CN112960910A - Long-acting easy-to-clean antifogging glass lens and manufacturing method thereof - Google Patents
Long-acting easy-to-clean antifogging glass lens and manufacturing method thereof Download PDFInfo
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- CN112960910A CN112960910A CN202110125804.4A CN202110125804A CN112960910A CN 112960910 A CN112960910 A CN 112960910A CN 202110125804 A CN202110125804 A CN 202110125804A CN 112960910 A CN112960910 A CN 112960910A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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- C03C17/25—Oxides by deposition from the liquid phase
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/213—SiO2
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/112—Deposition methods from solutions or suspensions by spraying
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
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Abstract
The invention relates to the technical field of optical glass antifogging, in particular to a long-acting easy-cleaning antifogging glass lens and a manufacturing method thereof. The manufacturing process of the glass lens comprises the process steps of optical cleaning agent ultrasonic cleaning, ultrasonic alkali cleaning and etching, vacuum plasma activation, nano super-hydrophilic anti-fog coating agent coating, baking and curing and the like. The thickness of the anti-fog film layer of the prepared nano long-acting easy-cleaning anti-fog lens is not more than 60 nanometers, and the optical performance of the glass is not influenced. The main material of the film layer is nano silicon dioxide, and the film layer is combined with the surface of the glass through chemical bonds, so that the film layer has excellent wear resistance and weather resistance. The nano long-acting easy-cleaning antifogging lens overcomes the defects of the existing glass antifogging scheme and meets the requirements of the precision optics field on the antifogging glass lens.
Description
Technical Field
The invention relates to the technical field of antifogging of optical glass, in particular to a long-acting easy-cleaning antifogging glass lens and a manufacturing method thereof.
Background
The antifogging of glass generally comprises several forms such as electrothermal antifogging, hydrophilic resin coating antifogging, surfactant coating antifogging and the like. The electric heating antifogging is an antifogging form which evaporates fog quickly by evaporating a semiconductor material such as a nano ITO layer on the surface of glass or attaching a PET film with a heating layer and electrifying and heating the glass. Besides the function of an electrothermal antifogging film only by electrifying, the light transmittance of the conductive film layer is not high, and the application of the conductive film layer in the optical field is limited due to poor durability. The hydrophilic resin coating realizes the antifogging by coating a layer of water-absorbing or hydrophilic modified resin coating on the surface of the glass, the thickness of the hydrophilic resin coating is usually more than 2 microns, the light transmittance of the hydrophilic resin coating is limited, the hardness of the hydrophilic resin coating is less than 1H, and after the surface is polished, the lens can only be used. The antifogging effect of the hydrophilic resin is attenuated along with the aging of the material, and the coating also has the problems of yellowing, cracking, peeling and the like. Surfactant coating antifogging can only be used as a temporary antifogging measure, because the surfactant cannot form effective combination with glass, and is easy to fall off, and the duration of the antifogging effect is difficult to exceed one week. In order to solve the above problems, there is an urgent need for an antifogging glass lens capable of improving the antifogging property of the glass lens and the scratch resistance of the glass lens.
Disclosure of Invention
The invention aims to overcome the defects of the existing glass antifogging scheme, provides an antifogging glass lens which is excellent in optical transmittance, wear-resistant, acid-base resistant, organic solvent resistant and long in service life, and meets the requirements of the precise optical field on the antifogging glass lens.
The purpose of the invention is realized by the following technical scheme: the utility model provides a long-acting antifog glass lens of easily cleaning, the glass lens includes glass matrix, glass micro-etching layer and the super hydrophilic antifog coating layer of nanometer, the glass matrix has at least one side surface to be equipped with glass micro-etching layer and the super hydrophilic antifog modified coating layer of nanometer.
Preferably, the thickness of the glass micro-etching layer is 30-60 nanometers, and the thickness of the nano super-hydrophilic anti-fog modified film layer is 10-60 nanometers.
Preferably, the glass microetching layer is formed by soaking the glass lens in a strong alkaline solution with ultrasonic alkali cleaning.
Preferably, the nano super-hydrophilic antifogging film layer is a non-continuous film layer formed by closely arranging hydrophilic modified nano silicon dioxide, and the nano silicon dioxide and the glass micro-etching layer are chemically combined through Si-O-Si bonds.
Preferably, the material of the glass substrate is one of tempered glass, common white glass, ultra-white glass, soda-lime glass, aluminum-silicon glass, quartz glass, crown optical glass and flint optical glass.
Preferably, the method for manufacturing the long-acting easy-cleaning antifogging glass lens comprises the following steps:
the method comprises the following steps: carrying out ultrasonic cleaning on the glass lens by using an optical cleaning agent;
step two: soaking the glass lens in a heated strong alkali solution, and performing ultrasonic alkali washing and etching;
step three: carrying out ultrasonic cleaning on the glass lens by using clean water and pure water, washing off alkali liquor residues on the surface of the glass lens, and then drying;
step four: activating the surface of the glass lens by using vacuum plasma equipment and introducing mixed gas of oxygen and argon in a certain proportion;
step five: coating a nano super-hydrophilic antifogging coating on the surface of the glass lens, and coating a nano super-hydrophilic antifogging coating agent on the surface of the glass lens in a spraying, dip-coating or smearing mode;
step six: standing the coated glass lens in a clean constant humidity environment for surface drying;
step seven: and placing the coated glass lens in a constant-temperature oven for baking and curing.
Preferably, the super-hydrophilic nano antifogging coating agent takes deionized water and an alcohol solvent as solvents and takes hydrophilic modified nano silicon dioxide as an effective component.
Preferably, the strong alkali solution is one or more of sodium hydroxide and potassium hydroxide, the concentration of the strong alkali solution is 20-30%, the heating temperature of the strong alkali solution is 60-90 ℃, and the time of ultrasonic alkali washing and etching is 30-60 seconds.
Preferably, the vacuum plasma equipment needs to adopt a radio frequency power supply, the plasma processing power is between 600-1000W, the background vacuum degree of the vacuum plasma box is between 10Pa and 35Pa, the ratio of the introduced oxygen to the argon is between 1: 0.5 and 1.2, the flow rate of the mixed gas is 180-300SCCM, and the processing time of the plasma activation is between 180-600 seconds.
Preferably, before the coated lens is placed in an oven for baking, the coated lens must be kept still and surface-dried in a clean environment, the relative humidity of the static environment is controlled to be 50-80%, and the standing time is 8-15 minutes.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the long-acting easy-cleaning antifogging glass lens perfectly solves the antifogging problem of the optical lens, the thickness of the nanometer super-hydrophilic antifogging film layer does not exceed 60 nanometers, the optical performance of the glass is not affected completely, and the nanometer super-hydrophilic antifogging film layer is mainly made of nanometer silicon dioxide and is combined with the surface of the glass through chemical bonds, so that the long-acting easy-cleaning antifogging glass lens has excellent wear resistance, acid and alkali resistance, organic solvent resistance and ageing resistance. The glass lens disclosed by the invention can prevent fog for a long time, the nano super-hydrophilic anti-fog film layer on the surface of the lens also has good cleanability, the lens glass sheet is stained with various stains when in use, the lens glass sheet can be recovered to be clean only by being wiped by wet cloth or being washed by clear water without using a cleaning agent, and the glass lens can be used in an environment frequently washed by rainwater and can also keep the surface clean and transparent for a long time.
(2) The invention provides a long-acting easy-cleaning antifogging glass lens and a preparation method thereof. And then more silicon hydroxyl groups with high reaction activity are formed on the surface of the glass through plasma activation. The core material of the nano super-hydrophilic antifogging coating agent adopted by the invention is nano silicon dioxide particles with one side provided with silicon hydroxyl and the other side provided with hydrophilic modified groups. After the coating material is coated on the surface of glass, nano silicon dioxide particles can be self-assembled on the surface of the glass, one side with silicon hydroxyl faces inwards, and the nano silicon dioxide particles and the silicon hydroxyl on the surface of the glass are subjected to condensation reaction to finally form a compact and firm nano super-hydrophilic anti-fog film layer.
Drawings
FIG. 1 is a schematic view of the structural principle of the nano-sized super-hydrophilic anti-fog film layer in the present invention;
FIG. 2 is a cross-sectional model view of a glass lens structure according to the present invention;
wherein, 1 is a glass lens; 2, a silicon hydroxyl group; 3, hydrophilic modified nano silicon dioxide; 4 a superhydrophilic modifying group.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "connected," and the like are to be construed broadly, such as "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance. Wherein the terms "first position" and "second position" are two different positions.
The invention provides a long-acting easy-cleaning antifogging glass lens which comprises a glass substrate, a glass micro-etching layer and a nano super-hydrophilic antifogging film layer, wherein the glass micro-etching layer and the nano super-hydrophilic antifogging modified film layer are arranged on the surface of at least one side of the glass substrate. The thickness of the glass micro-etching layer is 30-60 nanometers, and the thickness of the nano super-hydrophilic anti-fog modified film layer is 10-60 nanometers, so that the scratch resistance and the anti-fog performance of the glass lens are improved on the premise that the original light transmission performance of the glass lens is not influenced. The glass micro-etching layer is formed by soaking a glass lens in a strong alkali solution through ultrasonic alkali washing, the nano super-hydrophilic anti-fog film layer is a non-continuous film layer formed by closely arranging hydrophilic modified nano silica particles, and the nano silica and the glass micro-etching layer are chemically combined through Si-O-Si bonds formed by condensation of silicon hydroxyl groups on two sides, so that the formed nano super-hydrophilic anti-fog film layer is compact and firm, is good in wear resistance, does not influence the optical performance of the glass lens, and meets the requirements of the precision optics field on the anti-fog glass lens. Preferably, the glass substrate is made of one of tempered glass, common white glass, super-white glass, soda-lime glass, aluminum-silicon glass, quartz glass, crown optical glass and flint optical glass, so that the application range of the glass lens is further expanded.
A method for manufacturing a long-acting easy-cleaning antifogging glass lens comprises the following steps:
the method comprises the following steps: and (3) carrying out ultrasonic cleaning on the glass lens by using an optical cleaning agent, preferably, the ultrasonic frequency is 40-45KHz, the temperature of the optical cleaning agent is 40-80 ℃, and the cleaning time is 1-5min, so as to remove pollutants on the surface of the glass lens.
Step two: soaking a glass lens in a heated strong alkali solution, performing ultrasonic alkali washing etching, preferably, the strong alkali solution is one or more of sodium hydroxide and potassium hydroxide, the concentration of the strong alkali solution is between 20 and 30 percent, the heating temperature of the strong alkali solution is between 60 and 90 ℃, and the time of the ultrasonic alkali washing etching is 30 to 60 seconds, through the step, not only oily pollutants on the surface of the glass lens are removed, but also micro corrosion can be formed on the surface of the glass lens, so that microscopic roughness is caused on the surface of the glass lens, similar to sand blasting treatment before metal coating, on the premise of not damaging the optical performance of the glass lens, nano super-hydrophilic particles are embedded into a concave structure on the surface of the glass, and the reaction interface between the surface of the glass and the nano super-hydrophilic anti-fog material is increased, is beneficial to improving the coating density and the adhesive force of the super hydrophilic film.
Step three: and ultrasonically cleaning the glass lens by using clean water and pure water, washing off alkali liquor residues on the surface of the glass lens, and drying. Preferably, the glass lens can be subjected to ultrasonic cleaning twice by using clean water, and then the glass lens can be subjected to ultrasonic cleaning once by using pure water, wherein the ultrasonic frequency is 40-45KHz, the temperature of the clean water and the temperature of the pure water are 60-80 ℃, and the cleaning time is 3-8 min. The drying time of the lens is not more than 3min, the surface temperature of the lens is not more than 80 ℃, and the problem that the activity of the lens is lost due to dehydration of hydroxyl of a micro-corrosion layer on the surface caused by over-drying of the lens is avoided.
Step four: the method comprises the steps of using a vacuum plasma device, introducing mixed gas of oxygen and argon in a certain proportion to carry out activation treatment on the surface of the glass lens, wherein the vacuum plasma device needs to adopt a radio frequency power supply, the plasma treatment power is 600-1000W, the background vacuum degree of a vacuum plasma box is 10-35 Pa, the proportion of the introduced oxygen and the argon is 1: 0.5-1.2, the flow rate of the mixed gas is 180-300SCCM, and the treatment time of plasma activation is 180-600 seconds, so that the silicon hydroxyl density on the surface of the micro-etched layer on the glass lens is further increased.
Step five: the method comprises the following steps of coating a nano super-hydrophilic antifogging coating on the surface of a glass lens, and coating the nano super-hydrophilic antifogging coating on the surface of the glass lens in a spraying, dip-coating or smearing mode. The super-hydrophilic nano antifogging coating agent takes deionized water and an alcohol solvent as solvents, takes hydrophilic modified nano silicon dioxide as an effective component, and does not contain any organic film forming substance. The particle size of the super-hydrophilic modified nano silicon dioxide is 10-30 nanometers, and the super-hydrophilic modified nano silicon dioxide is synthesized by acid catalytic hydrolysis of tetraethoxysilane. Ethanol is added as a solvent in the synthesis process, and the generation speed and the particle size of the nano-silicon dioxide particles are controlled by adjusting the reaction temperature, the pH value and the proportion of the ethyl orthosilicate acid to the solvent and the water. After the nano silicon dioxide is synthesized, hydrophilic modifier is added. The hydrophilic modifier and silicon hydroxyl on the surface of the nano silicon dioxide particles are subjected to condensation reaction, so that the hydrophilic modifier is attached to the surface of the nano silicon dioxide particles. The single-side modification of the nano silicon oxide particles is realized by controlling the adding speed and the proportion of the modifier. One side of the modified nano silicon dioxide particle is silicon hydroxyl, and the other side is a super-hydrophilic modification group. After the nano super-hydrophilic antifogging coating agent is coated on the surface of activated glass, the side of the hydrophilic modified nano-silica with the super-hydrophilic modified groups faces outwards, the side with the hydroxyl groups faces inwards and is subjected to condensation reaction with silicon hydroxyl groups on a glass lens, and finally a layer of compact non-continuous film with super-hydrophilic surface is formed. After water vapor is condensed on the surface of the super-hydrophilic glass, the water vapor can be automatically spread and flattened to form a water film with uniform thickness. The water film can be regularly transmitted by light (less diffuse reflection and scattering), which is the principle of antifogging of the super-hydrophilic film. Furthermore, the film forming mechanism of the nano super-hydrophilic anti-fog film is different from that of the traditional organic resin coating agent, and the essence is that molecules on the surface of the glass are subjected to hydrophilic modification instead of coating the surface of the glass with a hydrophilic resin coating to form a film. Compared with the glass lens in the prior art, the hardness of the nano super-hydrophilic antifogging film on the surface of the glass lens is more than or equal to 7H, and the 1-level antifogging effect can be still maintained after the wet dust-free cloth loaded with 1000 g of weights is repeatedly rubbed for 3000 times. Compared with the anti-fog lens made of the hydrophilic resin coating, the anti-fog film disclosed by the invention has poor solvent resistance, and can still maintain the 1-level anti-fog effect after the dust-free cloth loaded with 1000 g of weight is repeatedly rubbed with the alcohol solvent for 1000 times.
Step six: the coated glass lens is statically placed in a clean constant-humidity environment to be surface-dried, preferably, before the coated glass lens is placed in an oven to be baked, the coated glass lens is statically placed in the clean environment to be surface-dried, the relative humidity of the static environment is controlled to be 50-80%, and the static time is 8-15 minutes, so that the nano super-hydrophilic antifogging coating agent is subjected to sufficient self-assembly reaction on the surface of the glass lens, and the film forming density of the nano super-hydrophilic antifogging film is improved.
Step seven: and (3) placing the coated glass lens in a constant-temperature oven for baking and curing, preferably, the baking temperature is 80-140 ℃, and the baking time is 1h, so that moisture generated by the bonding reaction of the nano particles and the surface of the glass is removed in an accelerated manner, the reaction is carried out more fully and completely, and the formed nano film layer is compact and firm.
Example 1:
the method for manufacturing the surface super-hydrophilic anti-fog glass lens provided by the embodiment comprises the following steps:
the method comprises the following steps: carrying out ultrasonic cleaning on the glass lens by using an optical cleaning agent, wherein the ultrasonic frequency is 40KHz, the temperature of the optical cleaning agent is 40 ℃, and the cleaning time is 1 min;
step two: soaking the glass lens in a heated strong alkali solution, and performing ultrasonic alkali washing etching, wherein the ultrasonic frequency is 40KHz, the concentration of the strong alkali solution is 20%, the temperature of the strong alkali solution is 60 ℃, and the alkali washing time is 15 seconds;
step three: carrying out ultrasonic cleaning on the glass lens by using clean water and pure water, washing off alkali liquor residues on the surface of the glass lens, and then drying, wherein the ultrasonic frequency is 40KHz, and the temperatures of the clean water and the pure water are 10 ℃;
step four: activating the surface of the glass lens by using vacuum plasma equipment and introducing mixed gas of oxygen and argon in a certain ratio, wherein the power is 600w, the activation time is 10min, the background vacuum degree of a vacuum plasma box is 10Pa, the ratio of the oxygen to the argon is 1: 0.5, and the flow rate of the mixed gas is 180 SCCM;
step five: coating a nano super-hydrophilic anti-fog coating on the surface of a glass lens, coating a nano super-hydrophilic anti-fog coating agent on the surface of the glass lens in a dip-coating mode, keeping the nano super-hydrophilic anti-fog coating agent to circularly flow in the dip-coating process, wherein the dip-coating time is 30 seconds, and after dip-coating, slowly pulling the glass lens out of a nano super-hydrophilic coating agent groove at the pulling speed of 2 cm/min;
step six: standing the coated glass lens in a clean constant-humidity environment for drying, wherein the constant-temperature environment is a thousand-level dust-free space with the temperature of 12 ℃ and the relative humidity of 50%, and the standing time is 10 min;
step seven: and (3) placing the coated glass lens in a constant-temperature oven for baking and curing, wherein the baking temperature is 80 ℃, and the baking time is 1 h.
The prepared glass lens is respectively tested for water contact angle, surface hardness, light transmittance, scratch resistance, solvent resistance, ultraviolet aging resistance and salt spray resistance. The test results are shown in table one.
Example 2:
the method for manufacturing the surface super-hydrophilic anti-fog glass lens provided by the embodiment comprises the following steps:
the method comprises the following steps: carrying out ultrasonic cleaning on the glass lens by using an optical cleaning agent, wherein the ultrasonic frequency is 43KHz, the temperature of the optical cleaning agent is 60 ℃, and the cleaning time is 3 min;
step two: soaking the glass lens in a heated strong alkali solution, and performing ultrasonic alkali washing etching, wherein the ultrasonic frequency is 43KHz, the concentration of the strong alkali solution is 25%, the temperature of the strong alkali solution is 75 ℃, and the alkali washing time is 23 seconds;
step three: carrying out ultrasonic cleaning on the glass lens by using clean water and pure water, washing off alkali liquor residues on the surface of the glass lens, and then drying, wherein the ultrasonic frequency is 43KHz, and the temperatures of the clean water and the pure water are 22 ℃;
step four: activating the surface of the glass lens by using vacuum plasma equipment and introducing mixed gas of oxygen and argon in a certain ratio, wherein the power is 800w, the activation time is 6min, the background vacuum degree of a vacuum plasma box is 22Pa, the ratio of the oxygen to the argon is 1: 0.9, and the flow rate of the mixed gas is 240 SCCM;
step five: the method comprises the following steps of coating a nano super-hydrophilic anti-fog coating on the surface of a glass lens, coating a nano super-hydrophilic anti-fog coating agent on the surface of the glass lens in a dip-coating mode, keeping the nano super-hydrophilic anti-fog coating agent to flow circularly in the dip-coating process, wherein the dip-coating time is 75 seconds, slowly lifting the glass lens out of a nano super-hydrophilic coating agent groove after dip-coating, and the lifting speed is 2 cm/min.
Step six: standing the coated glass lens in a clean constant-humidity environment for drying, wherein the constant-temperature environment is a thousand-level dust-free space with the temperature of 23 ℃ and the relative humidity of 50%, and the standing time is 10 min;
step seven: and (3) placing the coated glass lens in a constant-temperature oven for baking and curing, wherein the baking temperature is 110 ℃, and the baking time is 1 h.
The prepared glass lens is respectively tested for water contact angle, surface hardness, light transmittance, scratch resistance, solvent resistance, ultraviolet aging resistance and salt spray resistance. The test results are shown in table one.
Example 3:
the method for manufacturing the surface super-hydrophilic anti-fog glass lens provided by the embodiment comprises the following steps:
the method comprises the following steps: carrying out ultrasonic cleaning on the glass lens by using an optical cleaning agent, wherein the ultrasonic frequency is 45KHz, the temperature of the optical cleaning agent is 80 ℃, and the cleaning time is 5 min;
step two: soaking the glass lens in a heated strong alkali solution, and performing ultrasonic alkali washing etching, wherein the ultrasonic frequency is 45KHz, the concentration of the strong alkali solution is 30%, the temperature of the strong alkali solution is 90 ℃, and the alkali washing time is 30 seconds;
step three: carrying out ultrasonic cleaning on the glass lens by using clean water and pure water, washing off alkali liquor residues on the surface of the glass lens, and then drying, wherein the ultrasonic frequency is 45KHz, and the temperatures of the clean water and the pure water are 35 ℃;
step four: activating the surface of the glass lens by using vacuum plasma equipment and introducing mixed gas of oxygen and argon in a certain ratio, wherein the power is 1000w, the activation time is 8min, the background vacuum degree of a vacuum plasma box is 35Pa, the ratio of the oxygen to the argon is 1: 1.5, and the flow rate of the mixed gas is 300 SCCM;
step five: coating a nano super-hydrophilic anti-fog coating on the surface of a glass lens, coating a nano super-hydrophilic anti-fog coating agent on the surface of the glass lens in a spraying mode, wherein the aperture of a nozzle used for spraying is 0.5mm, the flow rate of the coating agent is 1ml/s, the air inlet pressure is 3bar, the distance between the nozzle and the lens is 10mm, the transverse moving speed of a spray gun is 2cm/s, and the nano super-hydrophilic anti-fog coating agent is sprayed transversely once;
step six: standing the coated glass lens in a clean constant-humidity environment for drying, wherein the constant-temperature environment is a thousand-level dust-free space with the temperature of 23 ℃ and the relative humidity of 50%, and the standing time is 10 min;
step seven: and (3) placing the coated glass lens in a constant-temperature oven for baking and curing, wherein the baking temperature is 140 ℃, and the baking time is 1 h.
The prepared glass lens is respectively tested for water contact angle, surface hardness, light transmittance, scratch resistance, solvent resistance, ultraviolet aging resistance and salt spray resistance. The test results are shown in table one.
Comparative example 1: a preparation method of antifogging glass comprises the steps of firstly selecting one of glass for producing mirrors, glasses lenses, automobile reflectors, window glass and optical instrument glass, wherein the specification of the glass is 1m multiplied by 1m, washing and drying the glass, and then carrying out hydroxylation treatment on the glass, wherein the specific hydroxylation method comprises the following steps: placing the glass in hydrogen peroxide at the temperature of 40-60 ℃, ultrasonically soaking for 30-40 min, taking out the hydrogen peroxide washed out of the surface to obtain hydroxylated glass, then selecting one surface as a front surface, coating a cross-linking agent on the selected front surface of the glass, wherein the cross-linking agent is a mixture of acrylic ester and aliphatic dicarboxylic anhydride, and the mass ratio of the acrylic ester to the aliphatic dicarboxylic anhydride is 1: 1-3. Irradiating the coated ultraviolet ray for 30min to cure the cross-linking agent layer 2, then plating an antifogging layer on the surface of the cross-linking agent layer, wherein the antifogging layer is a hydrophilic coating of polymer or monomer containing hydrophilic functional groups, irradiating the coated ultraviolet ray for 20min to cure the cross-antifogging layer 3, the coating structure formed by the cross-linking agent layer 2 and the cross-antifogging layer 3 is an antifogging coating 23, then spraying the cross-linking agent same as the cross-linking agent layer 2 on the surface of the antifogging coating 23 to activate the surface of the antifogging coating 23, treating for 25min under the action of ultrasound, wherein the ultrasonic frequency is 0.1-0.5 MHz, washing with water to remove the redundant cross-linking agent on the surface, then coating the surface of the antifogging coating 23 with hydrogel mixed by silicone gel and acrylamide in a mass ratio of 1:5, irradiating the coated ultraviolet ray for 35min to cure the hydrogel, then, the surface of the hydrogel coating layer is coated with PU emulsion, and because the concentration of the PU emulsion is higher, the water filled in the grid in the hydrogel coating layer is replaced to form a PU glue-gel structure, namely a protective layer 4, wherein the silica gel glue can effectively absorb water and play a role of water storage, so that the provided antifogging glass can have an antifogging function for a long time. The hydroxyl group on the surface of the activated antifogging coating 23 is combined with the hydroxyl, carboxyl and amino in the hydrogel coating layer through hydrogen bonds or covalent bonds, so that the adhesive force between the hydrogel coating layer and glass is greatly improved, the hydrogel coating layer is firmly adhered and is not easy to fall off
And respectively testing the water contact angle, the surface hardness, the light transmittance, the scratch resistance, the solvent resistance, the ultraviolet aging resistance and the salt spray resistance of the glass. The test results are shown in table one.
Water contact angle test method: the water contact angle of the antifogging wear-resistant resin coating is measured by adopting an automatic contact angle measuring instrument DSA-X plus of Bituo scientific instruments GmbH.
The light transmittance test method comprises the following steps: the original light transmittance of the glass substrate is 91.5 percent, and the light transmittance is measured after film coating.
Scratch resistance test method: and (3) loading a 1 kg weight on the water-wet dust-free cloth, performing wiping for 3000 times by a stroke of 6CM, and measuring the antifogging according to GBT 31726-.
Solvent resistance test method: the absolute ethyl alcohol wets the dust-free cloth to load a weight of 1 kilogram, the stroke is 6CM, and after 1000 times of wiping, the antifogging is measured according to GBT 31726-.
The ultraviolet aging resistance test method comprises the following steps: the irradiation of UVA-340 is 0.89W/square meter/min, and the antifogging is measured according to GBT 31726 once per minute after the irradiation is carried out for 240 hours.
The salt spray resistance test method comprises the following steps: the temperature of the salt spray box is 35 ℃, 5 percent sodium chloride solution is exposed for 120 hours, and then the antifogging is measured according to GBT 31726-.
Table one:
as shown in the table I, by adopting the long-acting easy-cleaning antifogging glass lens and the manufacturing method thereof, the prepared antifogging film layer on the surface of the glass lens has no influence on the light transmittance of a glass lens substrate, and the wear resistance, the alcohol washing resistance, the ultraviolet aging resistance and the salt fog resistance of the antifogging film layer can meet the requirements of precise optical precision for long-term use. As can be seen from the examples 1, 2 and 3, the scratch resistance, solvent resistance, ultraviolet aging resistance and salt fog resistance of the antifogging film layer on the surface of the glass lens are better than those of the glass and the antifogging material in the comparative example 1, so that the performance of the antifogging film plated on the glass lens is revolutionarily improved compared with the performance of the traditional various antifogging materials.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A long-acting easy-to-clean antifogging glass lens is characterized in that: the glass lens comprises a glass substrate, a glass micro-etching layer and a nano super-hydrophilic anti-fog film layer, wherein the glass substrate is provided with the glass micro-etching layer and the nano super-hydrophilic anti-fog modified film layer on at least one side surface.
2. The long-acting easy-to-clean anti-fog glass lens as claimed in claim 1, wherein: the thickness of the glass micro-etching layer is 30-60 nanometers, and the thickness of the nano super-hydrophilic anti-fog modified film layer is 10-60 nanometers.
3. The long-acting easy-to-clean anti-fog glass lens as claimed in claim 1, wherein: the glass microetching layer is formed by soaking a glass lens in a strong alkaline solution and performing ultrasonic alkali washing.
4. The long-acting easy-to-clean anti-fog glass lens as claimed in claim 1, wherein: the nano super-hydrophilic antifogging film layer is a non-continuous film layer formed by closely arranging hydrophilic modified nano silicon dioxide particles, and the nano silicon dioxide and the glass micro-etching layer are chemically combined through Si-O-Si bonds.
5. The long-acting easy-to-clean anti-fog glass lens as claimed in claim 1, wherein: the glass substrate is made of one of toughened glass, common white glass, super-white glass, soda-lime glass, aluminum-silicon glass, quartz glass, crown optical glass and flint optical glass.
6. The method for manufacturing the long-acting easy-cleaning antifogging glass lens according to any one of claims 1 to 5, comprising the following steps:
the method comprises the following steps: carrying out ultrasonic cleaning on the glass lens by using an optical cleaning agent;
step two: soaking the glass lens in a heated strong alkali solution, and performing ultrasonic alkali washing and etching;
step three: carrying out ultrasonic cleaning on the glass lens by using clean water and pure water, washing off alkali liquor residues on the surface of the glass lens, and then drying;
step four: using vacuum plasma equipment and introducing mixed gas of oxygen and argon in a certain proportion to carry out plasma activation treatment on the surface of the glass lens;
step five: coating a nano super-hydrophilic antifogging coating on the surface of the glass lens, and coating a nano super-hydrophilic antifogging coating agent on the surface of the glass lens in a spraying, dip-coating or smearing mode;
step six: standing the coated glass lens in a clean constant humidity environment for surface drying;
step seven: and placing the coated glass lens in a constant-temperature oven for baking and curing.
7. The method for manufacturing the long-acting easy-to-clean anti-fog glass lens according to claim 6, wherein the method comprises the following steps: the super-hydrophilic nano antifogging coating agent takes deionized water and an alcohol solvent as solvents, takes hydrophilic modified nano silicon dioxide as an effective component, and does not contain an organic film forming substance.
8. The method for manufacturing the long-acting easy-to-clean anti-fog glass lens according to claim 6, wherein the method comprises the following steps: the strong alkali solution is one or more of sodium hydroxide and potassium hydroxide, the concentration of the strong alkali solution is 20-30%, the heating temperature of the strong alkali solution is 60-90 ℃, and the time of ultrasonic alkali washing and etching is 30-60 seconds.
9. The method for manufacturing the long-acting easy-to-clean anti-fog glass lens according to claim 6, wherein the method comprises the following steps: the vacuum plasma equipment needs to adopt a radio frequency power supply, the plasma processing power is between 600 and 1000W, the background vacuum degree of the vacuum plasma box is between 10 and 35Pa, the ratio of the introduced oxygen to the argon is between 1 to 0.5 and 1.2, the flow rate of the mixed gas is 180 and 300SCCM, and the processing time of the plasma activation is between 180 and 600 seconds.
10. The method for manufacturing the long-acting easy-to-clean anti-fog glass lens according to claim 6, wherein the method comprises the following steps: before the coated lens is placed in an oven for baking, the coated lens is required to be kept stand and dried in a clean environment, the relative humidity of the standing environment is controlled to be 50-80%, and the standing time is 8-15 minutes.
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