Anti-dazzle stripping etching liquid suitable for high transmittance and preparation method of anti-dazzle stripping etching liquid

Abstract

The invention relates to the technical field of preparation of glass etching solutions, in particular to an anti-dazzle stripping etching solution suitable for high transmittance and a preparation method. The anti-dazzle stripping etching solution suitable for high transmittance comprises a substrate solution, a modified dispersion solution, a regulator and a stabilizer in parts by mass, the preparation method of the modified dispersion liquid comprises the following steps: adding molybdenum disulfide nanoparticles and povidone into an ethanol solution, and carrying out ultrasonic dispersion to obtain the dispersion liquid; adding N-aminoethyl-3-aminopropyl methyl dimethoxy silane into the dispersion liquid, raising the temperature of a reaction system to 60 DEG C, and keeping the temperature and stirring for 1 hour to obtain the modified dispersion liquid. The invention provides the anti-dazzle stripping etching solution suitable for high transmittance and the preparation method, so as to solve the problems that a non-fluorine etching solution in the related technology is relatively low in etching rate and cannot meet the balance of high transmittance and anti-dazzle performance.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of glass etching liquid preparation, in particular to a high-transmittance anti-glare stripping etching liquid and a preparation method thereof. BACKGROUND

[0002] In the field of glass processing, especially for the preparation of high-transmittance anti-glare glass, there are mainly mechanical methods and chemical methods. The mechanical methods mainly include sand blasting, sand grinding and air blowing, which can form an anti-glare structure, but the consistency of the surface roughness is poor. The chemical processing methods are various, mainly including chemical etching and glass surface coating, among which the chemical etching is the most commonly used, and generally includes fluorine-containing etching liquid and non-fluorine-containing etching liquid. The fluorine-containing etching liquid has greater harm and environmental risk, and the non-fluorine-containing etching liquid avoids the use of strong acid, but has a lower etching rate and cannot meet the large-scale production demand. On the other hand, in the process of chemical etching, the solubility of the salt (such as silicon fluoride) generated by the reaction of fluoride and glass is significantly different, and in the etching liquid, the silicon fluoride in some areas is easy to precipitate, hindering the etching reaction to continue, causing uneven etching, and seriously affecting the subsequent etching effect and product quality. SUMMARY

[0003] The application provides a high-transmittance anti-glare stripping etching liquid and a preparation method thereof, to solve the problem of low etching rate of non-fluorine-containing etching liquid and the inability to balance the high-transmittance and anti-glare performance in the prior art.

[0004] In a first aspect, a high-transmittance anti-glare stripping etching liquid is provided, which comprises, in terms of mass fraction: 65-75 parts of a base liquid, 25-35 parts of a modified dispersion liquid, 0.2-0.4 parts of an adjusting agent, and 1.2-1.8 parts of a stabilizing agent; The preparation method of the modified dispersion liquid comprises the following steps: Molybdenum disulfide nanoparticles and povidone are added to an ethanol solution, and a dispersion liquid is obtained after ultrasonic dispersion for 30 min, the mass ratio of the molybdenum disulfide nanoparticles to the povidone is (0.8-1):2, the mass-volume ratio of the molybdenum disulfide nanoparticles to the ethanol solution is 1 g:10 mL, and the concentration of the ethanol solution is 50 wt%; N-aminoethyl-3-aminopropyl methyldimethoxysilane is added to the dispersion liquid, the temperature of the reaction system is increased to 60 DEG C, and the temperature is kept for 1 h, to obtain a modified dispersion liquid, and the mass ratio of the N-aminoethyl-3-aminopropyl methyldimethoxysilane to the molybdenum disulfide nanoparticles is (0.8-1):1.

[0005] Preferably, the preparation method of the base liquid comprises: Magnesium fluosilicate is dissolved in deionized water at a mass ratio of (1-2):25 at 35°C to obtain a solution; Triethanolamine is added to the solution, and maleic anhydride is added after stirring for 30 min, and stirring is continued for 1 h to obtain a base solution, the mass ratio of triethanolamine to deionized water being (0.8-1):50, and the mass ratio of maleic anhydride to deionized water being (0.4-0.5):50.

[0006] Preferably, the preparation method of the modified dispersion solution further comprises the following steps before adding N-aminoethyl-3-aminopropyl methyldimethoxysilane to the dispersion solution: Trisodium citrate is added to the dispersion solution under stirring, and the pH value is adjusted to 5.5-6.0; The mass ratio of trisodium citrate to molybdenum disulfide nanoparticles is 0.5:1.

[0007] Preferably, the stirring speed is 150-200 r / min.

[0008] Preferably, the stabilizer is zinc borate.

[0009] Preferably, the stabilizer is a modified chitosan-disodium hydrogen phosphate composite system, and the preparation method thereof comprises the following steps: After chitosan is dissolved in a 2wt% acetic acid solution, sodium tripolyphosphate is added, and after reacting for 2 h, the product is washed and freeze-dried to obtain modified chitosan, the mass ratio of sodium tripolyphosphate to chitosan being 1:5, and the mass-volume ratio of chitosan to acetic acid solution being 1g:100mL; Modified chitosan and disodium hydrogen phosphate are mixed at a mass ratio of 3:2, and then ground to obtain a modified chitosan-disodium hydrogen phosphate composite system, the total mass of modified chitosan and disodium hydrogen phosphate being 10% of the mass of deionized water.

[0010] Preferably, the regulator is benzenesulfonamide.

[0011] In a second aspect, a preparation method for preparing the high-transmittance anti-glare stripping etching solution as described in any one of the above aspects is provided, and the preparation method comprises the following steps: The base solution is added to a reaction kettle, and stirred at a speed of 200 r / min, then the modified dispersion solution is added dropwise to the reaction kettle at a dropwise adding speed of 10 mL / min, and after the dropwise adding is completed, stirring is continued for 2-3 h; The regulator is continuously added to the reaction kettle to obtain a test solution, then the stabilizer is continuously added to the test solution, the pH value is adjusted to 3.8-4.2, and stirring is continued for 1 h to obtain the high-transmittance anti-glare stripping etching solution.

[0012] The technical scheme provided by the application brings the beneficial effects of: The application provides a high-transmittance anti-glare stripping etching liquid and a preparation method thereof. The application provides a high-transmittance anti-glare stripping etching liquid and a preparation method thereof.

[0013] In order to more clearly illustrate the technical solutions in the embodiments of the application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative labor.

[0014] Figure 1 The application provides a high-transmittance anti-glare stripping etching liquid and a preparation method thereof. DETAILED DESCRIPTION

[0015] In order to more clearly illustrate the technical solutions in the embodiments of the application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the application, and other drawings can be obtained by those skilled in the art without creative labor.

[0016] Referring to Figure 1 The application provides a high-transmittance anti-glare stripping etching liquid and a preparation method thereof.

[0017] Embodiment 1 The application provides a high-transmittance anti-glare stripping etching liquid and a preparation method thereof. 70g of the base solution was added into the reaction kettle and stirred at a rotation speed of 200 r / min, and then 30g of the modified dispersion solution was added dropwise into the reaction kettle at a dropping speed of 10 mL / min, and after the dropping was completed, the stirring was continued for 2h; First, 0.3g of benzene sulfonamide was added into the reaction kettle to obtain a test solution, and then 1.5g of the stabilizer was added into the test solution, and after the pH was adjusted to 4, the stirring was continued for 1h to obtain the high-transmittance anti-glare stripping etching solution.

[0018] The preparation method of the base solution is as follows: 7.5g of magnesium fluorosilicate was dissolved in 100g of deionized water at 35℃ to obtain a solution; 1.8g of triethanolamine was added into the solution, and after stirring for 30min, 0.9g of maleic anhydride was added, and the stirring was continued for 1h to obtain the base solution.

[0019] The preparation method of the modified dispersion solution is as follows: 5g of molybdenum disulfide nanoparticles and 11g of povidone were added into 50mL of an ethanol solution with a concentration of 50wt%, and after ultrasonic dispersion for 30min, a dispersion solution was obtained; 2.5g of trisodium citrate was added into the dispersion solution under the condition of stirring at a rotation speed of 200 r / min, and the pH value was adjusted to 5.7; 4.5g of N-aminoethyl-3-aminopropylmethyldimethoxysilane was further added into the dispersion solution, the temperature of the reaction system was increased to 60℃, and the stirring was continued for 1h at this temperature to obtain the modified dispersion solution.

[0020] The stabilizer is a modified chitosan-disodium hydrogen phosphate composite system, and the preparation method thereof is as follows: After 2g of chitosan was dissolved in 200mL of an acetic acid solution with a concentration of 2wt%, 0.4g of sodium tripolyphosphate was added, and after reaction for 2h, the modified chitosan was obtained by washing and freeze-drying; The modified chitosan-disodium hydrogen phosphate composite system was obtained by grinding 1.5g of the modified chitosan and 1g of disodium hydrogen phosphate.

[0021] Example 2 The difference between this example and Example 1 is that in the preparation of the modified dispersion solution, no trisodium citrate is added.

[0022] Example 3 The difference between this example and Example 1 is that the stabilizer is replaced by an equal amount of zinc borate.

[0023] Example 4 The preparation method of the high-transmittance anti-glare stripping etching solution provided in this example includes the following steps: 65g of the base solution was added into a reaction kettle, stirred at a rotation speed of 200 r / min, and then 25g of the modified dispersion liquid was added dropwise into the reaction kettle at a dropwise adding speed of 10 mL / min, and after the dropwise adding was completed, the stirring was continued for 2h; First, 0.2g of benzene sulfonamide was added into the reaction kettle to obtain a test solution, and then 1.2g of the stabilizer was added into the test solution, the pH was adjusted to 3.8, and the stirring was continued for 1h to obtain the high-transmittance anti-glare stripping etching liquid.

[0024] The base solution was prepared by the following method: 4g of magnesium fluorosilicate was dissolved in 100g of deionized water at 35℃ to obtain a solution; 1.6g of triethanolamine was added into the solution, and after stirring for 30min, 0.8g of maleic anhydride was added, and the stirring was continued for 1h to obtain the base solution.

[0025] The modified dispersion liquid was prepared by the following method: 5g of molybdenum disulfide nanoparticles and 12.5g of povidone were added into 50mL of an ethanol solution with a concentration of 50wt%, and after ultrasonic dispersion for 30min, a dispersion liquid was obtained; 2.5g of trisodium citrate was added into the dispersion liquid under the condition of stirring at 150r / min, and the pH value was adjusted to 5.8; 4g of N-aminoethyl-3-aminopropylmethyldimethoxysilane was further added into the dispersion liquid, the temperature of the reaction system was increased to 60℃, and the stirring was continued for 1h at this temperature to obtain the modified dispersion liquid.

[0026] The stabilizer was a modified chitosan-disodium hydrogen phosphate composite system, and the preparation method thereof was as follows: After 2g of chitosan was dissolved in 200mL of an acetic acid solution with a concentration of 2wt%, 0.4g of sodium tripolyphosphate was added, and after reaction for 2h, the modified chitosan was obtained by washing and freeze-drying; The modified chitosan-disodium hydrogen phosphate composite system was obtained by grinding 1.5g of the modified chitosan and 1g of disodium hydrogen phosphate after mixing.

[0027] Example 5 The preparation method of the high-transmittance anti-glare stripping etching liquid provided in this embodiment includes the following steps: 75g of the base solution was added into a reaction kettle, stirred at a rotation speed of 200 r / min, and then 35g of the modified dispersion liquid was added dropwise into the reaction kettle at a dropwise adding speed of 10 mL / min, and after the dropwise adding was completed, the stirring was continued for 3h; First, 0.4g of benzene sulfonamide was added into the reaction kettle to obtain a test solution, and then 1.8g of the stabilizer was added into the test solution, the pH was adjusted to 4.2, and the stirring was continued for 1h to obtain the high-transmittance anti-glare stripping etching liquid.

[0028] The base solution is prepared by the following method: 8 g of magnesium fluorosilicate is dissolved in 100 g of deionized water at 35℃ to obtain a solution; 2 g of triethanolamine is added to the solution, and after stirring for 30 min, 1 g of maleic anhydride is added, and stirring is continued for 1 h to obtain the base solution.

[0029] The modified dispersion is prepared by the following method: 5 g of molybdenum disulfide nanoparticles and 10 g of povidone are added to 50 mL of an ethanol solution with a concentration of 50 wt%, and after ultrasonic dispersion for 30 min, a dispersion is obtained; Under stirring at 200 r / min, 2.5 g of trisodium citrate is added to the dispersion, and the pH value is adjusted to 5.5; 5 g of N-aminoethyl-3-aminopropylmethyldimethoxysilane is further added to the dispersion, the temperature of the reaction system is raised to 60℃, and stirring is continued at this temperature for 1 h to obtain the modified dispersion.

[0030] The stabilizer is a modified chitosan-disodium hydrogen phosphate composite system, and its preparation method is the same as that of Example 1.

[0031] Comparative Example 1 The difference between it and Example 1 is that no triethanolamine and maleic anhydride are added in the preparation of the base solution.

[0032] Comparative Example 2 The difference between it and Example 1 is that in the preparation of the modified dispersion, silica nanoparticles are used instead of molybdenum disulfide nanoparticles, and no N-aminoethyl-3-aminopropylmethyldimethoxysilane is added.

[0033] Comparative Example 3 The difference between it and Example 1 is that no stabilizer is added, and in the modified dispersion, trisodium citrate is replaced with an equal amount of sodium citrate.

[0034] The etching solution prepared by the preparation method of Examples 1-5 and Comparative Examples 1-3 is tested.

[0035] Sodium-calcium glass is used as the substrate (100 mm x 100 mm x 1 mm), the surface of the substrate is first wiped with anhydrous ethanol to remove oil stains, and then placed in deionized water for ultrasonic cleaning for 10 min, and then wiped dry with a dust-free cloth. After drying, a pretreated substrate is obtained for use.

[0036] The etching solution prepared by the preparation method of Examples 1-5 and Comparative Examples 1-3 was poured into a glass container, and after being kept at 50°C, the pretreated glass substrate was put in to ensure complete immersion, and was slightly stirred (rotation speed 50 r / min) for 10 min. After taking out, the surface was repeatedly rinsed with deionized water to remove residual etching solution, and finally dried in a 60°C oven for 10 min. After cooling to room temperature, the sample to be tested was obtained, and the transmittance test and anti-glare haze test were carried out.

[0037] Transmittance test: According to GB / T 2410-2008 "Determination of Transmittance and Haze of Plastics", the transmittance expressed in percentage for each sample to be tested was calculated as follows:

[0038] In the formula, T t is the transmittance, T2 is the total transmitted light flux through the sample, and T1 is the incident light flux.

[0039] Anti-glare haze test: According to GB / T 2410-2008 "Determination of Transmittance and Haze of Plastics", the haze expressed in percentage for each sample to be tested was calculated as follows:

[0040] In the formula, H is the haze, T4 is the scattered light flux of the instrument and the sample, T2 is the total transmitted light flux through the sample, T3 is the scattered light flux of the instrument, and T1 is the incident light flux.

[0041] For the above transmittance and anti-glare haze tests, first adjust the haze meter zero point knob so that the galvanometer indication of the integrating sphere is zero in the dark, and when the light is unobstructed, adjust the instrument galvanometer indication to 100. Then follow Table 1 to read T1, T2, T3 and T4. The data reading steps are shown in Table 1.

[0042] Table 1

[0043] Etching rate test: Take sodium-calcium glass as the substrate (50 mm x 50 mm x 1 mm), first wipe the surface of the substrate with anhydrous ethanol to remove oil stains, then ultrasonic clean in deionized water for 10 min, dry with a dust-free cloth, and dry at 60°C to constant weight (difference between two consecutive weighings <0.5 mg). After cooling to room temperature, the pretreated substrate was obtained, and the weight was recorded as m1.

[0044] The etching solution prepared by the preparation method of examples 1-5 and comparative examples 1-3 was poured into a glass cup, and after being kept at 50℃, the pretreated substrate was put in to ensure complete immersion, and slightly stirred (rotation speed 50r / min) for 10min. After taking out, the surface was repeatedly washed with deionized water to remove the residual etching solution, and finally dried in a 60℃ oven for 10min, cooled to room temperature, and weighed as m2.

[0045] The etching rate (pm / min) was calculated as follows:

[0046] In the formula, p is the density of the glass (2.5g / cm 3 ), S is the total area of the pretreated substrate (52cm 2 ), and t is the etching time (10min).

[0047] The test results are shown in Table 2.

[0048] Table 2

[0049] It can be seen that the etching solution prepared in examples 1, 4 and 5 has a higher light transmittance in glass. Among them, the composition of the etching solution in example 4 is slightly adjusted, the etching rate and haze are slightly reduced, but the light transmittance is better; the concentration of the composition in example 5 is increased, the etching rate is increased, but the concentration is too high, which leads to an increase in surface roughness, a decrease in light transmittance, and an increase in haze.

[0050] From the comparison between example 2 and example 1, the modified dispersion liquid in example 2 does not add trisodium citrate to adjust the pH value, the acidity rises, which inhibits the dissociation of magnesium fluorosilicate to some extent, and reduces the etching rate; From the comparison between example 3 and example 1, the effect of zinc borate as a stabilizer is weaker than that of the modified chitosan-sodium hydrogen phosphate composite system, and the prepared etching solution has poor dispersibility. Compared with example 1, the etching rate and haze are reduced, and the light transmittance is reduced due to the unevenness of the surface.

[0051] In comparative example 1, triethanolamine and maleic anhydride are missing, the activity of fluoride ions is low, and the etching rate is extremely low; the etching is not uniform, which leads to a significant decrease in light transmittance and haze; In comparative example 2, the molybdenum disulfide nanoparticles are replaced by silicon dioxide nanoparticles, and N-aminoethyl-3-aminopropyl methyl dimethoxy silane is not added. The silicon dioxide nanoparticles cannot form an effective scattering structure, the haze is extremely low, and the anti-glare effect is poor; but the light transmittance of the etched glass is slightly improved due to the good surface flatness.

[0052] The system is unstable due to the lack of stabilizer in Comparative Example 3, and the pH adjustment function of the modified liquid is poor because the trisodium citrate in the modified liquid is replaced by sodium citrate. The etching rate fluctuates, the surface roughness increases, the light transmittance decreases, and the haze is too high. As a complexing agent, the carboxyl and hydroxyl groups in the molecule of trisodium citrate complex with the fluoride ions produced by the hydrolysis of magnesium fluosilicate and the metal ions (such as calcium and aluminum) in the glass to form a stable complex. On the one hand, it avoids the formation of insoluble fluorides (such as calcium fluoride and aluminum fluoride) by the reaction of fluoride ions with metal ions in the glass, preventing uneven etching caused by precipitation. On the other hand, it changes the chemical activity of the glass surface and promotes uniform etching reaction.

[0053] The high-transmittance anti-glare stripping etching liquid and its preparation method provided by the present application use magnesium fluosilicate instead of traditional highly toxic hydrofluoric acid as the main etching component in the base liquid, reducing the harm to the environment and the safety risk to the operator. At the same time, triethanolamine is added to complex with the magnesium ions produced by the hydrolysis of magnesium fluosilicate, changing the electron cloud distribution around the magnesium ions and promoting the dissociation of magnesium fluosilicate, effectively improving the activity of fluoride ions, and hydrolyzing maleic anhydride to generate maleic acid to maintain a weakly acidic environment of the system and further promote the continuous and stable etching reaction. Under the premise of environmental protection, the etching efficiency is also considered. The molybdenum disulfide nanoparticles in the modified dispersion liquid are dispersed in povidone. The molybdenum disulfide nanoparticles act as a template to guide the formation of uniform pits on the glass surface and achieve the anti-glare effect. After the hydrolysis of N-aminoethyl-3-aminopropylmethyldimethoxysilane, the silanol groups condense with the hydroxyl groups on the glass surface, and the amino groups react with the active sites on the surface of the molybdenum disulfide nanoparticles, allowing the nanoparticles to be directionally adsorbed on the glass surface and further accurately guiding the formation of pits, effectively balancing the high transmittance and anti-glare performance. The regulator benzene sulfonamide in the etching liquid reacts with the unetched silicon hydroxyl groups on the glass surface to form a temporary protective film, slowing down the local etching rate and preventing the local reaction from being too fast. The stabilizer has a buffering effect on the pH of the system, to some extent, ensuring the uniformity and stability of the etching.

[0054] The above description is merely a specific implementation of the present application, enabling those skilled in the art to understand or implement the present application. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A high-transmittance anti-glare stripping etching solution, characterized in that: In parts by mass, it includes: 65-75 parts of base liquid, 25-35 parts of modified dispersion liquid, 0.2-0.4 parts of regulator, 1.2-1.8 parts of stabilizer; The preparation method of the modified dispersion comprises the following steps: Molybdenum disulfide nanoparticles and povidone were added to an ethanol solution and ultrasonically dispersed for 30 minutes to obtain a dispersion. The mass ratio of the molybdenum disulfide nanoparticles to the povidone was (0.8-1):2, the mass volume ratio of the molybdenum disulfide nanoparticles to the ethanol solution was 1 g:10 mL, and the concentration of the ethanol solution was 50 wt %. N-aminoethyl-3-aminopropylmethyldimethoxysilane was added to the dispersion, the temperature of the reaction system was raised to 60° C., and the temperature was maintained and stirred for 1 hour to obtain a modified dispersion, wherein the mass ratio of the N-aminoethyl-3-aminopropylmethyldimethoxysilane to the molybdenum disulfide nanoparticles was (0.8-1):

1.

2. The high-transmittance anti-glare stripping etching solution according to claim 1, characterized in that: The preparation method of the base liquid comprises: Dissolve magnesium fluorosilicate in deionized water at a mass ratio of (1-2):25 at 35° C. to obtain a solution; Triethanolamine was added to the solution, and maleic anhydride was added after stirring for 30 minutes, and stirring was continued for 1 hour to obtain a base liquid, wherein the mass ratio of the triethanolamine to deionized water was (0.8-1):50, and the mass ratio of the maleic anhydride to deionized water was (0.4-0.5):

50.

3. The high-transmittance anti-glare stripping etching solution according to claim 1, characterized in that: In the preparation method of the modified dispersion, the following steps are further included before adding N-aminoethyl-3-aminopropylmethyldimethoxysilane to the dispersion: Under stirring conditions, adding trisodium citrate to the dispersion to adjust the pH value to 5.5-6.0; The mass ratio of the trisodium citrate to the molybdenum disulfide nanoparticles is 0.5:

1.

4. The high-transmittance anti-glare stripping etching solution according to claim 3, characterized in that: The stirring speed is 150-200 r / min.

5. The high-transmittance anti-glare stripping etching solution according to claim 1, characterized in that: The stabilizer is zinc borate.

6. The high-transmittance anti-glare stripping etching solution according to claim 1, characterized in that: The stabilizer is a modified chitosan-disodium hydrogen phosphate composite system, and its preparation method comprises the following steps: Chitosan was dissolved in a 2 wt % acetic acid solution, and sodium tripolyphosphate was added. After reacting for 2 h, the mixture was washed and freeze-dried to obtain modified chitosan. The mass ratio of sodium tripolyphosphate to chitosan was 1:5, and the mass volume ratio of chitosan to acetic acid solution was 1 g:100 mL. The modified chitosan and disodium hydrogen phosphate were mixed in a mass ratio of 3:2 and then ground to obtain a modified chitosan-disodium hydrogen phosphate composite system, wherein the total mass of the modified chitosan and disodium hydrogen phosphate was 10% of the mass of deionized water.

7. The high-transmittance anti-glare stripping etching solution according to claim 1, characterized in that: The regulator is benzenesulfonamide.

8. A preparation method for preparing the high-transmittance anti-glare peeling etching solution according to any one of claims 1 to 7, characterized in that: It includes the following steps: Add the base liquid to the reactor and stir at a speed of 200 r / min. Then add the modified dispersion to the reactor dropwise at a rate of 10 mL / min. After the addition is complete, continue stirring for 2-3 hours. The regulator was added to the reactor to obtain a test solution, and the stabilizer was added to the test solution to adjust the pH to 3.8-4.2, and the solution was stirred for 1 hour to obtain a high-transmittance anti-glare stripping etching solution.

Images