改性掺杂TiO 2溶胶的制备。
其中钛醇盐，结构式为Ti(OR) 4，R＝C xH 2x+1，其中，2≤x≤8。
所述反应原料按质量比钛醇盐∶尿素＝10～50∶1。
进一步地，本发明制备方法所述溶剂为乙醇、乙二醇、异丙醇、异丙二醇中的一种或其组合。所述抑制剂为硝酸、盐酸、硫酸、冰醋酸、乙酰丙酮、二乙醇胺、三乙醇胺中的一种或其组合。
该溶胶E用于二氧化钛杀菌消毒膜的制备。可以使用提拉浸渍、喷涂、滚涂、磁控溅射、气相沉积等的附着方式，将溶胶E中的有效成分附着至所需表面上，制得二氧化钛杀菌消毒膜，所述的表面可以是屏幕、灯以及其他发光元器件的表面。二氧化钛杀菌消毒膜厚度为100-500nm。
优选方案2
本实施例提供了一种优选的二氧化钛杀菌消毒膜制备方法，是通过水解钛醇盐合成制备氮掺杂的二氧化钛，通过镀膜或涂膜的方法将掺杂的二氧化钛材料镀层至所需的材料表面制备二氧化钛杀菌消毒膜。具体制备方法包括如下步骤：
(1)将钛醇盐加入溶剂中搅拌混合得到A液；按质量比钛醇盐∶溶剂＝1∶2～8。
(2)按1～2g/L的比例将Co(NO 3) 2*6H 2O和4～8g/L的比例将氢氟酸共同加入到A液中得到B’液，期间一直进行搅拌。
(3)将水、溶剂、抑制剂搅拌混合得到C’液；按质量比水∶溶剂∶抑制剂＝1～5∶4～18∶0.5～2。
(4)在30～60℃温度下，将混合好的C’液加入到混合好的B’液后，调节pH值为1～3，搅拌反应1～6h，制得呈透明的D’液。
(6)D’液在20～40℃下恒温陈化12-72h，得到溶胶E’，即完成改性掺杂TiO 2溶胶的制备。
该溶胶E用于抗菌与防蓝光层的制备。
其中钛醇盐，结构式为Ti(OR) 4，R＝C xH 2x+1，其中，2≤x≤8；
所述反应原料按质量比钛醇盐∶尿素＝10～50∶1。
本发明所述氢氟酸的质量百分比浓度为35％～45％。
本发明所述硝酸的质量百分比浓度为60％～80％。
进一步地，本发明制备方法所述溶剂为乙醇、乙二醇、异丙醇、异丙二醇中的一种或其组合。所述抑制剂为硝酸、盐酸、硫酸、冰醋酸、乙酰丙酮、二乙醇胺、三乙醇胺中的一种或其组合。
进一步地，步骤(4)中将C’溶液加入B’溶液的方式是滴加的方式。
该溶胶E’用于钴掺杂的二氧化钛杀菌消毒膜的制备。可以使用提拉浸渍、喷涂、滚涂、磁控溅射、气相沉积等的附着方式，将溶胶E’中的有效成分附着至所需表面上，制得二氧化钛杀菌消毒膜，所述的表面可以是屏幕、电子设备、瓷砖等表面。
应用本实施例方法制得的二氧化钛杀菌消毒膜，应用GB/T 38120-2019中的测试方法，对400-450nm波长的蓝光吸收率大于60％-80％，对450nm-500nm波长的蓝光吸收率小于30％。应用本实施例方法制得的二氧化钛杀菌消毒膜可以消耗屏幕产生的有害蓝光，同时利用这些有害蓝光作为光催化反应的光源，激发二氧化钛产生除菌的效果。另外不影响显示的效果。
优选方案3
本发明的一个实施例的技术方案中，涉及对二氧化钛进行氟硅烷改性的的方法，应用氟硅烷改性后的二氧化钛制得的二氧化钛杀菌消毒膜具有疏油、疏水性能，可以减少指纹的油脂在屏幕上的存留，并降低通过接触传播的机会，从而进一步提升抗致病菌的能力。本方法通过水解钛醇盐合成制备二氧化钛溶胶溶液；然后在二氧化钛表面接枝氟改性烷基硅烷而得到氟硅烷改性二氧化钛材料。具体制备方法包括如下步骤：
(1)将钛醇盐加入溶剂中搅拌混合得到A液；按质量比钛醇盐∶溶剂＝1∶2～8。
(2)向A液中加入尿素作为掺杂的氮源，并持续混合至尿素完全溶解后形成B液。或者按1～2g/L的比例将Co(NO 3) 2*6H 2O和4～8g/L的比例将氢氟酸共同加入到A液中得到B’液，期间一直进行搅拌。
(3)将水、溶剂、抑制剂搅拌混合得到C液；按质量比水∶溶剂∶抑制剂＝1～5∶4～18∶0.5～2。
(4)在30～60℃温度下，将C液加入到B液后，调节pH值为1～3，搅拌反应1～6h，制得呈透明的D液。或者在30～60℃温度下，将C液加入到B’液后，调节pH值为1～3，搅拌反应1～6h，制得呈透明的D’液。
(5)在D液中加入氟改性烷基硅烷，在35～55℃温度下搅拌反应2～6h。或在D’液中加入氟改性烷基硅烷，在35～55℃温度下搅拌反应2～6h。
(6)将(5)步骤完成后的D液在20～40℃下恒温陈化12～72h，得到溶胶E，即完成氮掺杂氟硅烷改性的TiO 2溶胶的制备。或将(5)步骤完成后的D’液在20～40℃下恒温陈化12～72h，得到溶胶E’，即完成钴掺杂氟硅烷改性的TiO 2溶胶的制备。
该溶胶E或E’用于抗菌与防蓝光层的制备。
其中钛醇盐，结构式为Ti(OR) 4，R＝C xH 2x+1，其中，2≤x≤8。
其中氟改性烷基硅烷，结构式为R f-(CH 2) n-Si(OR 1) 3，其中，R 1为甲基或乙基，R f为C mF 2m+1或C 6F 5，0≤n≤3，1≤m≤13，n、m均为整数；
所述反应原料按质量比钛醇盐∶氟改性烷基硅烷＝1～10∶1。
所述反应原料按质量比钛醇盐∶尿素＝10～50∶1。
本发明所述氢氟酸的质量百分比浓度为35％～45％。
本发明所述硝酸的质量百分比浓度为60％～80％。
进一步地，本发明制备方法所述溶剂为乙醇、乙二醇、异丙醇、异丙二醇中的一种或其组合。所述抑制剂为硝酸、盐酸、硫酸、冰醋酸、乙酰丙酮、二乙醇胺、三乙醇胺中的一种 或其组合。
进一步地，步骤(4)中将C溶液加入B溶液或者将C’溶液加入B’溶液的方式是滴加的方式。
实施例一
本实施例提供了一种氮掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与55g乙醇混合，混合10min以上后形成A液。
(2)向A液中加入0.5g尿素作为掺杂的氮源，并持续混合至尿素完全溶解后形成B液。
(3)将水15g蒸馏水、3g乙醇、2g乙酰丙酮，1mL质量分数为1％的聚乙二醇水溶液，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在30℃温度下，将混合后的C液加入到混合后的B液后，加入硝酸调节pH值为1，搅拌反应1h，制得呈透明的D液。
(5)将D液在25℃下恒温陈化24h，所得溶胶E，即完成氮掺杂TiO 2浸渍液的制备。
实施例二
本实施例提供了一种氮掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与60g乙醇混合，混合10min以上后形成A液。
(2)向A液中加入1g尿素作为掺杂的氮源，并持续混合至尿素完全溶解后形成B液。
(3)将水15g蒸馏水、5g乙醇、2g乙酰丙酮，1mL质量分数为1％的聚乙二醇水溶液，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在50℃温度下，将C液加入到B液后，加入硝酸调节pH值为2，搅拌反应6h，制得呈透明的D液。
(6)将D液在30℃下恒温陈化48h，所得溶胶E，即完成氮掺杂TiO 2浸渍液的制备。
实施例三
本实施例提供了一种氮掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与100g乙醇混合，混合10min以上后形成A液。
(2)向A液中加入2g尿素作为掺杂的氮源，并持续混合至尿素完全溶解后形成B液。
(3)将水15g蒸馏水、20g乙醇、3g乙酰丙酮，2mL质量分数为1％的聚乙二醇水溶液，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在50℃温度下，将C液加入到B液后，加入硝酸调节pH值为2，搅拌反应6h，制得呈透明的D液。
(5)将溶胶D在30℃下恒温陈化48h，所得溶胶E，即完成氮掺杂TiO 2浸渍液的制备。
实施例四
本实施例提供了一种钴掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与100g乙醇混合，混合10min以上后形成A液。
(2)向A液中加入0.5g的Co(NO 3) 2*6H 2O和2g的氢氟酸,并继续搅拌2小时进行水解反应并充分混合，得到B液。
(3)将水15g蒸馏水、20g乙醇、3g乙酰丙酮，2mL质量分数为1％的聚乙二醇水溶液，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在40℃温度下，将C液加入到B液后，加入硝酸调节pH值为2，搅拌反应2h，制得呈透明的D液。
(5)将溶胶D在30℃下恒温陈化48h，所得溶胶E，即完成钴掺杂TiO 2浸渍液的制备。
本实施例所述氢氟酸的质量百分比浓度为35％-45％。
实施例五
本实施例提供了一种钴掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与100g乙醇混合，混合10min以上后形成A液。
(2)向A液中加入0.5g的Co(NO 3) 2*6H 2O和2g的氢氟酸,并继续搅拌2小时进行水解反应并充分混合，得到B液。
(3)将水15g蒸馏水、20g乙醇、3g乙酰丙酮，2mL质量分数为1％的聚乙二醇水溶液，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在55℃温度下，将C液加入到B液后，加入硝酸调节pH值为5，搅拌反应3h，制得呈透明的D液。
(5)将溶胶D在40℃下恒温陈化36h，所得溶胶E，即完成钴掺杂TiO 2浸渍液的制备。
本实施例所述氢氟酸的质量百分比浓度为35％-45％。
实施例六
本实施例提供了一种钴掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与80g乙醇混合，混合20min以上后形成A液。
(2)向A液中加入0.5g的Co(NO 3) 2*6H 2O和2g的氢氟酸,并继续搅拌2小时进行水解反应并充分混合，得到B液。
(3)将水15g蒸馏水、20g乙醇、3g乙酰丙酮，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在45℃温度下，将C液加入到B液后，加入硝酸调节pH值为6，搅拌反应5h，制得呈透明的D液。
(5)将溶胶D在40℃下恒温陈化36h，所得溶胶E，即完成钴掺杂TiO 2浸渍液的制备。
本实施例所述氢氟酸的质量百分比浓度为35％-45％。
实施例七
本实施例提供了一种氮掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与55g乙醇混合，混合10min以上后形成A液。
(2)向A液中加入0.5g尿素作为掺杂的氮源，并持续混合至尿素完全溶解后形成B液。
(3)将水15g蒸馏水、3g乙醇、2g乙酰丙酮，1mL质量分数为1％的聚乙二醇水溶液，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在30℃温度下，将混合后的C液加入到混合后的B液后，加入硝酸调节pH值为1，搅拌反应1h，制得呈透明的D液。
(5)在D液中加入5g十三氟辛基三乙氧基硅烷，在45℃温度下搅拌反应3h。
(6)将步骤(5)得到的溶液在25℃下恒温陈化24h，所得溶胶E，即完成氮掺杂TiO 2浸渍液的制备。
实施例八
本实施例提供了一种钴掺杂二氧化钛浸渍液制备方法：
(1)将20g钛酸丁酯与100g乙醇混合，混合10min以上后形成A液。
(2)向A液中加入0.5g的Co(NO 3) 2*6H 2O和2g的氢氟酸,并继续搅拌2小时进行水解反应并充分混合，得到B液。
(3)将水15g蒸馏水、20g乙醇、3g乙酰丙酮，2mL质量分数为1％的聚乙二醇水溶液，并混合均匀并持续混合1h，直至形成透明的C液。
(4)在40℃温度下，将C液加入到B液后，加入硝酸调节pH值为2，搅拌反应2h，制得呈透明的D液。
(5)在D液中加入5g十三氟辛基三乙氧基硅烷，在35℃温度下搅拌反应3h。
(6)将步骤(5)得到的溶液在30℃下恒温陈化48h，所得溶胶E，即完成钴掺杂TiO 2浸渍液的制备。
本实施例所述氢氟酸的质量百分比浓度为35％-45％。
实施例九
本发明的一个实施例涉及的技术方案中，二氧化钛杀菌消毒膜制备的步骤如下，用于二氧化钛附着的材料称之为载体，载体可以是玻璃、有机玻璃等材料：
(1)使用蒸馏水清洗载体；蒸馏水清洗后使用0.5-2mol/L的稀盐酸浸泡载体1-3h，以去除其表面的碱性及酸性条件下可溶解的杂质，载体浸泡后取出仍用蒸馏水润洗。
(2)使用质量分数为10-20％的丙酮溶液中浸泡载体1-2h，以去除其表面的有机杂质，浸泡后取出仍用蒸馏水润洗。
(3)将清洗干净的载体用质量分数为10-20％的氢氟酸刻蚀1-2h，刻蚀的目的是使载体表面有一定的粗糙性，有这样利于增加二氧化钛的负载量与负载牢固性；
(4)刻蚀完成后将载体取出并用蒸馏水润洗干净，放入超声清洗仪中，清洗温度设定为50-60℃，频率50kHz，清洗30-60min。清洗完成后将载体移入恒温鼓风干燥箱中在80-100℃下干燥3-6h，冷却后用于负载掺杂的二氧化钛。
(5)附着方式是通过提拉浸渍的方式将掺杂的二氧化钛附着于载体的表面，将配置好的含有二氧化钛的溶胶装入液槽中；将载体垂直插放于定制卡篮中，将卡篮浸渍于液槽中，直至液体全部浸没载体，浸渍时间3-10分钟。
(6)将整卡篮提拉出液面并转移到沥干槽沥干至载体表面表干；将整卡篮转移至烤箱中煅烧并冷却，最后得到附着有掺杂的二氧化钛镀层的载体。
步骤(5)所述二氧化钛的溶胶是氮掺杂或钴掺杂的二氧化钛溶胶。
步骤(6)的煅烧条件为，在载体为玻璃的情况下下，400-600℃煅烧20-40分钟。
优选的，步骤6的煅烧条件为从室温以4～6℃/min升温到95℃～105℃，然后以6～8℃/min升温到195℃～205℃，在195℃～205℃保温10～15min；之后以8～9℃/min升温到395℃～405℃，在395℃～405℃保温10～15min；之后再以8～9℃/min升温到495℃～505℃；再以5～6℃/min升温到600～800℃，并保温30～40min。
应用本实施例制备的二氧化钛杀菌消毒膜厚度为200nm，二氧化钛杀菌消毒膜经过热处理后中含有硅氧烷键，可以使得二氧化钛牢靠的与玻璃相连。经过热处理的二氧化钛的晶型 结构是锐钛矿型。
实施例十
二氧化钛杀菌消毒膜步骤如下：
(1)使用蒸馏水清洗载体；蒸馏水清洗后使用1mol/L的稀盐酸浸泡透明层2h，以去除其表面的碱性及酸性条件下可溶解的杂质，浸泡后取出仍用蒸馏水润洗；
(2)稀盐酸浸泡后使用质量分数为15％的丙酮溶液中浸泡载体2h，以去除其表面的有机杂质，浸泡后取出仍用蒸馏水润洗。
(3)将清洗干净的载体用质量分数为10％的氢氟酸刻蚀2h，刻蚀的目的是使载体表面有一定的粗糙性，有这样利于增加二氧化钛的负载量与负载牢固性；
(4)刻蚀完成后将载体取出并用蒸馏水润洗干净，放入超声清洗仪中，清洗温度设定为60℃，频率50kHz，清洗40min。清洗完成后将载体移入恒温鼓风干燥箱中在90℃下干燥4h，冷却后用于附着掺杂的二氧化钛。
(5)附着方式是通过提拉浸渍的方式将掺杂的二氧化钛附着载体的表面，将配置好的浸渍液装入液槽中；将载体垂直插放于定制卡篮中，将卡篮浸渍于液槽中，直至液体全部浸没载体，浸渍时间5分钟。所述浸渍液使用氮掺杂或者钴掺杂的二氧化钛制备方案制备的溶胶。
(6)将整卡篮提拉出液面并转移到沥干槽沥干至载体层表面表干；将整卡篮转移至烤箱中煅烧并冷却，最后得到附着经掺杂的二氧化钛镀层。所述煅烧的条件为，从室温以5℃/min升温到100℃℃，然后以8℃/min升温到200℃，在200℃保温15min；之后以10℃/min升温到400℃，在400℃保温15min；之后再以8℃/min升温到500℃；再以5℃/min升温到600℃，并保温30min。
应用本实施例制备的二氧化钛杀菌消毒膜厚度为130nm。
实施例十一
为增二氧化钛杀菌消毒膜的防静电性能，可以减少屏幕对病菌、灰尘颗粒的吸附，进一步增强其抗菌的效果，所述掺杂的二氧化钛镀层中包含氧化铬、硫化锌、氧化锆或它们的组合物组成的导电粒子，这些微粒子使得掺杂的二氧化钛镀层的具备防静电性能。
为了减少掺杂的二氧化钛镀层中导电粒子的散射，导电粒子的平均粒径为0.01～1μm。这是由于如果微粒子的平均粒径小于0.01μm时，导电粒子的表面能很大，很容易发生多个粒子团聚而使透光率下降。而如果导电粒子的平均粒径大于1μm时，随着粒径的增大，光散射增强，也会降低镀层的透光率。优选的微粒子的平均粒径为0.05～0.15μm，更优选0.05～0.1μm。含有导电粒子的二氧化钛杀菌消毒膜厚度为400nm。
实施例十二
应用二氧化钛杀菌消毒膜的屏幕，可以在屏幕玻璃的表面采用刻蚀法和涂布法，增加其粗糙度而具备防眩光的效果。利用腐蚀性的药液处理玻璃表面，使玻璃表面经过腐蚀后形成 凹凸不平的微结构而具有散射光的效果。本方法由于与掺杂二氧化钛镀层步骤中使用的化学药剂有重合，因此可以结合掺杂二氧化钛镀层步骤，使得玻璃载体在具备防蓝光和除菌的功能外，还可以具备防眩光的功能。
载体表面蚀刻形成微观结构的工艺步骤及配方如下：先在玻璃制品上涂上一层石蜡，在石蜡表面刻画出矩阵点，露出所需蚀刻的玻璃部分，将玻璃制品浸渍于配制好的蚀刻液中15分钟，最终洗净蚀刻液与石蜡，得到经过蚀刻的玻璃纸制品。蚀刻液的配方为：3％-6％盐酸，0.5％-3％氢氟酸，0.03％-0.1％酸洗缓蚀剂。一种优选的蚀刻液的配方为：4％-5％盐酸，1％氢氟酸，0.05％酸洗缓蚀剂。具有防眩光功能的二氧化钛杀菌消毒膜厚度为300nm。
实施例十三
本发明的一个实施例的技术方案中，涉及一种屏幕的杀菌消毒方法，当检测到屏幕近距离有遮挡物的情况下，如屏幕扣在桌面上的情况、手机在兜内的情况等，则可以提高光源的功率，增强除菌效果。
在检测到屏幕附近无人的情况下，如屏幕附近10、20分钟无人情况，则可以提高光源的功率，利用无人的时间增强除菌效果。
在检测到屏幕设备处于充电状态下，则可以提高光源功率，增强除菌效果。
光谱吸收数据
对实施一、实施例二与实施例三的方法制得的样品进行DRS测试，以考察氮元素的掺杂量对样品的吸收波长的影响，表征结果如图1、图2、图3所示，纯净二氧化钛的禁带宽度为3.2eV，因此其最大吸收波长538nm，而从图1中可以看出，实施例一的最大吸收波长大约在400nm左右，实施例二、实施例三样品对应的DRS谱图是图2和图3，实施例二、实施例三最大吸收波长分别为435nm与457nm。经过氮掺杂的二氧化钛与纯二氧化钛相比已发生明显的红移。DRS的结果表明掺杂氮元素可以有效使二氧化钛的吸收波长增大，向可见光方向发生红移。

Claims (15)

  1. 一种应用于屏幕的二氧化钛杀菌消毒膜，其特征在于，所述杀菌消毒膜含有氮掺杂或金属掺杂的二氧化钛，所述金属包括铁、铬、钴、钼。
  2. 如权利要求1所述的二氧化钛杀菌消毒膜，其特征在于，所述二氧化钛杀菌消毒膜对400-450nm波长的光吸收率大于60％，对450nm以上波长吸收率小于30％。
  3. 如权利要求2所述的二氧化钛杀菌消毒膜，其特征在于，所述二氧化钛杀菌消毒膜的厚度为100-500nm。
  4. 如权利要求2所述的二氧化钛杀菌消毒膜，其特征在于，所述二氧化钛杀菌消毒膜中含有硅氧烷键，二氧化钛的晶型结构为锐钛矿型。
  5. 如权利要求2所述的二氧化钛杀菌消毒膜，其特征在于，所述二氧化钛是氮掺杂的纳米二氧化钛，所述氮掺杂的二氧化钛制备方法如下：
    S1.将钛醇盐与溶剂混合得到A液，按质量比钛醇盐∶溶剂＝1∶2～8；
    S2.A液中加入尿素，得到B液；
    S3.水、溶剂、抑制剂混合得到C液，按质量比水∶溶剂∶抑制剂＝1～5∶4～18∶0.5～2；
    S4.在30～60℃温度下，将C液加入B液后，调节pH值为1～3，搅拌反应1～6h，得到D液；
    S5.将D液20～40℃下恒温陈化12～72h，得到包含氮掺杂的纳米二氧化钛溶胶E。
  6. 如权利要求2所述的二氧化钛杀菌消毒膜，其特征在于，所述二氧化钛是钴掺杂的纳米二氧化钛，所述钴掺杂的二氧化钛的制备方法如下：
    M1.将钛醇盐与溶剂混合得到A液，按质量比钛醇盐∶溶剂＝1∶2～8；
    M2.A液中加入钴金属化合物，得到B’液；
    M3.水、溶剂、抑制剂混合得到C’液，按质量比水∶溶剂∶抑制剂＝1～5∶4～18∶0.5～2；
    M4.在30～60℃温度下，将C’液加入B’液后，调节pH值为1～3，搅拌反应1～6h，得到D’液；
    M5.将D’液20～40℃’下恒温陈化12～72h，得到包含钴掺杂的纳米二氧化钛溶胶E’。
  7. 如权利要求5或6所述的方法，其特征在于，所述溶剂为乙醇、乙二醇、异丙醇、异丙二醇中的一种或其组合。
  8. 如权利要求5或6所述的二氧化钛杀菌消毒膜，其特征在于，所述抑制剂为硝酸、盐酸、 硫酸、冰醋酸、乙酰丙酮、二乙醇胺、三乙胺中的一种或其组合。
  9. 如权利要求5或6所述的二氧化钛杀菌消毒膜，其特征在于，所述纳米二氧化钛镀层的制备方法还包括使用提拉浸渍、喷涂、滚涂或磁控溅射、气相沉积的方法，将溶改性的纳米二氧化钛进行附着。
  10. 如权利要求9所述的二氧化钛杀菌消毒膜，其特征在于，所述的提拉浸渍包括煅烧步骤，煅烧条件为400-600℃煅烧20-40分钟。
  11. 如权利要求5所述的二氧化钛杀菌消毒膜，其特征在于，在步骤S4与步骤S5之间还包括，在D液中加入氟改性烷基硅烷，并在35～55℃温度下搅拌反应2～6h。
  12. 如权利要求6所述的二氧化钛杀菌消毒膜，其特征在于，在步骤M4与步骤M5之间还包括，在D’液中加入氟改性烷基硅烷，并在35～55℃温度下搅拌反应2～6h。
  13. 如权利要求11或12所述的二氧化钛杀菌消毒膜，其特征在于，所述氟改性烷基硅烷的结构式为R f-(CH 2) n-Si(OR 1) 3，其中，R 1为甲基或乙基，R f为C mF 2m+1或C 6F 5，0≤n≤3，1≤m≤13，n、m均为整数。
  14. 一种利用屏幕光杀菌消毒的屏幕，其特征在于，所述屏幕带有权利要求1-6任意一项所述二氧化钛杀菌消毒膜。
  15. 权利要求1-6任一项所述二氧化钛杀菌消毒膜在屏幕中的应用。
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