High-wear-resistance coating liquid for glass storage bottle as well as preparation method and use method of high-wear-resistance coating liquid
By using coating solution made of ammonia, ethyl orthosilicate, anhydrous ethanol and polyacrylic acid, a highly wear-resistant glass storage bottle coating is generated, which solves the problem of weak binding force of the existing film layer, and achieves efficient reduction of ion precipitation and improvement of wear resistance.
Patent Information
- Application Number
- CN202510170935.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-17
- Publication Date
- 2025-05-30
AI Technical Summary
The film layer after the inner surface treatment of existing glass storage bottles has weak bonding force with the glass, which can easily lead to the film layer falling off and contaminate the storage.
The coating solution made of ammonia water, ethyl orthosilicate (TEOS), anhydrous ethanol and polyacrylic acid (PAA) is used to form a hollow spherical structure of SiO2 by alkali catalyzing, and the post-acid catalyzed to form a chain structure, connecting SiO2 hollow spheres to form a highly wear-resistant coating.
The prepared coating layer is dense and uniform, which can effectively reduce the ionic precipitation of glass storage bottles, and has high wear resistance, which is not easy to fall off during use, and the water resistance level reaches HC1 level, and there is no obvious fall off after 20 friction cycles.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field of glass material coating, and relates to a coating solution for a highly wear-resistant glass storage bottle, and a preparation method and a use method thereof. Background Art
[0002] Glass has excellent thermal stability, chemical stability, optical, mechanical and other properties, and is an excellent packaging and storage material. However, with the continuous application of glass storage materials, the performance of glass storage bottles can no longer meet the strict storage requirements of some high-end materials (such as photoresist, etc.) for indicators such as gold impurity precipitation and particle size, and the inner surface of the glass storage bottle needs to be treated.
[0003] The common inner surface treatment methods of glass storage bottles mainly include frosting (de-alkalization) treatment and silicification treatment. The silicification treatment can meet the requirements for the precipitation of metal ions and other impurities on the inner surface of the glass storage bottle, but the prepared film layer has a weak bonding force with the glass matrix, and the film layer is likely to fall off during use, causing pollution to the contained substances. Summary of the Invention
[0004] The purpose of the present invention is to make up for the problem of weak bonding force between the film layer of existing glass storage and glass, and to provide a coating solution for a highly wear-resistant glass storage bottle, and a preparation method and a use method thereof.
[0005] In order to achieve the above purpose, the technical solution adopted by the present invention is as follows: A coating solution for a highly wear-resistant glass storage bottle, which is characterized in that it is made of raw materials with the following weight ratio: 1%-5% ammonia water, 0.1%-1% tetraethyl orthosilicate (TEOS), 93%-97% absolute ethanol, 0.01%-1% polyacrylic acid (PAA).
[0006] Further, the coating solution for a highly wear-resistant glass storage bottle is characterized in that it is made of raw materials with the following weight ratio: 3%-5% ammonia water, 0.5%-0.8% tetraethyl orthosilicate (TEOS), 93%-95% absolute ethanol, 0.01%-0.05% polyacrylic acid (PAA).
[0007] Further, the concentration of the ammonia water is 25-28%.
[0008] A preparation method of a coating solution for a highly wear-resistant glass storage bottle, which is characterized in that it includes the following steps: (1) Dissolve 0.01%-1% polyacrylic acid (PAA) in 1%-5% concentrated ammonia water, stir with a glass rod for one minute, then add 93%-97% absolute ethanol, and mix evenly with a magnetic stirrer. The rotation speed of the magnetic stirrer is 550-650 r / min; After mixing, measure 0.5% - 0.8% tetraethyl orthosilicate (TEOS), and while stirring magnetically, add TEOS dropwise to the mixed solution. Add it in small amounts multiple times to ensure that TEOS does not undergo hydrolysis (for example, add 0.2 mL - 0.3 mL each time), and the interval time is 1 hour; After the addition of TEOS is completed, continue magnetic stirring for 10 - 15 hours to form a nano - silica sol; Acidify the nano - silica sol: Heat the obtained nano - silica sol to 75 - 85 °C by water bath heating, and carry out condensation reflux for 10 - 15 hours to remove ammonia water in the sol. After cooling to room temperature, slowly add 0.1 mol / L dilute hydrochloric acid to the sol, measure the change in the pH of the sol with a pH meter, and finally adjust the pH value of the sol to 2; Then measure and add 0.5% - 0.8% tetraethyl orthosilicate (TEOS), and add it dropwise to the prepared nano - silica solution. Add it in small amounts multiple times to ensure that TEOS does not undergo hydrolysis, with an interval of 1 hour. After the addition is completed, continue magnetic stirring for 6 hours, and let it stand and age for seven days before use.
[0009] The mechanism of the coating solution in the present invention is as follows: Tetraethyl orthosilicate TEOS first undergoes base - catalyzed reaction in an ethanol solution containing a templating agent polyacrylic acid (PAA) to form SiO 2 with a closed hollow spherical structure. Then, adjust the pH of the solution to acidic, and add TEOS again for acid - catalyzed reaction to form a chain - like structure, connecting the SiO in the sol 2 hollow silica spheres. After sufficient reaction, a coating for reducing ion precipitation is prepared by the dipping method, and the templating agent PAA is removed by heat treatment oxidation to prepare a high - wear - resistant coating for glass storage bottles.
[0010] A method for using a coating solution for a high - wear - resistant glass storage bottle, including a glass bottle, characterized by the following steps: (1) Clean and dry the inner surface of the glass bottle; (2) Fill the glass bottle with the coating solution, and then pour out the excess coating solution; (3) Place the glass bottle with the coating solution inside in an oven for drying; (4) Then place the dried glass bottle in a muffle furnace for sintering, take it out and cool it to room temperature to obtain a high - wear - resistant glass storage bottle.
[0011] Further, in step (1), the glass bottle is made of the following raw materials by mass percentage: SiO 2 60 - 70%, Al 2 O 3 1 - 3%, B 2 O 3 0.1 - 1%, Na 2O 7 - 15%, K 2 O 0.1 - 1%, MgO 1 - 5%, CaO 7 - 15%, BaO 0.1% - 1%, Fe 2 O 3 0.1 - 1%.
[0012] Furthermore, the glass bottle in step (1) is made of raw materials with the following mass percentages: SiO 2 63 - 68%, Al 2 O 3 1.5 - 2.5%, B 2 O 3 0.3 - 0.8%, Na 2 O 10 - 12%, K 2 O 0.3 - 0.8%, MgO 2 - 4%, CaO 9 - 13%, BaO 0.5% - 0.8%, Fe 2 O 3 0.5 - 0.8%.
[0013] Furthermore, in step (3), the drying temperature is 50°C - 65°C, and the drying time is 4 - 8 min.
[0014] Furthermore, in step (4), the sintering temperature of the muffle furnace is 280 - 320°C, and the sintering time is 1 - 2 h.
[0015] Furthermore, a highly wear - resistant glass storage bottle obtained in step (4) has a water resistance grade of HC1, and after 20 friction cycle periods, the coating does not fall off.
[0016] The innovation of the present invention lies in providing a coating solution. This coating solution uses PAA as a template agent to form the core of silica spheres. On this basis, by adjusting the amount of TEOS, the wall thickness and clustering degree of the silica spheres are adjusted to prepare silica sol with controllable wall thickness and uniform dispersion. After sintering, the film layer is dense, which can effectively reduce the ion precipitation of the glass storage bottle; the silica sol grown by the acid - catalyzed sol - gel process forms a linear chain structure, and a strong adhesion force is generated between the formed coating and the substrate. Therefore, the glass coating generated by the acid - catalyzed sol has high wear resistance and is not easy to fall off during use.
[0017] The beneficial effects of the present invention: 1. Compared with other coating solutions, the coating solution of the present invention prepares a dense and uniform film layer, which can meet the stringent requirements of the contained substances for the precipitation of metal ions in the glass bottle; 2. The coating layer formed by the coating solution of the present invention is a hollow silica sphere coating layer after sintering. Compared with other solid silica sphere coating layers, it is not easy to fall off, and the film layer is still dense after being worn; 3. The water resistance level of the glass storage bottle produced by the present invention can reach HC1 level after the alkali dissolution water resistance test. After 20 friction cycles, the glass surface is almost completely covered with nano hollow silicon balls under SEM, and the particles are stacked in an interlaced manner without any coating shedding. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 This is a diagram of the amount of hydrochloric acid used in the alkaline dissolution and water resistance test of Examples 1 to 4; Figure 2 This is a SEM image of the inner surface of the glass storage bottle after coating in Example 1; Figure 3 This is a SEM image of the inner surface of the glass storage bottle after coating in Example 2; Figure 4 This is a SEM image of the inner surface of the glass storage bottle after coating in Example 3; Figure 5 This is a SEM image of the inner surface of the glass storage bottle after coating in Example 4; Figure 6 This is a SEM image of the inner surface of the glass storage bottle after coating in Example 5; Figure 7 This is the SEM image of the inner surface of the glass storage bottle after 20 times of friction in Example 1; Figure 8 This is the SEM image of the inner surface of the glass storage bottle after 20 times of friction in Example 2; Figure 9 This is the SEM image of the inner surface of the glass storage bottle after 20 times of friction in Example 3; Figure 10 This is the SEM image of the inner surface of the glass storage bottle after 20 times of friction in Example 4;
[0019] Figure 11 This is the SEM image of the inner surface of the glass storage bottle of Example 5 after 20 times of friction. DETAILED DESCRIPTION
[0020] The present invention will be further described below in conjunction with embodiments: Example 1
[0021] A method for preparing a highly wear-resistant coating solution for a glass storage bottle comprises the following steps: (1) Dissolve 0.1 g of PAA in 14 mL of concentrated ammonia water, stir with a glass rod for one minute, then add 300 mL of ethanol and mix evenly with a magnetic stirrer at a speed of 600 r / min; (2) After mixing, take 2.0 mL of TEOS and add it dropwise to the mixed solution while magnetically stirring. Add 0.2 mL to 0.3 mL of TEOS each time with an interval of 1 hour. After the addition of TEOS is completed, continue magnetic stirring for 12 hours to form a nano-silica sol; (4)Acidify the nano-silica sol: Heat the obtained nano-silica sol to 80 °C by water bath, and carry out condensation reflux for 12 hours to remove ammonia water in the sol. After cooling to room temperature, slowly add 0.1 mol / L dilute hydrochloric acid to the sol, and measure the change of the pH value of the sol with a pH meter. Finally, adjust the pH value of the sol to 2; (5)Then measure 0.4 mL of absolute ethanol and add it dropwise to the prepared nano-silica solution. Each time 0.1 mL is added, with an interval of 1 hour. After the addition is completed, continue magnetic stirring for 6 hours, and let it stand and age for seven days for later use.
[0022] A method for using a coating solution for a highly wear-resistant glass storage bottle, with the mass percentages of the glass bottle used as follows: SiO 2 67%, Al 2 O 3 2%, B 2 O 3 0.5%, Na 2 O 10%, K 2 O 1%, MgO 2.5%, CaO 10%, BaO 1%, Fe 2 O 3 1%; Specifically, it includes the following steps: (1)Fill the glass bottle with deionized water, then put it into an ultrasonic cleaner for ultrasonic cleaning. The ultrasonic time is 15 min - 30 min, and the ultrasonic frequency is 80 KHZ. After cleaning, dry it; (2)Fill the glass bottle with the coating solution, and then pour out the excess coating solution; (3)After the glass bottle is naturally dried, put it into an oven at 50 °C for baking for 5 min, then put it into a muffle furnace at 300 °C for sintering for 1 h, take it out and cool to room temperature, and carry out performance testing after drying; (4)Subsequently, put the dried glass bottle into the muffle furnace for sintering again, take it out and cool to room temperature to obtain a highly wear-resistant glass storage bottle, and carry out performance testing on the glass storage bottle. Example 2
[0023] A preparation method of a coating solution for a highly wear-resistant glass storage bottle, including the following steps: (1)Dissolve 0.1 g of PAA in 14 mL of concentrated ammonia water, stir with a glass rod for one minute, then add 300 mL of ethanol, and mix evenly with a magnetic stirrer. The rotation speed of the magnetic stirrer is 600 r / min; After mixing, measure 2.0 mL of TEOS, and while stirring magnetically, add TEOS dropwise to the mixed solution, with each addition being 0.2 mL to 0.3 mL and the interval time being 1 hour; After the addition of TEOS is completed, continue magnetic stirring for 12 hours to form a nano-silica sol; Acidify the nano-silica sol: Heat the obtained nano-silica sol in a water bath at 80 °C and carry out condensation reflux for 12 hours to remove ammonia water in the sol. After cooling to room temperature, slowly add 0.1 mol / L dilute hydrochloric acid to the sol, and measure the change in the pH of the sol with a pH meter, and finally adjust the pH value of the sol to 2; Then measure 0.4 mL of TEOS and add it dropwise to the prepared nano-silica solution, with each addition being 0.1 mL and the interval being 1 hour. After the addition is completed, continue magnetic stirring for 6 hours, and let it stand and age for seven days for later use.
[0024] A method for using a coating solution for a highly wear-resistant glass storage bottle, and the mass percentages of the glass bottle used are as follows: SiO 2 67%, Al 2 O 3 2%, B 2 O 3 0.5%, Na 2 O 10%, K 2 O 1%, MgO 2.5%, CaO 10%, BaO 1%, Fe 2 O 3 1%; Specifically, it includes the following steps: (1) Fill the glass bottle with deionized water, then put it into an ultrasonic cleaner for ultrasonic cleaning. The ultrasonic time is 15 min - 30 min, and the ultrasonic frequency is 80 KHZ. After cleaning, dry it; (2) Fill the glass bottle with the coating solution, and then pour out the excess coating solution; (3) After the glass bottle is naturally dried, put it into an oven at 50 °C for baking for 5 min, then put it into a muffle furnace at 300 °C for sintering for 1 h, take it out and cool it to room temperature, and conduct performance testing after drying; (4) Then put the dried glass bottle into the muffle furnace for sintering again, take it out and cool it to room temperature to obtain a highly wear-resistant glass storage bottle, and conduct performance testing on the glass storage bottle.
[0025] Examples 3 - 5 Examples 3 - 5 of the present invention are the same as Example 2, except that when acidifying the nano-silica sol in Examples 3 - 5, the amounts of TEOS used in Examples 3 - 5 are 0.8 mL, 1.2 mL, and 1.6 mL respectively.
[0026] The obtained glass bottles were subjected to an alkali dissolution water resistance test, and the results are as follows Figure 1 shown; the morphology of the inner surface of the coated glass storage bottle under a scanning electron microscope is as follows Figures 2 - 6 shown. A 100 g weight was adhered to the outer surface of the obtained glass storage bottle with double-sided tape, and the weighted glass was placed horizontally on a 600-mesh fine sandpaper. After the specimen was evenly pushed horizontally by about 10 cm, it was rotated clockwise by about 90°, and then evenly pushed by about 10 cm again to ensure that the coating could be worn in all directions. Each wear cycle in the horizontal and vertical directions was defined as one wear cycle. After 20 wear cycles, the morphology of the inner surface of the glass storage bottle under a scanning electron microscope is as follows Figures 7 - 11 shown.
[0027] From Figure 1 it can be seen that although the water resistance performance of Example 1 has been improved, it still fails to reach Class HC1. The alkali dissolution experiments of Examples 2 to 5 can all reach Class HC1. From Figures 2 - 6 , Figures 7 - 11 it can be seen that after 20 frictions, the film layer of Example 2 peeled off, and no obvious film layer peeling phenomenon occurred in Examples 2 to 5.
[0028] The above content is only an example and illustration of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar methods to replace them. As long as they do not deviate from the invention or exceed the scope defined by this claim book, they should all fall within the protection scope of the present invention.
Claims
1. A highly wear-resistant coating solution for glass storage bottles, characterized in that The invention is prepared from the following raw materials in the following weight proportions: 1%-5% ammonia water, 0.1%-1% ethyl orthosilicate, 93%-97% anhydrous ethanol and 0.01%-1% polyacrylic acid.
2. A highly wear-resistant coating solution for glass storage bottles according to claim 1, characterized in that The invention is prepared from the following raw materials in the following weight proportions: 3%-5% ammonia water, 0.5%-0.8% ethyl orthosilicate, 93%-95% anhydrous ethanol and 0.01%-0.05% polyacrylic acid.
3. A highly wear-resistant coating solution for glass storage bottles according to claim 1 or 2, characterized in that: The concentration of the ammonia water is 25-28%.
4. A method for preparing a highly wear-resistant coating solution for glass storage bottles, characterized in that The steps include: (1) Dissolve 0.01%-1% polyacrylic acid in 1%-5% concentrated ammonia water, stir with a glass rod for one minute, then add 93%-97% anhydrous ethanol, and mix evenly with a magnetic stirrer at a speed of 550-650 r / min; (2) After mixing, measure 0.5%-0.8% of ethyl orthosilicate and add it dropwise to the mixed solution while magnetically stirring. Add it in small amounts and multiple times to ensure that TEOS does not hydrolyze. The interval time is 1 hour. (3) After the addition of TEOS is completed, continue magnetic stirring for 10 to 15 hours to form a nano-silica sol; (4) Acidification of the nano-silica sol: The obtained nano-silica sol is heated in a water bath at 75-85°C, condensed and refluxed for 10-15 hours to remove the ammonia in the sol, and after cooling to room temperature, 0.1 mol / L dilute hydrochloric acid is slowly added to the sol, and the pH change of the sol is measured by an acidometer, and the pH value of the sol is finally adjusted to 2; (5) Then, add 0.5%-0.8% ethyl orthosilicate dropwise to the prepared nano-silica solution. Add in small amounts and multiple times at intervals of 1 hour to ensure that TEOS does not hydrolyze. After the addition is complete, stir magnetically for 6 hours and allow to stand for 7 days before use.
5. A method for using a highly wear-resistant coating solution for a glass storage bottle according to claim 1 or 4, comprising a glass bottle, characterized in that The steps include: (1) Clean and dry the inner surface of the glass bottle; (2) Fill the glass bottle with the coating solution and then pour out the excess coating solution; (3) Place the glass bottle with the coating liquid inside into a drying oven; (4) The dried glass bottle is then placed in a muffle furnace for sintering, taken out and cooled to room temperature, thereby obtaining a highly wear-resistant glass storage bottle.
6. The method for using the highly wear-resistant coating solution for glass storage bottles according to claim 5, characterized in that: In step (1), the glass bottle is made of the following raw materials in percentage by mass: SiO2 60-70%, Al2O3 1-3%, B2O3 0.1-1%, Na2O 7-15%, K2O 0.1-1%, MgO 1-5%, CaO 7-15%, BaO 0.1%-1%, and Fe2O3 0.1-1%.
7. The method for using the highly wear-resistant coating solution for glass storage bottles according to claim 5, characterized in that: In step (1), the glass bottle is made of the following raw materials in percentage by mass: SiO2 63-68%, Al2O3 1.5-2.5%, B2O3 0.3-0.8%, Na2O 10-12%, K2O 0.3-0.8%, MgO 2-4%, CaO 9-13%, BaO 0.5%-0.8%, and Fe2O3 0.5-0.8%.
8. The method for using the highly wear-resistant coating solution for glass storage bottles according to claim 5, characterized in that: In step (3), the drying temperature is 50°C-65°C, and the drying time is 4-8 minutes.
9. The method for using the highly wear-resistant coating solution for glass storage bottles according to claim 5, characterized in that: In the step (4), the sintering temperature of the muffle furnace is 280-320° C., and the sintering time is 1-2 hours.
10. The method for using the highly wear-resistant coating solution for glass storage bottles according to any one of claims 5 to 9, characterized in that: The highly wear-resistant glass storage bottle obtained in step (4) has a water resistance grade of HC1, and the coating does not fall off after 20 friction cycles.