CN111205677A - Silicon oxide-zirconium oxide composite sol for lens film, preparation method and application method thereof - Google Patents

Silicon oxide-zirconium oxide composite sol for lens film, preparation method and application method thereof Download PDF

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CN111205677A
CN111205677A CN202010022995.7A CN202010022995A CN111205677A CN 111205677 A CN111205677 A CN 111205677A CN 202010022995 A CN202010022995 A CN 202010022995A CN 111205677 A CN111205677 A CN 111205677A
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唐正霞
陈晓玉
王威
戴旭
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Jinling Institute of Technology
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Abstract

The invention discloses a silicon oxide-zirconium oxide composite sol for a lens film, a preparation method and an application method thereof, belonging to the technical field of film preparation. The method comprises the following steps: step one, measuring water and absolute ethyl alcohol, and uniformly mixing to prepare an ethanol solution; step two, dropwise adding Tetraethoxysilane (TEOS) into the ethanol solution, and uniformly stirring to prepare TEOS alcohol solution; step three, weighing zirconium oxychloride (ZrOCl)2·8H2O) is dissolved in distilled water to prepare ZrOCl2An aqueous solution; step four, TEOS alcoholic solution and ZrOCl2Uniformly mixing the aqueous solution, and magnetically stirring for 3-4 hours at normal temperature; step five, dripping a silane coupling agent into the mixed solution while stirring, and continuously stirring for 30 minutes; step six, stopping stirring, standing and aging for 1-3 daysTo obtain the silica-zirconia composite sol. The invention prepares the silicon oxide/zirconium oxide hardened composite film by zirconium oxychloride and tetraethoxysilane, and the silicon zirconium composite film obviously improves the hardness of a resin matrix on the basis of not reducing the transmissivity.

Description

Silicon oxide-zirconium oxide composite sol for lens film, preparation method and application method thereof
Technical Field
The invention belongs to the technical field of film preparation, and particularly relates to a silicon oxide-zirconium oxide composite sol for a lens film, a preparation method and an application method thereof.
Background
After 1970, resin materials began to appear and replace glass materials as new materials for lenses, and the application of resin lenses led to rapid development of vision technology due to the light weight, excellent optical properties such as light transmittance and dispersion, and good impact resistance of resin materials.
There are generally three types of resin lenses: allyl diglycol carbonate (CR-39), polymethyl methacrylate (PMMA) and Polycarbonate (PC). Compared with the traditional glass lens, the resin lens is widely applied to the market due to the advantages, but the resin lens has low surface hardness and is easy to scratch, so that the service life of the resin lens is short, and therefore, the surface hardening treatment is very important for the resin lens.
The hardness of the resin material is not as good as that of the glass material, but after the surface of the resin material is subjected to organic silicification treatment, a protective layer is formed on the inner surface and the outer surface of the resin material after a hard film is prepared, and the existence of the protective layer greatly increases the friction resistance of the resin material, so that the friction resistance of the surface of the resin material can be very close to that of a common glass lens.
Currently, the hardness of the resin is increased by modifying the surface interface of the lens material. Because the nano silicon dioxide has excellent performance, the preparation of the silicon oxide hardened film on the resin substrate becomes a new research hotspot. However, it has been found that, because the resin substrate and the silicon oxide have a large difference, how to increase the bonding force between the surface of the resin lens and the silicon oxide becomes an important problem in the thin film plating process.
As described above, although resin is a widely used material for a viewing lens, hardening is an indispensable process due to low hardness of resin, and an antireflection coating treatment is required after the hardening process in order to increase the transmittance. In actual production, hard coating and antireflection film are added in two steps, the hard coating is plated by using a dip plating hard coating liquid heating and curing method, and the antireflection film is plated by using a physical vapor deposition method, so that equipment is expensive and the operation is complex.
Disclosure of Invention
The invention aims to solve the technical problems in the background technology and provides a low-cost method for preparing a film with a hardening and anti-reflection composite function on a resin substrate in one step.
The invention is realized by the following technical scheme: the preparation method of the silicon oxide-zirconium oxide composite sol applied to the lens film specifically comprises the following steps:
step one, measuring water and absolute ethyl alcohol, and uniformly mixing to prepare an ethanol solution;
step two, dropwise adding Tetraethoxysilane (TEOS) into the ethanol solution, and uniformly stirring to prepare TEOS alcohol solution;
step three, weighing zirconium oxychloride (ZrOCl)2·8H2O) is dissolved in distilled water to prepare ZrOCl2An aqueous solution;
step four, TEOS alcoholic solution and ZrOCl2Uniformly mixing the aqueous solution, and magnetically stirring for 3-4 hours at normal temperature;
step five, dripping a silane coupling agent into the mixed solution while stirring, and continuously stirring for 25-40 minutes;
and step six, stopping stirring, standing and aging for 1-3 days to obtain the silicon oxide-zirconium oxide composite sol.
In further examples, the volume ratio of water to absolute ethanol is as follows:
Vwater (W)∶VEthanol＝1∶15～1∶5；
The volume ratio of the absolute ethyl alcohol to the tetraethoxysilane is as follows:
Vethanol∶VTetraethoxysilane＝4∶1～6∶1；
The volume ratio of the silane coupling agent to the tetraethoxysilane is as follows:
Vsilane coupling agent∶VTetraethoxysilane＝6∶26～8∶27
In a further embodiment, the molar ratio of the zirconium oxychloride to the tetraethoxysilane is 1: 0.5 to 1: 2.
In a further embodiment, hydrolysis and condensation reactions occur;
wherein the hydrolysis reaction is as follows:
Si(OC2H5)4+H2O→Si(OC2H5)3OH+C2H5OH
Zr4++(16-x)H2O+xC2H5OH→[Zr4(OH)8(H2O)16-X(C2H5OH)X]8+；
the condensation reaction is as follows:
2Si(OC2H5)3OH→[(OC2H5)3-Si-O-Si-(OC2H5)3]+H2O
[Zr4(OH)8(H2O)16-X(C2H5OH)X]Cl8→
[Zr4(OH)12(C2H5OH)X(H2O)12-X]Cl4+4HCl；
the generated HCl is used for adjusting the pH value of the sol to make the sol acidic.
In a further embodiment, the hydrolysis and condensation reactions occur simultaneously with the following reactions:
(1) hydrolysis of polysiloxanes to give C2H5OH：
≡Si-OC2H5+H2O→≡Si-OH+C2H5OH
(2) Decomposition of the zirconium salt complex produces HCl:
[Zr4(OH)12(C2H5OH)X(H2O)12-X]Cl4→[Zr4(OH)12(C2H5OH)X(H2O)8-X]+4HCl
(3) the surface ethoxy group undergoes oxidation reaction in air to generate peroxide:
≡Si-OC2H5+O2→≡Si-OC2H4-O-OH→≡Si-OH+CH3COOH。
a composite sol of silicon oxide and zirconium oxide for the film of lens is prepared from water, absolute alcohol, ethyl orthosilicate, zirconium oxychloride and silane coupling agent.
The use of the silica-zirconia composite sol for a lens film as described above in a lens film.
In a further embodiment, the method specifically comprises the following steps:
101, ultrasonically cleaning a resin substrate for 4-6min by using a washing powder solution;
step 102, washing the substrate with distilled water;
103, putting the cleaned resin substrate into NaOH solution to perform ultrasonic cleaning for 4-6 min;
104, ultrasonically cleaning the resin substrate in distilled water at normal temperature for 4-6min to remove NaOH residues;
105, ultrasonically cleaning the mixture for 4-6min by using absolute ethyl alcohol at normal temperature;
step 106, taking out the resin sheet and drying the resin sheet for later use;
step 107, coating the prepared silica-zirconia composite sol on the surface of resin;
and 108, putting the resin coated with the sol into an oven at the temperature of 60-80 ℃ for annealing for 60-70 minutes.
In a further embodiment, the coating in step 107 is performed by dip-coating.
In a further embodiment, the spin coating in step 107 is performed.
The invention has the beneficial effects that: according to the invention, the silicon oxide/zirconium oxide hardened composite film is prepared by zirconium oxychloride and tetraethoxysilane, and a hydrolysate of tetraethoxysilane is self-condensed and a coordination ion is self-condensed to generate autocatalytic H & lt + & gt in the process so as to adjust the pH value of the whole sol; and M (H) formed by hydrolysis2O)n z+The product M (OH) is dehydrated or alcoholyzed intermolecularlynDealcoholizing to form-M-O-M-network structure to ensure the silicon-zirconium composite film onThe hardness of the resin matrix is obviously improved on the basis of not reducing the transmissivity; the silane coupling agent is added to strengthen the connection strength between the film and the resin and prevent the film from falling off.
Drawings
FIG. 1 is a graph showing the transmittance of films of various silane coupling agents.
FIG. 2 is a graph comparing the transmittance of films prepared at different aging times.
FIG. 3 is a graph comparing the transmittance curves of the films of example 8 at different annealing temperatures.
FIG. 4 is a graph comparing the transmittance curves of the films of example 9 at different annealing temperatures
Detailed Description
The invention is further described in the following description with reference to the figures.
First, the applicant found through research and reading that: resin materials begin to appear and replace glass materials to be used as new materials of lenses, and because the resin materials are light in weight, excellent in optical properties such as light transmittance and dispersion and good in impact resistance, the application of the resin lenses enables the visual technology to be rapidly developed, and the resin lenses are generally divided into three types: allyl diglycol carbonate (CR-39), polymethyl methacrylate (PMMA) and Polycarbonate (PC).
Compared with the traditional glass lens, the resin lens is widely applied to the market due to the advantages, but the resin lens has low surface hardness and is easy to scratch, so that the service life of the resin lens is short, and therefore, the surface hardening treatment is very important for the resin lens. The hardness of the resin material is not as good as that of the glass material, but after the surface of the resin material is subjected to organic silicification treatment, a protective layer is formed on the inner surface and the outer surface of the resin material after a hard film is prepared, and the existence of the protective layer greatly increases the friction resistance of the resin material, so that the friction resistance of the surface of the resin material can be very close to that of a common glass lens.
Currently, the hardness of the resin is increased by modifying the surface interface of the lens material. Because the nano silicon dioxide has excellent performance, the preparation of the silicon oxide hardened film on the resin substrate becomes a new research hotspot.
In the prior art, PC resin is often used asA lens material having a molecular structure:
Figure BDA0002361469070000041
the optical properties of PC are excellent: its refractive index is very high, 1.586; the impact resistance is very strong and is much higher than that of CR-39; the weight is very light, and is 57% lighter than that of a common glass sheet; ultraviolet resistance; the softening temperature is about 140 ℃, and is higher than the heat-resistant temperature of PMMA. However, PC materials have a low hardness and poor wear resistance. Hardening treatment of the PC resin is very necessary.
However, it has been found that it is difficult to achieve a good bonding strength between the film and the substrate due to the large difference between the resin substrate and the silicon oxide. In actual production, hard coating and antireflection film are added in two steps, the hard coating is plated by using a dip plating hard coating liquid heating and curing method, and the antireflection film is plated by using a physical vapor deposition method, so that equipment is expensive and the operation is complex. In the conventional sol-gel method, the film is easy to fall off due to overheating because the high-temperature condition is generally kept in the film process.
Therefore, the applicant has developed a method for preparing a film having a hardening and anti-reflection composite function on a resin substrate in one step by a simple and low-cost method.
Example 1
The preparation method of the silicon oxide-zirconium oxide composite sol applied to the lens film specifically comprises the following steps:
step one, measuring water and absolute ethyl alcohol, and uniformly mixing to prepare an ethanol solution: vWater (W)∶VEthanol＝1∶4；
Step two, dropwise adding Tetraethoxysilane (TEOS) into the ethanol solution, and uniformly stirring to prepare TEOS alcohol solution: vEthanol∶VTetraethoxysilane＝5∶1；
Step three, weighing zirconium oxychloride (ZrOCl)2·8H2O) is dissolved in distilled water to prepare ZrOCl2An aqueous solution; the molar ratio of the zirconium oxychloride to the tetraethoxysilane is 1: 1;
step four, TEOS alcoholic solution and ZrOCl2Mixing the aqueous solution uniformly, and heating at room temperatureStirring for 3.5 hours by magnetic force;
step five, dripping a silane coupling agent into the mixed solution while stirring, and continuously stirring for 30 minutes; vSilane coupling agent∶VTetraethoxysilane＝7∶25；
And step six, stopping stirring, standing and aging for 2 days to obtain the silicon oxide-zirconium oxide composite sol.
During the whole process described above, the following hydrolysis of the metal inorganic salt takes place:
Si(OC2H5)4+H2O→Si(OC2H5)3OH+C2H5OH
Zr4++(16-x)H2O+xC2H5OH→[Zr4(OH)8(H2O)16-X(C2H5OH)X]8+；
meanwhile, the hydrolysate which is hydrolyzed or condensed forms a-M-O-M-network structure which is used for forming a grabbing function with the substrate material, so that the substrate material is prevented from being separated after film forming.
2Si(OC2H5)3OH→[(OC2H5)3-Si-O-Si-(OC2H5)3]+H2O；
[Zr4(OH)8(H2O)16-X(C2H5OH)X]Cl8→
[Zr4(OH)12(C2H5OH)X(H2O)12-X]Cl4+4 HCl; the HCl generated in the process can be just regulated to make the reaction system acidic.
At the same time as the hydrolysis and condensation reactions take place, the following reactions also occur:
(1) hydrolysis of polysiloxanes to give C2H5OH：
≡Si-OC2H5+H2O→≡Si-OH+C2H5OH
(2) Decomposition of the zirconium salt complex produces HCl:
[Zr4(OH)12(C2H5OH)X(H2O)12-X]Cl4→[Zr4(OH)12(C2H5OH)X(H2O)8-X]+4HCl
(3) the surface ethoxy group undergoes oxidation reaction in air to generate peroxide:
≡Si-OC2H5+O2→≡Si-OC2H4-O-OH→≡Si-OH+CH3COOH。
the silica-zirconia composite sol for the lens film obtained by the preparation method is used for the lens film and has the effects of increasing the reflection and hardening.
The specific method for applying the sol to the lens film comprises the following steps: 101, ultrasonically cleaning a resin substrate for 5min by using a washing powder solution;
102, washing the PC resin substrate with distilled water;
103, putting the cleaned PC resin substrate into NaOH solution for ultrasonic cleaning for 5 min;
104, ultrasonically cleaning the resin substrate in distilled water at normal temperature for 5min to remove NaOH residues;
105, ultrasonically cleaning the glass substrate for 5min by using absolute ethyl alcohol at normal temperature;
step 106, taking out the resin sheet and drying the resin sheet for later use;
step 107, coating the prepared silicon oxide-zirconium oxide composite sol on the surface of resin by adopting a dip-coating method;
step 108, the resin coated with the sol is placed in an oven at 70 ℃ for annealing for 60 minutes.
Wherein the dipping and pulling method comprises the following steps: the cleaned substrate is soaked in the prepared sol and is uniformly pulled after being soaked for a period of time, and then a layer of uniform water film is formed on the surface of the substrate.
Example 2
The present embodiment is different from embodiment 1 in that: step one, measuring water and no waterUniformly mixing water and ethanol to prepare an ethanol solution: vWater (W)∶VEthanol1: 15; the other steps were the same as in example 1.
Example 3
The present embodiment is different from embodiment 1 in that: step one, measuring water and absolute ethyl alcohol, and uniformly mixing to prepare an ethanol solution: vWater (W)∶VEthanol1: 5; the other steps were the same as in example 1.
The influence of the ratio of water to absolute ethyl alcohol on the adhesion of the film was investigated by examples 1 to 3, and the adhesion of the film was measured, typically by cross-hatch. The testing method comprises the steps of cutting and penetrating a film according to a lattice pattern by using a tool with a certain specification, then sticking the film by using an adhesive tape with a certain viscosity, and judging whether the adhesive force of the film is good or not by using a falling area.
When the volume ratio of water to ethanol is 1: 15 or 1: 5, the dissolving speed of the tetraethoxysilane is slow after the tetraethoxysilane is dripped into the ethanol solution, and the reaction rate is influenced. And the film plated under the alcohol-water ratio has poor adhesive force, and the film is easy to fall off.
When the volume ratio of water to ethanol is 1: 4, the dissolving speed of the tetraethoxysilane in the solution is obviously accelerated, and the reaction rate is proper.
Table 1 shows the adhesion test results of the cross-cut method for different alcohol-water ratios. As can be seen from the table, the adhesive force difference measured under different alcohol-water ratios is very large, when the ratio of alcohol to water is 20ml to 5ml, the falling area of the film is less than 5%, and the adhesive force of the film is good; when the water is added excessively or the ethanol is added excessively, the falling area of the film is 20-30%, the adhesive force is poor, and the film capacity falls off. For this purpose, the solvent ratio, i.e. alcohol to water, is finally determined to be an optimum ratio of 4: 1.
Table 1 adhesion force test table for different water-alcohol ratios
Figure BDA0002361469070000071
The molecular formula of the silane coupling agent is Y (CH2)nSiX3Where n is 0 to 3; x is usually chloro, methoxy, ethoxyHydrolyzable groups such as methoxy ethoxy and acetoxy, which upon hydrolysis generate silanol (Si (OH)3) And combines with the inorganic substance to form the siloxane. Y is usually an organic functional group such as a vinyl group, an amino group, an epoxy group, a methacryloxy group, a mercapto group or a ureido group, and can be reacted with and bonded to an organic substance such as a resin. Therefore, through the silane coupling agent, a 'molecular bridge' can be erected between the interfaces of the inorganic substance and the organic substance, and the two materials with different properties are connected together to improve the performance of the composite material and increase the bonding strength.
Example 4
The present embodiment is different from embodiment 1 in that: step five in example 1 was omitted, and the other steps were the same as in example 1.
The influence of the silane coupling agent on the transmittance and hardness of the film was investigated by examples 1 and 4.
Transmittance measurements were performed on the uncoated PC resin, the PC resin in example 1, and the PC resin in example 4. As shown in fig. 1, it was found that: in the wavelength range of 500nm-760nm, the average transmittance of the PC resin without coating is 89%, and after the coating is not added with the coupling agent, the transmittance is reduced by 78% and 11%. When the coupling agent was added to the precursor, the average transmittance of the PC resin was 85%, which decreased by 4%. The silane coupling agent therefore has a positive effect on the film transmission.
The hardness test was performed on the PC resin without plating, the PC resin in example 1, and the PC resin in example 4.
The test was performed with a pencil hardness tester on the resin substrate before and after coating. The film was scratched with a pencil of known hardness at a load, starting with the hardest pencil, each grade of pencil scratching 5 traces of about 3mm long at a rate of about 1mm per second until the film was not scratched, at which point the hardness of the pencil represented the hardness of the film (hardness from 8B to 8H, softest 8B, hardest 8H).
As can be seen from Table 2, the hardness of the resin coated with the coupling agent and without the coupling agent is improved compared with that of the resin coated with the coupling agent. In contrast, the hardness of the film is better after the silane coupling agent is added, and is improved to 1H from 4-5B of the uncoated film.
Table 2 shows the hardness values of various coupling agents (500 g load)
Figure BDA0002361469070000072
Figure BDA0002361469070000081
The addition of a certain amount of silane coupling agent to the precursor sol greatly improves the transmittance and hardening effect of the silica/zirconia composite film, because the silane coupling agent increases the bonding force between the film and the resin substrate.
Example 5
The present embodiment is different from embodiment 1 in that: and step six, stopping stirring, standing and aging for 1 day to obtain the silicon oxide-zirconium oxide composite sol. The other steps were the same as in example 1.
Example 6
The present embodiment is different from embodiment 1 in that: and step six, stopping stirring, standing and aging for 3 days to obtain the silicon oxide-zirconium oxide composite sol. The other steps were the same as in example 1.
The effect of aging time on film transmission was investigated by comparing example 1, example 5 and example 6.
As shown in FIG. 2, the film prepared after aging for 1 day had the worst transmittance under the same annealing temperature and solution formulation, the film prepared when the aging time was increased to 2 days had the transmittance increased, and the film had the transmittance deteriorated when the aging time was continuously increased to 3 days. It can be seen that the aging time has a large effect on the film transmittance, and that excessively short and long aging times reduce the film transmittance. The analysis reason is as follows: when the aging time is too short, the sol is not aged sufficiently, and the hydrolytic polycondensation reaction is not sufficient; when the aging time is too long, the sol is excessively aged, so that the viscosity of the sol is excessively high, resulting in a decrease in the transmittance of the film.
Example 7
The present embodiment is different from embodiment 1 in that: step 108, the resin coated with the sol is placed in an oven at 60 ℃ for annealing for 60 minutes. The other steps were the same as in example 1.
Example 8
The present embodiment is different from embodiment 1 in that: and 108, annealing the resin coated with the sol in an oven at 80 ℃ for 60 minutes. The other steps were the same as in example 1.
The effect of annealing time on film transmission was investigated by comparing example 1, example 7 and example 8.
As can be seen from FIG. 3, when the annealing temperature was 60 ℃, the average transmittance of the resin in the wavelength range of 500nm to 760nm was about 83%, and the film decreased the transmittance of the resin. When the annealing temperature is 70 ℃, the average transmittance of the resin in the wavelength range of 500nm to 760nm is 89%, and the film does not play a role in anti-reflection and does not reduce the transmittance of the resin alone. When the annealing temperature is 80 ℃, the average transmittance of the resin in the wavelength range of 500nm to 760nm is reduced to 75%, which may be caused by the increase in temperature, the increase in solvent volatilization speed, the increase in internal stress, and the increase in defects of the film, resulting in the reduction in transmittance. The transmittance of the film is highest when the film is annealed at an annealing temperature of 70 ℃.
The effect of annealing time on film hardness was investigated by comparing example 1, example 7 and example 8. The film hardness was measured with a pencil hardness tester. Table 3 shows that the ratio of coupling agent to tetraethoxysilane added is 7: 25, and the hardness measured after annealing at 60 ℃, 70 ℃ and 80 ℃ for 1 hour, respectively. As can be seen from the table, the difference of the hardness between the films at different annealing temperatures is not large, the hardness of the film annealed at 60 ℃ is HB, the hardness of the film is slightly improved along with the increase of the annealing temperature, and the hardness of the film annealed at 70 ℃ and 80 ℃ reaches 1H. Considering the transmittance and the hardness together, the optimal annealing temperature is determined to be 70 ℃.
TABLE 3 hardness tester at different annealing temperatures (load 500g)
Figure BDA0002361469070000091
Example 9
The present embodiment is different from embodiment 1 in that: step 107, the prepared silica-zirconia composite sol is coated on the surface of the resin by a spin coating method, and other steps are the same as those in example 1.
The spin coating method is to put the substrate into a spin coater, then to drop the sol solution on the surface of the substrate, and then to form a layer of uniform film on the substrate under the action of centrifugal force by mechanical rotation.
By studying the throwing rate of the spin-coating film at different annealing temperatures, it can be seen from fig. 4 that the difference of the anti-reflection rate of the film at different annealing temperatures is not large. The film prepared by the spin coating method has an anti-reflection effect within the wavelength range of 380nm-500nm, but has no anti-reflection effect within the wavelength range of 500nm-760 nm.
The hardness of the spin-coated film at different annealing temperatures was examined, and it can be seen from Table 4 that the spin-coated film has a hardening effect. However, at different annealing temperatures, the hardness of the spin-coating method coating is generally lower than that of the dip-coating method coating, and the analysis reason is that: spin coating film formation is a uniform film layer formed by high-speed centrifugation in a spin coater, and the film layer is thin, so that the film layer is greatly influenced by the hardness of a substrate, and the hardness is low.
TABLE 3.4 hardness tester (load 500g) for different coating modes at different annealing temperatures
Figure BDA0002361469070000092
Figure BDA0002361469070000101
Example 10
The preparation method of the silica sol applied to the lens film specifically comprises the following steps:
1) 5ml of tetraethoxysilane is dripped into 25ml of absolute ethyl alcohol, then magnetic stirring is carried out, and 1.4ml of silane coupling agent is dripped in the stirring process;
2) magnetically stirring at room temperature for 30min, and adjusting pH to 2.5 with hydrochloric acid;
3) continuously stirring for 3 hours at 50 ℃ by magnetic force;
4) standing and aging the precursor sol at room temperature for about 2 d;
5) the prepared sol was coated on the resin surface and annealed in an oven at 70 ℃ for 60 min.
Use of the silica sol for a lens film as described above in a lens film.
In a further embodiment, the method specifically comprises the following steps:
101, ultrasonically cleaning a resin substrate for 5min by using a washing powder solution;
step 102, washing the substrate with distilled water;
103, putting the cleaned resin substrate into NaOH solution for ultrasonic cleaning for 5 min;
104, ultrasonically cleaning the resin substrate in distilled water at normal temperature for 5min to remove NaOH residues;
105, ultrasonically cleaning the glass substrate with absolute ethyl alcohol for 5min at normal temperature
Step 106, taking out the resin sheet and drying the resin sheet for later use;
step 107, coating the prepared silica-zirconia composite sol on the surface of resin;
step 108, the resin coated with the sol is placed in an oven at 70 ℃ for annealing for 60 minutes.
That is, a PC resin with a silicon oxide film was prepared, and the film on the PC resin was observed simultaneously with example 1, and it was found that: in example 10, the surface of the silicon oxide film on the PC substrate was entirely flat but partially bulged, and the surface of the silicon zirconium composite film on the PC substrate in example 1 was smooth and flat without significant impurities and defects.
In summary, the dip-coating method is used for preparing the silicon-zirconium composite film on the PC resin, and the optimal conditions are as follows: when adding silane coupling agent, the ratio of silicon and alcohol is 5: 1, the ratio of silicon and zirconium is 1: 1, the ratio of alcohol and water is 4: 1, the aging time of sol is 2 days, and the annealing temperature of the film is 70 ℃. The transmittance of the PC resin for preparing the silicon-zirconium composite film under the optimal condition is about 89%, and although the anti-reflection effect is not obvious, the transmittance of the substrate is not reduced. The hardness of the film measured by a pencil hardness meter is increased by 5 grades from 4B before film coating, and reaches 1H. The silicon-zirconium composite film can obviously improve the hardness of a resin matrix on the basis of not reducing the transmittance.
By using the same preparation method to plate the silicozirconium composite film on the CR-39 resin, the transmissivity and the hardness of the CR-39 substrate are both obviously improved.

Claims (10)

1. The preparation method of the silicon oxide-zirconium oxide composite sol applied to the lens film is characterized by comprising the following steps:
step one, measuring water and absolute ethyl alcohol, and uniformly mixing to prepare an ethanol solution;
step two, dropwise adding Tetraethoxysilane (TEOS) into the ethanol solution, and uniformly stirring to prepare TEOS alcohol solution;
step three, weighing zirconium oxychloride (ZrOCl)2·8H2O) is dissolved in distilled water to prepare ZrOCl2An aqueous solution;
step four, TEOS alcoholic solution and ZrOCl2Uniformly mixing the aqueous solution, and magnetically stirring for 3-4 hours at normal temperature;
step five, dripping a silane coupling agent into the mixed solution while stirring, and continuously stirring for 25-40 minutes;
and step six, stopping stirring, standing and aging for 1-3 days to obtain the silicon oxide-zirconium oxide composite sol.
2. The method for preparing the silica-zirconia composite sol for lens films according to claim 1, wherein the volume ratio of water to absolute ethyl alcohol is as follows:
Vwater (W)∶VEthanol＝1∶15～1∶5；
The volume ratio of the absolute ethyl alcohol to the tetraethoxysilane is as follows:
Vethanol∶VTetraethoxysilane＝4∶1～6∶1；
The volume ratio of the silane coupling agent to the tetraethoxysilane is as follows:
Vsilane coupling agent∶VTetraethoxysilane＝6∶26～8∶27。
3. The method of claim 1, wherein the molar ratio of the zirconium oxychloride to the tetraethoxysilane is 1: 0.5 to 1: 2.
4. The method for preparing a silica-zirconia composite sol for a lens film according to claim 1, wherein a hydrolysis reaction and a condensation reaction are generated;
wherein the hydrolysis reaction is as follows:
Si(OC2H5)4+H2O→Si(OC2H5)3OH+C2H5OH；
Zr4++(16-x)H2O+xC2H5OH→[Zr4(OH)8(H2O)16-X(C2H5OH)X]8+；
the condensation reaction is as follows:
2Si(OC2H5)3OH→[(OC2H5)3-Si-O-Si-(OC2H5)3]+H2O；
[Zr4(OH)8(H2O)16-X(C2H5OH)X]Cl8→[Zr4(OH)12(C2H5OH)X(H2O)12-X]Cl4+4HCl；
the generated HCl is used for adjusting the pH value of the sol to make the sol acidic.
5. The method of claim 4, wherein the hydrolysis and condensation reactions are carried out simultaneously with the following reaction:
(1) hydrolysis of polysiloxanes to give C2H5OH：
≡Si-OC2H5+H2O→≡Si-OH+C2H5OH
(2) Decomposition of the zirconium salt complex produces HCl:
[Zr4(OH)12(C2H5OH)X(H2O)12-X]Cl4→[Zr4(OH)12(C2H5OH)X(H2O)8-X]+4HCl
(3) the surface ethoxy group undergoes oxidation reaction in air to generate peroxide:
≡Si-OC2H5+O2→≡Si-OC2H4-O-OH→≡Si-OH+CH3COOH。
6. the composite silica-zirconia sol for lens film is prepared with water, anhydrous alcohol, ethyl orthosilicate, zirconium oxychloride and silane coupling agent.
7. Use of the silica-zirconia composite sol for lens films according to claim 6 in lens films.
8. The use of the silica-zirconia composite sol for a lens film according to claim 7, which comprises the following steps:
101, ultrasonically cleaning a resin substrate for 4-6min by using a washing powder solution;
step 102, washing the resin substrate clean with distilled water;
103, putting the cleaned resin substrate into NaOH solution to perform ultrasonic cleaning for 4-6 min;
104, ultrasonically cleaning the resin substrate in distilled water at normal temperature for 4-6min to remove NaOH residues;
105, ultrasonically cleaning the mixture for 4-6min by using absolute ethyl alcohol at normal temperature;
step 106, taking out the resin sheet and drying the resin sheet for later use;
step 107, coating the prepared silica-zirconia composite sol on the surface of resin;
and 108, putting the resin coated with the sol into an oven at the temperature of 60-80 ℃ for annealing for 60-70 minutes.
9. The use of the silica-zirconia composite sol for an ophthalmic lens film according to claim 8, wherein said coating in step 107 is performed by dip-coating.
10. The use of the silica-zirconia composite sol for an ophthalmic lens film according to claim 8, wherein the coating in the step 107 is a spin coating method.
CN202010022995.7A 2020-01-09 2020-01-09 Silicon oxide-zirconium oxide composite sol for lens film, preparation method and application method thereof Withdrawn CN111205677A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112454952A (en) * 2020-11-17 2021-03-09 广西浦晶光学有限公司 Production process of PC film glasses
CN112759388A (en) * 2021-01-05 2021-05-07 北京化工大学 ZrO preparation by adopting sol-gel method2-SiO2Method for coating binary mixed sol
CN114656846A (en) * 2020-12-23 2022-06-24 上海沪正实业有限公司 Stainless steel composite functional coating and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112454952A (en) * 2020-11-17 2021-03-09 广西浦晶光学有限公司 Production process of PC film glasses
CN114656846A (en) * 2020-12-23 2022-06-24 上海沪正实业有限公司 Stainless steel composite functional coating and preparation method thereof
CN112759388A (en) * 2021-01-05 2021-05-07 北京化工大学 ZrO preparation by adopting sol-gel method2-SiO2Method for coating binary mixed sol

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