Glass etching liquid composition, glass etching liquid and preparation method and application thereof
By preparing a glass etching liquid composition containing a specific composition, the problem of poor etching effect of microcrystalline glass in the prior art is solved, and the smooth feel and flash sand effect are achieved, while improving the anti-fingerprint and Scratch resistance.
Patent Information
- Application Number
- CN202411308190.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-19
- Publication Date
- 2024-12-10
AI Technical Summary
The existing glass etching liquid is difficult to effectively etch on the surface of the crystal-crystalline glass, especially the etching of crystal-crystalline glass with specific textures is not effective.
Provided is a glass etching solution composition containing 25-37% ammonium fluoride salt, 3-8% alkali metal fluoride salt, 33-50% inorganic acid, 2-10% FeCl3 and ZnCl2, 5- A glass etching liquid was obtained by ripening the components at 10% by weight of viscosity regulator and 5-10% by weight of bentonite, and the glass was etched using it.
The obtained etched microcrystalline glass has a smooth feel, a flash sand effect, a delicate touch, and has good anti-fingerprint, anti-pollution and scratch resistance.
Smart Images
Figure CN119101522A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of glass etching, and in particular to a glass etching liquid composition, a glass etching liquid, and a preparation method and application thereof. Background Art
[0002] Glass-ceramics refers to a basic glass with a specific composition and a nucleating agent. It has the dual characteristics of glass and ceramics. It has both the basic properties of glass and the polycrystalline characteristics of ceramics. It is a unique new type of material. The extremely low expansion coefficient and denser fine wool microstructure of the surface of glass-ceramics give it good corrosion resistance and heat resistance. Therefore, it is widely used and is often used as the mainstream material in the glass substrate processing industry for consumer electronic products.
[0003] However, when microcrystalline glass needs to be etched, since the crystal nucleus density of microcrystalline glass is higher than that of existing conventional ordinary glass, the existing conventional ordinary glass etching solution is difficult to etch the surface of microcrystalline glass, especially for etching microcrystalline glass with specific texture. Summary of the invention
[0004] The purpose of the present invention is to overcome the problem that the existing etching solution is difficult to etch on the surface of microcrystalline glass and the etching effect is poor.
[0005] In order to achieve the above object, the first aspect of the present invention provides a glass etching liquid composition, which contains 25-37wt% of ammonium fluoride salt, 3-8wt% of alkali metal fluoride salt, 33-50wt% of inorganic acid, 2-10wt% of FeCl3 and ZnCl2, 5-10wt% of viscosity regulator, 5-10wt% of bentonite and the balance of water, based on the total weight of the composition.
[0006] The second aspect of the present invention provides a method for preparing a glass etching liquid, the method comprising: ripening the components in the glass etching liquid composition described in the first aspect to obtain the glass etching liquid.
[0007] The third aspect of the present invention provides a glass etching solution prepared by the method described in the second aspect.
[0008] The fourth aspect of the present invention provides use of the glass etching liquid described in the third aspect in etching microcrystalline glass.
[0009] The glass etching liquid provided by the present invention can etch the surface of microcrystalline glass, and the obtained etched microcrystalline glass has a smooth feel and a flash sand effect. The obtained microcrystalline flash sand glass reflects bright light under light, has a unique visual appeal, and a delicate touch that makes people feel smooth and comfortable. At the same time, it has good anti-fingerprint, anti-pollution and anti-scratch properties. BRIEF DESCRIPTION OF THE DRAWINGS
[0010] Figure 1 Microscopic characterization diagram of the samples prepared in Examples 1-6.
[0011] Figure 2 This is a microscopic characterization diagram of the sample prepared in Comparative Example 1.
[0012] Figure 3 This is a microscopic characterization diagram of the sample prepared in Comparative Example 2.
[0013] Figure 4 This is a microscopic characterization diagram of the sample prepared in Comparative Example 3.
[0014] Figure 5 This is a microscopic characterization diagram of the sample prepared in Comparative Example 4.
[0015] Figure 6 This is a microscopic characterization diagram of the sample prepared in Comparative Example 5.
[0016] Figure 7 This is a microscopic characterization diagram of the sample prepared in Comparative Example 6.
[0017] Figure 8 This is a microscopic characterization diagram of the sample prepared in Comparative Example 7. DETAILED DESCRIPTION
[0018] The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.
[0019] As mentioned above, the first aspect of the present invention provides a glass etching liquid composition, based on the total weight of the composition, the glass etching liquid composition contains 25-37wt% of ammonium fluoride salt, 3-8wt% of alkali metal fluoride salt, 33-50wt% of inorganic acid, 2-10wt% of FeCl3 and ZnCl2, 5-10wt% of viscosity regulator, 5-10wt% of bentonite and the balance of water.
[0020] The surface of the microcrystalline glass is etched using the glass etching liquid composition. The etched microcrystalline glass has a smooth feel and a flash sand effect. The microcrystalline flash sand glass reflects bright light under light, has a unique visual appeal, and a delicate touch that makes people feel smooth and comfortable. It also has good anti-fingerprint, anti-pollution and anti-scratch properties.
[0021] Preferably, based on the total weight of the composition, the glass etching solution contains 25-32wt% of ammonium fluoride salt, 3-5wt% of alkali metal fluoride salt, 33-50wt% of inorganic acid, 3-8wt% of FeCl3 and ZnCl2, 5-8wt% of viscosity modifier, 5-10wt% of bentonite and the balance of water. The inventors found that in this preferred case, the obtained microcrystalline frosted glass has a more uniform sand effect and a more delicate feel.
[0022] In the present invention, ammonium fluoride salt is used as the main raw material of the glass etching liquid composition, which can promote the dissolution and etching of the surface of microcrystalline glass; it helps to improve the wettability and permeability of the etching liquid to the microcrystalline glass, making the etching more uniform. In the present invention, if the content of ammonium fluoride salt is too high, the saturation of the etching liquid will be too high, the etching reaction will be unstable, and the frosted surface will easily have poor color; if the content of ammonium fluoride salt is too low, sand leakage will occur, and it will be visually seen as light-transmitting spots on the frosted surface.
[0023] Compared with NaHF2, KHF2, LiHF2, etc., ammonium fluoride is selected mainly because NH4 + It is strongly hydrophilic and is weakly acidic upon hydrolysis.
[0024] In addition, compared with ammonium salts such as NH4Cl, ammonium fluoride salts can provide fluoride ions (F - ), chemically reacts with the silicon oxide on the surface of the microcrystalline glass, which is beneficial for full contact with the surface of the microcrystalline glass.
[0025] Preferably, the ammonium fluoride salt is selected from at least one of NH4HF2 and NH4F, mainly because NH4HF2 and NH4F have lower costs.
[0026] In the present invention, the alkali metal fluoride salt, in addition to providing fluoride ions, can also help improve the transparency of the etching solution, reduce the generation of impurities and precipitates, and help maintain the stability of the etching solution.
[0027] Preferably, the alkali metal fluoride salt is selected from at least one of NaF and KF. More preferably, the alkali metal fluoride salt is NaF. Since KF has stronger chemical activity and stronger corrosiveness than NaF, while NaF is milder than KF, it is more suitable for the glass etching solution composition system of the present invention.
[0028] In the present invention, the viscosity regulator can prevent the glass etching liquid from settling easily, and at the same time provide a solid surface in the glass etching liquid, attracting active molecules to react with silicon oxide and metal oxide on the surface of the microcrystalline glass to form crystals, stabilize the crystal nucleus, and thus improve the etching effect of the microcrystalline glass.
[0029] Preferably, the viscosity modifier is selected from at least one of barium sulfate and carboxymethyl cellulose. This is mainly because barium sulfate and carboxymethyl cellulose have fine particle sizes, are difficult to dissolve in water, are almost not ionized in water, have large specific surface area and dispersibility, and can provide more favorable conditions for uniform etching.
[0030] More preferably, the viscosity modifier is barium sulfate. Compared with other viscosity modifiers, barium sulfate has a greater cost advantage.
[0031] In the present invention, the chloride ions in FeCl3 and ZnCl2 have a small radius and strong penetrability, so they will be preferentially adsorbed on the surface of the product, and can squeeze out the oxygen atoms in the metal oxide, providing a fast channel for active molecules and surface reactions. Zinc chloride and ferric chloride are used in conjunction to promote the formation of ultrafine frosting layers and control crystal nucleus growth. If the content of both is too low, the crystals on the sample surface are incomplete; if the content is too high, the crystal uniformity is destroyed.
[0032] Preferably, the mass ratio of the FeCl3 to ZnCl2 is (0.5-2): 1. The inventors found that under this preferred condition, the obtained glass etching solution can make the sanding effect more uniform.
[0033] In the present invention, the etching system is an inorganic acid system, which is mainly because the inorganic acid can quickly provide active hydrogen ions to react with ammonium fluoride salts and alkali metal fluoride salts to generate hydrofluoric acid to etch glass.
[0034] Preferably, the inorganic acid is a mixture of concentrated hydrochloric acid and an oxygen-containing inorganic acid. As mentioned above, chloride ions have a small radius and strong penetration, so they will be preferentially adsorbed on the surface of the product, and can exclude oxygen atoms in metal oxides, providing a quick channel for active molecules and surface reactions. Preferably, hydrochloric acid can promote each other with FeCl3 and ZnCl2 in the etching solution system, provide more chloride ions, and thus provide more etching points in the etching system to adapt to the etching of microcrystalline glass, which has the dual characteristics of glass and ceramics.
[0035] Preferably, the inorganic acid is a mixture of concentrated hydrochloric acid and oxygen-containing inorganic acid in a mass ratio of (1.67-4.375): 1. The inventors found that when the concentrated hydrochloric acid and the oxygen-containing inorganic acid are in the range of (1.67-4.375): 1, and cooperate with FeCl3 and ZnCl2 in the etching solution system, the microcrystalline glass flash sand effect obtained after etching meets the requirements, and the etching efficiency is high.
[0036] Preferably, the oxygen-containing inorganic acid is selected from at least one of sulfuric acid, nitric acid, perchloric acid, boric acid, phosphoric acid and bromic acid. The inventors have found that adding an inorganic acid with strong oxidizing ability or strong cleaning ability to the etching system can form a more ideal flash sand effect.
[0037] More preferably, the oxygen-containing inorganic acid is a combination of nitric acid and sulfuric acid. The inventors further found that the use of sulfuric acid and nitric acid in the oxygen-containing inorganic acid can further improve the etching effect of microcrystalline glass, mainly because the strong oxidizing property of nitrate ions in nitric acid and the strong cleaning ability of sulfuric acid on the glass surface and the ability to promote the conversion of pitting corrosion into surface corrosion overlap each other.
[0038] Further preferably, the acidic system of the glass etching liquid composition of the present invention is a tri-acid etching system composed of concentrated hydrochloric acid, nitric acid and sulfuric acid, wherein, based on the total weight of the glass etching liquid composition, the content of concentrated hydrochloric acid is 25-35wt%, the content of nitric acid is 6-10wt%, and the content of sulfuric acid is 2-5wt%.
[0039] More preferably, the mass ratio of nitric acid to sulfuric acid in the oxygen-containing inorganic acid is 1.5-4: 1. The inventors found that under this preferred condition, the obtained glass etching solution can make the sanding effect more uniform.
[0040] The concentrated hydrochloric acid, nitric acid and sulfuric acid used in this application form a three-acid etching system that can create a strong acid environment for the etching liquid, and at the same time has strong oxidizing ability and strong cleaning ability. The obtained glass etching liquid can further promote the formation of an ideal flash sand effect and improve the etching effect of microcrystalline glass.
[0041] In the present invention, the bentonite in the etching system has excellent suspension and good cation exchange capacity, which is beneficial to maintaining the stability of the etching solution.
[0042] In the present invention, the etching of microcrystalline glass is carried out by using a ferric chloride-zinc chloride-strong acid etching system. Under the synergistic effect of ferric chloride, zinc chloride, strong acid and fluoride salt, the surface of the microcrystalline glass can be etched and the growth of crystal nuclei can be controlled to generate microcrystalline flash sand glass with a specific texture.
[0043] As mentioned above, the second aspect of the present invention provides a method for preparing a glass etching solution, the method comprising: ripening the components in the glass etching solution composition described in the first aspect to obtain a glass etching solution.
[0044] Preferably, the aging conditions include: temperature of 35-45° C., time of 48-72 h, and stirring frequency of 30-50 Hz.
[0045] As mentioned above, the third aspect of the present invention provides a glass etching solution prepared by the method described in the second aspect.
[0046] As mentioned above, the fourth aspect of the present invention provides the use of the glass etching liquid described in the third aspect in etching microcrystalline glass.
[0047] The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, the raw materials used are all commercially available analytically pure products.
[0048] The etched microcrystalline glass in the following examples and comparative examples contains 62wt% SiO2, 15wt% Al2O3, 15wt% Li2O, 2wt% K2O, 2wt% Na2O, 1wt% CaO, and 3wt% ZrO2.
[0049] Concentrated hydrochloric acid: provided by a hydrochloric acid solution with a mass fraction of 37wt%.
[0050] Sulfuric acid: provided by a 40wt% sulfuric acid solution.
[0051] Nitric acid: provided by a nitric acid solution with a mass fraction of 68wt%.
[0052] Citric acid: provided by a citric acid solution with a mass fraction of 37 wt%.
[0053] Example 1
[0054] This example is used to illustrate that the glass etching liquid composition of the present invention is used to prepare a glass etching liquid according to the formula and process parameters in Table 1, and to etch microcrystalline glass according to the following method.
[0055] The etching method of the microcrystalline glass comprises the following steps:
[0056] (1) adding each component in the glass etching liquid composition shown in Table 1 into a aging tank for aging to obtain a glass etching liquid;
[0057] (2) The non-etched area of the glass-ceramics is protected by screen printing with acid-resistant ink;
[0058] (3) cleaning the microcrystalline glass area to be etched with a mixture of sulfuric acid (concentration of 40 wt %) and hydrofluoric acid (concentration of 9 wt %) in a volume ratio of 5:8, and then wet etching with a glass etching solution;
[0059] The wet etching conditions are: time 90s, temperature 18°C;
[0060] (4) The wet-etched glass-ceramics are cleaned with deionized water and then dried in a drying furnace.
[0061] Unless otherwise specified, the remaining embodiments and comparative examples are carried out using the same process as that of Example 1, except that the formula of the glass etching liquid composition and the process parameters for preparing the glass etching liquid are different, as shown in Table 1.
[0062] Table 1
[0063]
[0064]
[0065] Comparative Example 1
[0066] This comparative example is carried out in a similar manner to Example 1, except that NaHF2 of equal mass is used to replace NH4HF2 in Example 1; the remaining steps are the same as those in Example 1.
[0067] Comparative Example 2
[0068] This comparative example is carried out in a similar manner to Example 1, except that citric acid of equal mass is used to replace the concentrated hydrochloric acid in Example 1; the remaining steps are the same as those in Example 1.
[0069] Comparative Example 3
[0070] This comparative example is carried out in a similar manner to Example 1, except that lithium chloride of equal mass is used to replace FeCl3 in Example 1; the remaining steps are the same as those in Example 1.
[0071] Comparative Example 4
[0072] This comparative example is carried out in a similar manner to Example 1, except that the glass etching solution composition in this comparative example contains 15 wt % of BaSO4; the remaining steps are the same as those in Example 1.
[0073] Comparative Example 5
[0074] This comparative example is carried out in a similar manner to Example 1, except that the glass etching liquid composition in this comparative example does not contain bentonite; and the remaining steps are the same as those in Example 1.
[0075] Comparative Example 6
[0076] This comparative example is carried out by a method similar to that of Example 1, except that: the formula of the glass etching liquid composition; specifically, this comparative example is carried out by using an existing common glass etching liquid, wherein the common glass etching liquid contains 15wt% NH4HF2, 25wt% Na2SiF6, 20wt% HCl, 5wt% HNO3, 15wt% H2O, 5wt% feldspar powder, 3wt% CaF2, 4wt% KF, and 8wt% BaSO4;
[0077] The remaining steps are the same as those in Example 1.
[0078] Comparative Example 7
[0079] This comparative example is carried out in a similar manner to Example 1, except that the total content of the inorganic acid is adjusted to 52wt%. Specifically, the glass etching liquid composition in this comparative example contains 42wt% of concentrated hydrochloric acid, 7wt% of nitric acid, and 3wt% of sulfuric acid; the remaining steps are the same as in Example 1.
[0080] Test Case
[0081] The performance of the samples prepared in the above example (10mm×10mm microcrystalline glass after wet etching) was tested, wherein the roughness was characterized by a roughness shape measuring instrument 1400G; the haze was characterized by a BYK transmission haze meter; the transmittance was characterized by a transmittance tester-Jiu Zong. At the same time, the unetched microcrystalline glass raw material (white glass) was tested, and the results are shown in Table 2.
[0082] Table 2
[0083]
[0084] Table 2
[0085] Performance parameters Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Roughness / μm 3.12 0.85 1.96 3.21 2.02 2.42 2.19 Haze / % 93.8 68.2 83.9 91.8 89.6 93.6 89.1 Transmittance / % 58 80 66 68 58 52 76 Appearance NG NG NG NG NG NG NG
[0086] Note: OK in Table 2 means no appearance defects and uniform sanding effect, NG means there are appearance defects such as different colors, white spots, fine stripes, sand leakage, uneven flash, poor sanding, etc.
[0087] At the same time, the present invention Figures 1 to 8 The laser confocal microscope (OLYMPUS OLS-4100 laser confocal microscope) microscopic characterization diagrams of the samples prepared in Examples 1-6 and Comparative Examples 1 to 7 are provided as examples.
[0088] Figure 1 The microscopic characterization diagram of the samples prepared in Examples 1-6 is shown in FIG. Figure 1 It can be seen that the crystals (hexagonal pyramid particles) are sharp-edged, the sand effect is uniform and has sufficient coverage.
[0089] Figure 2 This is a microscopic characterization diagram of the sample prepared in Comparative Example 1. Figure 2 It can be seen that after etching, the surface crystals of the microcrystalline glass present a cross structure and feel rough.
[0090] Figure 3 This is a microscopic characterization diagram of the sample prepared in Comparative Example 2. Figure 3 It can be seen that after etching, the surface of the microcrystalline glass is in a state of multiple intersecting microstructures.
[0091] Figure 4 This is a microscopic characterization diagram of the sample obtained in Comparative Example 3. Figure 4It can be seen that after etching, multiple flash points are visible on the surface of the microcrystalline glass, but the crystal edges are not clear.
[0092] Figure 5 This is a microscopic characterization diagram of the sample prepared in Comparative Example 4. Figure 5 It can be seen that after etching, the crystals on the surface of the microcrystalline glass are of different sizes and uneven sparkle.
[0093] Figure 6 This is a microscopic characterization diagram of the sample obtained in Comparative Example 5. Figure 6 It can be seen that the surface sand effect of the microcrystalline glass is uneven and sand is leaking after etching.
[0094] Figure 7 This is a microscopic characterization diagram of the sample prepared in Comparative Example 6. Figure 7 It can be seen that after etching, the surface of the microcrystalline glass presents a large number of flaky structures and the crystals are disordered.
[0095] Figure 8 This is a microscopic characterization diagram of the sample obtained in Comparative Example 7. Figure 8 It can be seen that scratches and pits appear on the surface of the microcrystalline glass after etching.
[0096] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.
Claims
1. A glass etching liquid composition, characterized in that: Based on the total weight of the composition, the glass etching liquid composition contains 25-37wt% of ammonium fluoride salt, 3-8wt% of alkali metal fluoride salt, 33-50wt% of inorganic acid, 2-10wt% of FeCl3 and ZnCl2, 5-10wt% of viscosity regulator, 5-10wt% of bentonite and the balance of water.
2. The glass etching liquid composition according to claim 1, characterized in that: Based on the total weight of the composition, the glass etching solution contains 25-32wt% of ammonium fluoride salt, 3-5wt% of alkali metal fluoride salt, 33-50wt% of inorganic acid, 3-8wt% of FeCl3 and ZnCl2, 5-8wt% of viscosity regulator, 5-10wt% of bentonite and the balance of water.
3. The glass etching liquid composition according to claim 1, characterized in that: The inorganic acid is a mixture of concentrated hydrochloric acid and an oxygen-containing inorganic acid; Preferably, the inorganic acid is a mixture of concentrated hydrochloric acid and oxygen-containing inorganic acid in a mass ratio of (1.67-4.375):
1.
4. The glass etching liquid composition according to claim 1 or 2, characterized in that: The oxygen-containing inorganic acid is selected from at least one of sulfuric acid, nitric acid, perchloric acid, boric acid, phosphoric acid and bromic acid; and / or The ammonium fluoride salt is selected from at least one of NH4HF2 and NH4F; and / or The alkali metal fluoride salt is selected from at least one of NaF and KF; and / or The viscosity modifier is selected from at least one of barium sulfate and carboxymethyl cellulose.
5. The glass etching liquid composition according to claim 4, characterized in that: The oxygen-containing inorganic acid is a combination of nitric acid and sulfuric acid; Preferably, based on the total weight of the glass etching liquid composition, the content of concentrated hydrochloric acid is 25-35wt%, the content of nitric acid is 6-10wt%, and the content of sulfuric acid is 2-5wt%; More preferably, the mass ratio of nitric acid to sulfuric acid in the oxygen-containing inorganic acid is 1.5-4:
1.
6. The glass etching liquid composition according to claim 1 or 2, characterized in that: The mass ratio of the FeCl3 to ZnCl2 is (0.5-2):
1.
7. A method for preparing a glass etching solution, characterized in that: The method comprises: ripening the components in the glass etching liquid composition according to any one of claims 1 to 6 to obtain the glass etching liquid.
8. The method according to claim 7, characterized in that The aging conditions include: temperature of 35-45° C., time of 48-72 hours, and stirring frequency of 30-50 Hz.
9. The glass etching solution prepared by the method described in claim 7 or 8.
10. Use of the glass etching liquid according to claim 9 in etching microcrystalline glass.