Anti-reflection film coating liquid as well as preparation method and application thereof

Abstract

The invention provides an anti-reflection film coating liquid as well as a preparation method and application thereof, and the preparation method comprises the following steps: carrying out first mixing on water, an organic solvent, a siloxane compound and a catalyst, and aging to obtain the anti-reflection film coating liquid, the solubility of the catalyst in the organic solvent is less than or equal to 5g / 100g organic solvent. According to the preparation method disclosed by the invention, the film-forming property of the anti-reflection film coating liquid obtained by the preparation method is good, the performance of a coating film layer is not influenced, and the obtained coating film layer has good transmittance, hardness, adhesive force and aging resistance; the problems of strong odor, environmental pollution and the like caused by using catalysts such as hydrochloric acid and ammonia water are avoided, and the method is low in cost, simple in process, free of corrosion of base materials and wide in application.

Description

Technical Field

[0001] This invention belongs to the field of antireflective coating solution technology, specifically relating to an antireflective coating solution, its preparation method, and its application. Background Technology

[0002] Anti-reflective coatings reduce reflected light and increase incident light, and are widely used in various fields such as mobile phone lenses, eyeglasses, car windows, and camera lenses. The transmittance of commonly used optical glass is around 92% because its refractive index is usually above 1.5. When light enters the glass from the air, it is reflected, resulting in energy loss and a decrease in resolution. Anti-reflective coatings, on the other hand, typically have a refractive index of around 1.3. When an anti-reflective coating is applied to the surface of optical glass, the interference of light cancels out reflection, effectively eliminating light reflection and allowing more light to pass through the medium, thus achieving an anti-reflective effect.

[0003] The synthesis method of antireflective coating solutions is usually the sol-gel method. Raw materials include siloxanes, organic solvents, water, and catalysts. Depending on the catalyst, it is divided into acidic and basic catalytic systems. Hydrochloric acid is commonly used as a catalyst in acidic catalytic systems, while ammonia is commonly used in basic catalytic systems. Besides hydrochloric acid and ammonia, other acidic or basic compounds are also used as catalysts. For example, the pH adjuster used in CN109694594A includes one or more of ammonia, sodium hydroxide, triethanolamine, triethylamine, hydrochloric acid, acetic acid, nitric acid, sulfuric acid, or phosphoric acid. Another example is the catalyst used in CN110591516A, which includes one or more of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, or citric acid. However, the catalysts are mostly volatile and have an irritating odor, which is not conducive to their use. Secondly, the catalysts can corrode some substrates, causing damage to the substrates and limiting the application of the coating solution. Thirdly, the catalysts cannot be effectively removed from the product after the coating solution is synthesized, and may even remain in the coating layer, especially affecting the anti-reflective film's aging resistance. In addition, the catalysts are difficult to process and recycle.

[0004] Therefore, developing a low-cost, environmentally friendly method for preparing antireflective coating solutions that avoids the impact of catalyst residue on the performance of antireflective coatings is an urgent problem to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an antireflective coating solution, its preparation method, and its applications. The antireflective coating solution obtained by the described method exhibits excellent film-forming properties without affecting the performance of the coating layer. Compared to antireflective coating solutions prepared using hydrochloric acid or ammonia as catalysts, the coating layer prepared using the antireflective coating solution described in this invention has comparable or superior transmittance, hardness, adhesion, and aging resistance. It avoids the problems of strong odor and environmental unfriendliness caused by using catalysts such as hydrochloric acid and ammonia, and is also low-cost, simple to process, does not corrode the substrate, and has wide applications.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides a method for preparing an antireflective coating solution, the method comprising the following steps:

[0008] Water, organic solvent, siloxane compound and catalyst are mixed for the first time and aged to obtain the antireflective coating solution; the solubility of the catalyst in organic solvent is ≤5g / 100g organic solvent.

[0009] In this invention, a catalyst with low solubility in organic solvents is used to synthesize the coating solution through a heterogeneous reaction, avoiding the odor problem caused by using catalysts such as hydrochloric acid or ammonia, thus minimizing environmental pollution. Secondly, the catalyst is easy to remove, the post-processing is simple, and it does not leave any residue in the coating solution, solving the problem of catalyst residue in the film layer causing a decline in the performance of the coating layer. The film-forming properties are good, and the resulting coating layer has comparable or better transmittance, hardness, adhesion, and aging resistance. Thirdly, the catalyst can be recycled and reused, facilitating storage and transportation, and effectively reducing costs.

[0010] In this invention, the solubility of the catalyst in an organic solvent is ≤5g / 100g of organic solvent, for example, it can be 0.001g / 100g, 0.002g / 100g, 0.004g / 100g, 0.006g / 100g, 0.008g / 100g, 0.01g / 100g, 0.02g / 100g, 0.04g / 100g, 0.06g / 100g, 0.08g / 100g, 0.1g / 100g, or 0.2g. / 100g organic solvent, 0.4g / 100g organic solvent, 0.6g / 100g organic solvent, 0.8g / 100g organic solvent, 1g / 100g organic solvent, 1.2g / 100g organic solvent, 1.4g / 100g organic solvent, 1.6g / 100g organic solvent, 1.8g / 100g organic solvent, 2g / 100g organic solvent, 2.5g / 100g organic solvent, 3g / 100g organic solvent, 3.5g / 100g organic solvent, 4g / 100g organic solvent, 4.5g / 100g organic solvent, 5g / 100g organic solvent, etc.

[0011] In this invention, the solubility refers to the solubility at 25°C.

[0012] Preferably, the solubility of the catalyst in an organic solvent is ≤1.2g / 100g organic solvent.

[0013] Preferably, the first mixing method includes:

[0014] Water and organic solvent are premixed, then a catalyst is added, and the pH of the solution is adjusted to 4–10, for example, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, etc.; subsequently, siloxane compounds are added and mixed.

[0015] Preferably, the catalyst comprises a strong base-weak acid salt, which includes any one or a combination of at least two of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, or sodium acetate.

[0016] Preferably, when the catalyst is a strong base-weak acid salt, the molar ratio of the added water, organic solvent and siloxane compound is (1-3):(20-40):1, wherein the specific values ​​of (1-3) can be, for example, 1, 1.2, 1.4, 1.6, 1.8, 2, 2.2, 2.4, 2.6, 2.8, 3, etc.; and the specific values ​​of (20-40) can be, for example, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, etc.

[0017] Preferably, when the catalyst is a strong base-weak acid salt, the first mixing method includes: premixing water and an organic solvent, adding the catalyst thereto, and adjusting the pH of the solution to 9-10, for example, 9, 9.2, 9.4, 9.6, 9.8, 10, etc.

[0018] Preferably, the catalyst comprises a strong acid-weak base salt, which includes any one or a combination of at least two of barium nitrate, lead nitrate, strontium nitrate, zinc sulfate, copper sulfate, magnesium sulfate, nickel sulfate, or manganese sulfate.

[0019] Preferably, when the catalyst is a strong acid-weak base salt, the molar ratio of the added water, organic solvent and siloxane compound is (2-5):(10-30):1, wherein the specific values ​​of (2-5) can be, for example, 2, 2.2, 2.4, 2.6, 2.8, 3, 3.2, 3.4, 3.6, 3.8, 4, 4.2, 4.4, 4.6, 4.8, 5, etc.; and the specific values ​​of (10-30) can be, for example, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, etc.

[0020] Preferably, when the catalyst is a strong acid-weak base salt, the first mixing method includes: premixing water and an organic solvent, adding the catalyst thereto, and adjusting the pH value of the solution to 4-6, for example, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.2, 5.4, 5.6, 5.8, 6, etc.

[0021] Preferably, the organic solvent includes alcohol solvents.

[0022] Preferably, the alcohol solvent includes at least one of methanol, ethanol, isopropanol, or butanol.

[0023] Preferably, the siloxane compound includes any one or a combination of at least two of the following: tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptoethyltrimethoxysilane, mercaptoethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, or aminopropylmethyldimethoxysilane.

[0024] Preferably, the method for adding the siloxane compound includes dropwise addition.

[0025] Preferably, the mixing time is 6 to 24 hours, for example, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, etc.

[0026] In this invention, the dropwise addition is carried out under stirring conditions, and the mixing time refers to the time after the dropwise addition is completed, during which stirring and mixing continues for 6 to 24 hours.

[0027] Preferably, the aging temperature is room temperature, and the aging time is 24 to 72 hours, for example, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, 42 hours, 44 hours, 46 hours, 48 ​​hours, 50 hours, 52 hours, 54 hours, 56 hours, 58 hours, 60 hours, 62 hours, 64 hours, 66 hours, 68 hours, 70 hours, 72 hours, etc.

[0028] Preferably, the aging process further includes a step of removing the catalyst.

[0029] Preferably, the method for removing the catalyst includes at least one of centrifugation, settling, vacuum filtration, or filtration.

[0030] In this invention, the catalyst is dried and then recycled.

[0031] Preferably, the antireflective coating solution includes at least one of an acidic antireflective coating solution, an alkaline antireflective coating solution, or an acid-base mixed antireflective coating solution; the preparation method of the acid-base mixed antireflective coating solution includes: mixing the acidic antireflective coating solution and the alkaline antireflective coating solution to obtain the acid-base mixed antireflective coating solution.

[0032] In this invention, when the catalyst is a strong acid-weak base salt, an acidic antireflective coating solution is obtained; when the catalyst is a strong base-weak acid salt, an alkaline antireflective coating solution is obtained; the obtained acidic and alkaline antireflective coating solutions are mixed to obtain an acid-base mixed antireflective coating solution; the alkaline antireflective coating solution prepared by the above method does not need to be removed by an ammonia removal process before being mixed with the acidic antireflective coating solution, making the process simpler.

[0033] As a preferred technical solution of the present invention, the preparation method includes the following steps:

[0034] Water and organic solvent are premixed, a catalyst is added, and the pH of the solution is adjusted. Then, a siloxane compound is added and mixed for 6–24 h. The mixture is then aged at room temperature for 24–72 h, and the catalyst is removed to obtain the antireflective coating solution. The solubility of the catalyst in the organic solvent is ≤5 g / 100 g of organic solvent. When the catalyst is a strong acid-weak base salt, the pH of the solution is adjusted to 4–6, and the molar ratio of water, organic solvent, and siloxane compound is (2–5):(10–30):1. When the catalyst is a strong base-weak acid salt, the pH of the solution is adjusted to 9–10, and the molar ratio of water, organic solvent, and siloxane compound is (1–3):(20–40):1.

[0035] In this invention, in order to store the obtained antireflective coating solution for a long time, a small amount of strong acid-weak base salt or strong base-weak acid salt can be added as a stabilizer to prevent the antireflective coating solution from gelling due to long-term storage. This stabilizer can be removed before use.

[0036] In a second aspect, the present invention provides an antireflective coating solution, wherein the antireflective coating solution is an antireflective coating solution prepared using the method described in the first aspect.

[0037] Thirdly, the present invention provides an antireflective film, which is prepared by using the antireflective film coating solution described in the second aspect.

[0038] The numerical range described in this invention includes not only the point values ​​listed above, but also any point values ​​within the numerical ranges not listed above. Due to space limitations and for the sake of brevity, this invention will not exhaustively list all the specific point values ​​included in the range.

[0039] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0040] The method for preparing the antireflective coating solution provided by this invention uses a catalyst with low solubility in organic solvents to synthesize the antireflective coating solution through a heterogeneous reaction, avoiding the odor problem caused by using catalysts such as hydrochloric acid or ammonia, thus minimizing environmental pollution. Secondly, the catalyst is easy to remove, the post-processing is simple, and it leaves little or no residue in the antireflective coating solution, solving the problem of catalyst residue in the film layer causing a decline in coating layer performance. The film-forming properties are good, and compared with antireflective coating solutions prepared using hydrochloric acid or ammonia as catalysts, the coating layer prepared using the method of this invention has comparable or better transmittance, hardness, adhesion, and aging resistance. Thirdly, the catalyst can be recycled and reused, facilitating storage and transportation, and effectively reducing costs. Detailed Implementation

[0041] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0042] Example 1

[0043] This embodiment provides a method for preparing an acidic antireflective coating solution, the method comprising the following steps:

[0044] The antireflective coating solution was prepared according to the molar ratio of tetraethoxysilane (TEOS):water:ethanol of 1:3:20. Specifically, the following steps were taken: water and ethanol were mixed and stirred until homogeneous; copper sulfate was then added, and the pH of the solution was tested using pH paper until it reached pH 5; stirring was continued until homogeneous. TEOS was added dropwise to the solution, and stirring was continued for 8 hours after the addition was complete. The solution was then aged at room temperature for 24 hours. The catalyst solids in the solution were filtered through a 200-mesh filter to obtain the antireflective coating solution with the catalyst removed. The catalyst solids after filtration were dried at 80°C and then recycled. To further remove any remaining trace amounts of catalyst in the solution, the temperature could be lowered to allow the catalyst to precipitate out of the solution, and then the precipitated catalyst was filtered and recovered.

[0045] Example 2

[0046] This embodiment provides a method for preparing an alkaline antireflective coating solution, the preparation method comprising the following steps:

[0047] The antireflective coating solution was prepared according to the molar ratio of tetraethoxysilane (TEOS):water:ethanol of 1:2:30. Specifically, the following steps were taken: water and ethanol were mixed and stirred evenly, potassium carbonate was added, and the pH of the solution was tested with pH paper until the pH value of the solution was 10. Then, stirring was continued until the solution was homogeneous. TEOS was added dropwise to the solution. After the addition was completed, stirring was continued for 8 hours. The solution was then placed at room temperature and aged for 48 hours. The catalyst solid in the solution was filtered through a 200-mesh filter to obtain the antireflective coating solution with the catalyst removed. The catalyst solid after filtration was dried at 80°C and then recycled.

[0048] Example 3

[0049] This embodiment provides a method for preparing an acidic antireflective coating solution, the method comprising the following steps:

[0050] The antireflective coating solution was prepared according to the molar ratio of methyltriethoxysilane:water:isopropanol of 1:5:30. Specifically, the following steps were taken: water and isopropanol were mixed and stirred evenly, then barium nitrate was added, and the pH of the solution was tested with pH paper until the pH value of the solution was 4. After that, stirring was continued until uniform. Methyltriethoxysilane was added dropwise to the solution. After the addition was completed, stirring was continued for 12 hours. The solution was then placed at room temperature and aged for 36 hours. The catalyst solid in the solution was filtered through a 200-mesh filter to obtain the antireflective coating solution with the catalyst removed. The catalyst solid after filtration was dried at 80°C and then recycled.

[0051] Example 4

[0052] This embodiment provides a method for preparing an alkaline antireflective coating solution, the preparation method comprising the following steps:

[0053] The antireflective coating solution was prepared according to the molar ratio of aminopropyltriethoxysilane:water:ethanol of 1:1:20. Specifically, the following steps were taken: water and ethanol were mixed and stirred evenly, sodium acetate was added, and the pH of the solution was tested with pH paper until the pH value of the solution was 9. Then, stirring was continued until homogeneous. Aminopropyltriethoxysilane was added dropwise to the solution. After the addition was completed, stirring was continued for 12 hours. The solution was then placed at room temperature and aged for 60 hours. The catalyst solid in the solution was filtered through a 200-mesh filter to obtain the antireflective coating solution with the catalyst removed. The catalyst solid after filtration was dried at 80°C and then recycled.

[0054] Example 5

[0055] This embodiment provides a method for preparing an acid-base mixed antireflective coating solution. The preparation method includes: mixing the acidic antireflective coating solution obtained in Example 1 with the alkaline antireflective coating solution obtained in Example 2 at a volume ratio of 1:1 for 2 hours to obtain the acid-base mixed antireflective coating solution.

[0056] Comparative Example 1

[0057] This comparative example provides a method for preparing an acidic antireflective coating solution. The only difference between this method and Example 1 is that the copper sulfate is replaced with calcium nitrate, and the amount is adjusted to adjust the pH of the solution to 5. All other steps are the same as in Example 1.

[0058] Comparative Example 2

[0059] This comparative example provides a method for preparing an alkaline antireflective coating solution. The only difference between this method and Example 2 is that the potassium carbonate is replaced with potassium acetate, and the content is adjusted to adjust the pH value of the solution to 10. All other steps are the same as in Example 2.

[0060] Comparative Example 3

[0061] This comparative example provides a method for preparing an acidic antireflective coating solution. The only difference between this method and Example 1 is that the copper sulfate is replaced with hydrochloric acid (mass fraction of 36%), and the pH of the solution is adjusted to 5. All other steps are the same as in Example 1.

[0062] Comparative Example 4

[0063] This comparative example provides a method for preparing an alkaline antireflective coating solution. The only difference between this method and Example 2 is that the potassium carbonate is replaced with ammonia (25% by mass), and the pH of the solution is adjusted to 10. All other steps are the same as in Example 2.

[0064] Performance testing

[0065] The antireflective coating solutions obtained by the preparation methods provided in Examples 1-5 and Comparative Examples 1-4 were coated onto 300mm×300mm ultra-white non-tempered glass. After the ethanol evaporated and the glass was naturally dried, the following performance tests were performed after standing for 5 minutes.

[0066] (1) Film forming performance: Visually inspect the surface condition of the coating layer. If there are no abnormalities such as cracks, missing parts, particles, or radial patterns on the surface of the coating layer, it is marked as "qualified". If at least one abnormality such as cracks, missing parts, particles, or radial patterns appears on the surface of the coating layer, it is marked as "unqualified".

[0067] (2) Transmittance: Tested using a UV-Vis spectrophotometer.

[0068] (3) Hardness: Pencil hardness, tested according to GB-T 6739-2022 standard, coating solutions with a hardness of 3H or higher can be used normally.

[0069] (4) Adhesion: Cross-cut test, calibrated according to the paint film cross-cut test standard GB / T9286-1998; the grades are divided into 0-5, with grade 0 being the best.

[0070] (5) Aging resistance (DH1000 test): After 1000 hours of accelerated aging under the conditions of temperature 85±5℃ and humidity 85±5%, the transmittance is tested.

[0071] The specific test results are shown in Table 1. "-" indicates that no test was conducted because the adhesion of the alkaline antireflective coating solution was not up to standard and no aging resistance test was performed.

[0072] Table 1

[0073]

[0074] As shown in Table 1, the antireflective coating solution prepared by the present invention using a catalyst with specific solubility in organic solvents through heterogeneous reaction not only produces coatings with comparable or better performance compared to catalysts such as hydrochloric acid or ammonia, but also has low odor, is environmentally friendly, has simple post-treatment, is easy to remove, can be recycled and reused, and has lower cost.

[0075] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above descriptions are merely specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing an antireflective coating solution, characterized in that, The preparation method includes the following steps: Water, organic solvent, siloxane compound and catalyst are first mixed and aged to obtain the antireflective coating solution; The catalyst has a solubility in organic solvents of ≤5g / 100g organic solvent.

2. The preparation method according to claim 1, characterized in that, The solubility of the catalyst in organic solvents is ≤1.2g / 100g organic solvent; Preferably, the first mixing method includes: Water and organic solvent are premixed, then a catalyst is added, the pH of the solution is adjusted to 4-10, and then siloxane compounds are added and mixed.

3. The preparation method according to claim 2, characterized in that, The catalyst comprises a strong base weak acid salt, which includes any one or a combination of at least two of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, or sodium acetate. Preferably, the molar ratio of the added water, organic solvent and siloxane compound is (1-3):(20-40):1; Preferably, the first mixing method includes: premixing water and an organic solvent, adding a catalyst thereto, and adjusting the pH of the solution to 9-10.

4. The preparation method according to claim 2, characterized in that, The catalyst comprises a strong acid-weak base salt, which includes any one or a combination of at least two of barium nitrate, lead nitrate, strontium nitrate, zinc sulfate, copper sulfate, magnesium sulfate, nickel sulfate, or manganese sulfate. Preferably, the molar ratio of the added water, organic solvent and siloxane compound is (2-5):(10-30):1; Preferably, the first mixing method includes: premixing water and an organic solvent, adding a catalyst thereto, and adjusting the pH of the solution to 4-6.

5. The preparation method according to claim 1, characterized in that, The organic solvent includes alcohol solvents; Preferably, the alcohol solvent includes at least one selected from methanol, ethanol, isopropanol, or butanol; Preferably, the siloxane compound includes any one or a combination of at least two of the following: tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptoethyltrimethoxysilane, mercaptoethyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, or aminopropylmethyldimethoxysilane.

6. The preparation method according to claim 2, characterized in that, The method of adding the siloxane compound includes dropwise addition; The mixing time is 6 to 24 hours, and the aging temperature is room temperature; the aging time is 24 to 72 hours.

7. The preparation method according to any one of claims 1 to 6, characterized in that, The aging process also includes a step of removing the catalyst; Preferably, the method for removing the catalyst includes at least one of centrifugation, settling, vacuum filtration, or filtration; Preferably, the antireflective coating solution includes at least one of an acidic antireflective coating solution, an alkaline antireflective coating solution, or an acid-base mixed antireflective coating solution. The preparation method of the acid-base mixed antireflective coating solution includes: mixing the acidic antireflective coating solution and the alkaline antireflective coating solution to obtain the acid-base mixed antireflective coating solution.

8. The preparation method according to any one of claims 1 to 7, characterized in that, The preparation method includes the following steps: Water and organic solvent are premixed, a catalyst is added, the pH of the solution is adjusted, and then a siloxane compound is added and mixed for 6–24 h. The mixture is then aged at room temperature for 24–72 h, and the catalyst is removed to obtain the antireflective coating solution. The solubility of the catalyst in the organic solvent is ≤5 g / 100 g organic solvent. When the catalyst is a strong acid-weak base salt, the pH of the solution is adjusted to 4-6, and the molar ratio of the added water, organic solvent and siloxane compound is (2-5):(10-30):

1. When the catalyst is a strong base-weak acid salt, the pH of the solution is adjusted to 9-10, and the molar ratio of the added water, organic solvent and siloxane compound is (1-3):(20-40):

1.

9. An antireflective coating solution, characterized in that, The antireflective coating solution is an antireflective coating solution prepared using the method described in any one of claims 1 to 8.

10. An antireflective film, characterized in that, The antireflective film is prepared using the antireflective film coating solution described in claim 9.

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