Oxidation-discoloration-resistant ultra-white glass cooker glass panel and preparation method thereof

Abstract

The invention discloses an anti-oxidation discoloration ultra-white glass cooker glass panel and a preparation method, and relates to the technical field of cooker glass panels. The kitchen range glass panel comprises a glass panel and a coating, wherein the coating is prepared from the following raw materials in parts by mass: 30-50 parts of acrylic acid modified organic silicon resin, 20-40 parts of silica sol, 10-25 parts of glass powder, 5-15 parts of high-temperature-resistant pigment, 0.5-2 parts of a dispersing agent, 0.3-1.5 parts of a flatting agent, 0.2-1 part of a defoaming agent, 15-30 parts of a solvent and 1-2 parts of an antioxidant. Compared with the prior art that a traditional coating is prone to losing gloss and yellowing due to high-temperature failure and antioxidant volatilization, the cooker glass panel can resist oxidation corrosion for a long time under the long-term high-temperature working condition after being coated with the coating, the undesirable phenomena related to structural damage of the coating are greatly reduced, and the stable performance is maintained.

Description

Technical Field

[0001] This invention relates to the field of cooktop panel technology, specifically to an anti-oxidation and color-changing ultra-white glass cooktop panel and its preparation method. Background Technology

[0002] With the rapid development of the kitchen appliance industry, glass cooktop panels have become widely used in household gas stoves, integrated cooktops, and other products due to their advantages of being aesthetically pleasing, transparent, easy to clean, and wear-resistant. However, during long-term use, the glass panel must withstand multiple tests, including high-temperature baking, corrosion from gas combustion products, and daily friction. Among these, oxidation and aging are the core issues affecting its service life and performance stability.

[0003] Existing cooktop glass panel coatings mostly use common silicone resins and epoxy resins as film-forming substrates, combined with conventional inorganic pigments and additives. Under high-temperature environments, the resin molecules in these coatings are prone to chain breakage. Simultaneously, substances such as oxygen, carbon dioxide, and water vapor produced by gas combustion accelerate the oxidative decomposition of the coating, leading to phenomena such as loss of gloss, yellowing, cracking, and even peeling. Furthermore, the antioxidants used in traditional coatings are mostly general-purpose hindered phenolic and phosphite compounds, which lack sufficient high-temperature resistance and are prone to volatilization or failure under the high-temperature operating conditions of cooktops, failing to maintain the coating's antioxidant protective effect in the long term.

[0004] Meanwhile, the pigment components in existing coatings are prone to changes in crystal structure or chemical properties under high-temperature oxidation environments, leading to color fading, reduced hiding power, and affecting the uniformity of the cooktop's appearance. Some coatings increase the proportion of inorganic fillers to improve temperature resistance, but this can easily lead to reduced coating adhesion and decreased flexibility, making them more susceptible to damage during alternating hot and cold cycles, further exacerbating oxidation and corrosion.

[0005] Currently, the market demands increasing durability, safety, and aesthetics from cooktop products. Traditional cooktop glass panels can no longer meet the oxidation resistance requirements under long-term high-temperature use. Developing a cooktop glass panel that is high-temperature resistant, has long-lasting anti-oxidation effects, strong adhesion, and stable appearance has become a pressing technical problem to be solved in the industry. Summary of the Invention

[0006] The purpose of this invention is to address the problems existing in the prior art by providing an anti-oxidation and color-changing ultra-white glass cooktop panel and its preparation method. The coating of this glass panel can resist oxidation and erosion for a long time under high temperature conditions, avoiding loss of gloss, yellowing, and cracking. At the same time, it ensures pigment stability and strong coating adhesion, adapting to the long-term use needs of cooktops and solving the problems of poor oxidation resistance and insufficient high temperature resistance of traditional coatings.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is: an anti-oxidation and color-changing ultra-white glass cooktop panel, comprising a glass panel and a coating, wherein the coating is prepared from raw materials comprising the following parts by weight: 30-50 parts of acrylic modified silicone resin, 20-40 parts of silica sol, 10-25 parts of glass powder, 5-15 parts of high-temperature resistant pigment, 0.5-2 parts of dispersant, 0.3-1.5 parts of leveling agent, 0.2-1 part of defoamer, 15-30 parts of solvent, and 1-2 parts of antioxidant; The antioxidant is a compound represented by Formula 1; The structure of Equation 1 is as follows: ; In Formula 1, R1 is a substituent, and R1 is any one of alkyl, hydroxyl, and hydrogen from C1 to C6.

[0008] Furthermore, the anti-oxidation and color-changing ultra-white glass cooktop coating is a cured coating.

[0009] Furthermore, the solid content of the acrylic-modified silicone resin is 50±5%.

[0010] Furthermore, the SiO2 content in the silica sol is 30±5%.

[0011] Furthermore, the high-temperature resistant pigment is at least one of iron oxide-based inorganic pigments, cobalt-aluminum-based inorganic pigments, or chromium-tin-based inorganic pigments.

[0012] Furthermore, the iron oxide inorganic pigment is any one of iron oxide red, iron oxide yellow, iron oxide black, and iron oxide brown.

[0013] Furthermore, the cobalt-aluminum inorganic pigment is either cobalt aluminum blue or cobalt aluminum green.

[0014] Furthermore, the chromium-tin inorganic pigment is either chromium tin red or chromium tin violet.

[0015] Furthermore, the dispersant is one or more of the following: sodium polyacrylate solution, sodium polycarboxylate solution, Dow 731A, BYK-155, BYK-190, and BYK-192.

[0016] Furthermore, the leveling agent is BYK-337.

[0017] Furthermore, the defoamer is KS-604; The solvent is one or a mixture of several of propylene glycol methyl ether acetate and diethylene glycol butyl ether acetate.

[0018] Furthermore, the antioxidant is any one of the compounds shown in the following structures: ; .

[0019] Furthermore, the coating preparation method includes the following steps: S1. Add the acrylic-modified silicone resin, silica sol, and 1 / 2 part by mass of solvent to a stirring tank, and stir and mix at a speed of 300-500 rpm for 20-40 minutes to obtain premix A; S2. Add the glass powder, high-temperature resistant pigment, dispersant, residual solvent and antioxidant to the premix A, increase the speed to 800-1200 rpm, and continue stirring for 30-60 minutes to obtain mixed slurry B; S3. Transfer the mixed slurry B to a sand mill for grinding and dispersion until the fineness is ≤15μm to obtain slurry C; S4. Add the leveling agent and defoamer to the slurry C, stir at a speed of 400-600 rpm for 20-40 minutes to mix it evenly, and then filter it to obtain the antioxidant and color-changing ultra-white glass cooktop panel.

[0020] Furthermore, S1 and S2 are performed under a nitrogen atmosphere.

[0021] A method for preparing an anti-oxidation and color-changing ultra-white glass cooktop panel includes the following steps: applying a coating to the surface of the glass panel, and after curing, obtaining a coating thickness of 50μm.

[0022] This invention systematically solves the technical problems of poor high-temperature oxidation resistance, easy loss of gloss and yellowing, cracking and peeling, pigment fading and insufficient adhesion of traditional cooktop glass panel coatings through the synergistic effect of various raw materials and functions. It uses acrylic-modified silicone resin with a solid content of 50±5% as the core film-forming substrate, combined with silica sol. The mass ratio of the two is balanced. The resin provides good flexibility and substrate adhesion for the coating, while the silica sol forms a dense network structure through cross-linking with the resin, effectively blocking the penetration of oxidizing media such as oxygen and water vapor generated by gas combustion, and preventing the resin molecular chains from breaking at high temperatures. At the same time, glass powder improves the coating's hardness and wear resistance, and because its dosage is controlled within a reasonable range, it does not damage the coating's flexibility. Combined with high-temperature resistant iron oxide-based, cobalt-aluminum-based, or chromium-tin-based inorganic pigments, it ensures the stability of the pigment crystal structure and chemical properties under high-temperature oxidation conditions. To prevent color fading and reduced hiding power, a specific structure of antioxidants is heat-resistant and non-volatile, precisely capturing free radicals generated during coating oxidation and effectively inhibiting resin oxidation and decomposition, thus overcoming the shortcomings of traditional general-purpose antioxidants that fail at high temperatures. Dispersants ensure uniform dispersion of solid components such as glass powder and pigments, while leveling agents and defoamers synergistically optimize film formation, preventing defects such as bubbles and sagging in the coating. Solvents adjust the viscosity of the system to ensure full integration of all components. Combined with a nitrogen atmosphere preparation process to reduce oxidation loss during raw material premixing, a synergistic system of "dense film barrier - long-lasting antioxidant inhibition - stable functional filling - uniformly dispersed film formation" is ultimately formed. This allows the coating to maintain good oxidation stability under long-term high-temperature conditions while also possessing strong adhesion, flexibility, and consistent appearance, fully adapting to the needs of cooktop use.

[0023] Compared with the prior art, the beneficial effects of the present invention are: 1. Significantly improved oxidation resistance and high temperature stability: Compared with the problems of traditional coatings in the prior art that are prone to failure due to high temperature and loss of gloss and yellowing due to antioxidant volatilization, the coating of the present invention can resist oxidation erosion for a long time under long-term high temperature conditions, greatly reduce the adverse phenomena related to coating structure damage, and maintain stable performance.

[0024] 2. Enhanced pigment and appearance stability: Unlike existing coating pigments that are prone to structural or property changes and color fading under high-temperature oxidation, this invention uses high-temperature resistant inorganic pigments in combination with a synergistic film-forming system, which can better maintain pigment stability, ensure coating color and hiding power, and maintain consistent appearance.

[0025] 3. Superior physical properties and durability of the coating: Overcoming the shortcomings of existing technologies that add inorganic fillers to improve temperature resistance, resulting in decreased coating adhesion and reduced flexibility, this invention optimizes the raw material ratio to ensure coating hardness and wear resistance while taking into account adhesion and flexibility, reducing the risk of damage in alternating hot and cold environments and improving overall durability. Attached Figure Description

[0026] Figure 1 This is the NMR spectrum of compound 3 described in this invention.

[0027] Figure 2 This is the NMR spectrum of antioxidant 1 as described in this invention. Detailed Implementation

[0028] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] Preparation Example 1: Preparation of Antioxidant 1: ; The CAS number of compound 1 is: 2044977-63-9; The CAS number for compound 2 is: 1359843-89-2; Under a nitrogen atmosphere, 5 g of compound 1, 3.81 g of compound 2, and 80 ml of a composite solution (a mixture of toluene and water, with a volume ratio of toluene to water of 3:1) were added sequentially to the reaction system. After thorough mixing, the nitrogen atmosphere was purged twice. Under nitrogen protection, 0.55 g of tetra(triphenylphosphine)palladium was added to the reaction system, and the nitrogen atmosphere was purged twice again. The mixture was heated to 105 °C and refluxed for 10 hours. The heating was then turned off, and the mixture was cooled to room temperature. The mixture was allowed to stand and separated. The aqueous phase was extracted twice with ethyl acetate. The organic phases were combined, washed three times with water, and evaporated to dryness. The mixture was then subjected to silica gel column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to obtain 5.49 g of compound 3. The mass spectrometry (MS+1:424) and NMR results are shown in the figure. Figure 1 .

[0030] ; The CAS number for compound 4 is 95-88-5; Under a nitrogen atmosphere, 1.89 g of compound 4 was dissolved in 60 ml of toluene. Then, 5.49 g of compound 3, the prepared solution, 2.49 g of sodium tert-butoxide, 0.35 g of tris(dibenzylacetone)palladium, and 0.07 g of tri-tert-butylphosphine were added sequentially to the reaction system. The mixture was stirred thoroughly, heated to 120 °C, and refluxed for 12 h. After the reaction was complete, the temperature was slightly lowered, and the mixture was filtered through silica gel. The filtrate was cooled to room temperature, washed three times with water, and the organic phase was retained. The aqueous phase was then extracted with ethyl acetate. The combined organic phases were dried over anhydrous magnesium sulfate, evaporated to dryness, and subjected to silica gel column chromatography. A mixture of petroleum ether and ethyl acetate was used as the eluent, and the solution was concentrated to obtain 5.35 g of antioxidant 1. Mass spectrometry (MS+1): 532; NMR results are shown below. Figure 2 .

[0031] Preparation Examples 2-4: In Preparation Examples 2-4, antioxidants 2-4 were prepared sequentially, following the preparation method of Preparation Example 1, except that compound 4 was replaced. The rest remained the same as in Preparation Example 1. See Table 1 for details.

[0032] Table 1 Example 1: Coating preparation: 1. Raw material components: Acrylic-modified silicone resin: 40 parts (50% solid content); Silica sol: 30 parts (SiO2 content 30%) Glass powder: 18 parts; High-temperature resistant pigment: 10 parts (iron oxide red, iron oxide inorganic pigment); Dispersant: 1.2 parts (BYK-155); Leveling agent: 0.8 parts (BYK-337); Defoamer: 0.6 parts (Shin-Etsu KS-604); Solvent: 22 parts (propylene glycol methyl ether acetate); Antioxidant: 1.5 parts (antioxidant 1 prepared in Preparation Example 1).

[0033] 2. Preparation method: S1. Purge the air into the stirred tank with nitrogen three times to maintain the nitrogen atmosphere. Add the above-mentioned acrylic modified silicone resin, silica sol and 11 parts of solvent (1 / 2 part by mass of solvent). Adjust the speed to 400 rpm and stir for 30 minutes to obtain premix A. S2. Maintaining a nitrogen atmosphere, add glass powder, iron oxide red, BYK-155 dispersant, the remaining 11 parts of solvent and antioxidant 1 to premix A in sequence. Increase the speed to 1000 rpm and continue stirring for 45 minutes to obtain mixed slurry B. S3. Transfer the mixed slurry B to a sand mill for grinding and dispersion treatment. During the process, take samples to test the fineness until the fineness of the slurry is ≤12μm to obtain slurry C; S4. Add BYK-337 leveling agent and KS-604 defoamer to slurry C, adjust the speed to 500 rpm, stir for 30 minutes to make it fully mixed, then filter with a 100-mesh filter and collect the filtrate to obtain the coating.

[0034] Examples 2-4: Referring to the preparation method of Example 1, antioxidant 1 was replaced sequentially with antioxidant 2-antioxidant 4, and the rest remained the same as in Example 1.

[0035] Comparative Example 1: Referring to the preparation method of Example 1, antioxidant 1 was replaced with antioxidant 1010 in sequence, and the rest remained the same as in Example 1.

[0036] Comparative Example 2: Referring to the preparation method of Example 1, antioxidant 1 was replaced with antioxidant 168 in sequence, and the rest remained the same as in Example 1.

[0037] Comparative Example 3: Referring to the preparation method of Example 1, antioxidant 1 was replaced with antioxidant BHT in sequence, and the rest remained the same as in Example 1.

[0038] Comparative Example 4: The preparation method of Example 1 was followed, but without the addition of antioxidant 1, and the rest remained the same as in Example 1.

[0039] Performance testing: Test sample: The coatings prepared in the examples and comparative examples were applied to the surface of the glass panel and cured to obtain an anti-oxidation and color-changing ultra-white glass cooktop panel with a coating thickness of 50 μm.

[0040] 1. High-temperature oxidation performance test: The test sample was placed in an 80℃ high-temperature chamber and kept at a constant temperature for 2000 hours. After being taken out and cooled to room temperature, the color difference change ΔE and surface condition of the sample were measured. The data are shown in Table 2.

[0041] 2. Alternating hot and cold cycle test: The test sample was first placed in a -20℃ low temperature chamber for 8 hours, and then placed in an 80℃ high temperature chamber for 8 hours. The cycle was repeated 1000 times. The color difference change ΔE and surface condition of the sample were detected. The data are shown in Table 2.

[0042] Table 2 In the examples, the coating on the glass panel surface prepared showed a smoother color difference in both high-temperature oxidation and alternating hot and cold oxidation tests. The surface remained flat and intact, without any defects such as loss of gloss, yellowing, cracking, or peeling. The color stability and structural integrity were excellent. In contrast, the comparative examples using traditional antioxidants or without antioxidants showed more obvious color difference changes in both types of tests. The surface showed varying degrees of loss of gloss and yellowing, and some even cracked. The comparative examples without antioxidants showed severe loss of gloss, deep yellowing, and obvious cracking and peeling. The overall oxidation resistance and environmental stability were far inferior to those of the examples.

[0043] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. An anti-oxidation and color-changing ultra-white glass cooktop panel, comprising a glass panel and a coating, characterized in that, The coating is prepared from raw materials comprising the following parts by weight: 30-50 parts acrylic modified silicone resin, 20-40 parts silica sol, 10-25 parts glass powder, 5-15 parts high-temperature resistant pigment, 0.5-2 parts dispersant, 0.3-1.5 parts leveling agent, 0.2-1 part defoamer, 15-30 parts solvent, and 1-2 parts antioxidant; The antioxidant is a compound represented by Formula 1; The structure of Equation 1 is as follows: ; In Formula 1, R1 is a substituent, and R1 is any one of alkyl, hydroxyl, and hydrogen from C1 to C6.

2. The anti-oxidation and color-changing ultra-white glass cooktop panel according to claim 1, characterized in that, The solid content of the acrylic-modified silicone resin is 50±5%.

3. The anti-oxidation and color-changing ultra-white glass cooktop panel according to claim 1, characterized in that, The SiO2 content in the silica sol is 30±5%.

4. The anti-oxidation and color-changing ultra-white glass cooktop panel according to claim 1, characterized in that, The high-temperature resistant pigment is at least one of iron oxide inorganic pigments, cobalt aluminum inorganic pigments, or chromium tin inorganic pigments.

5. The anti-oxidation and color-changing ultra-white glass cooktop panel according to claim 1, characterized in that, The dispersant is one or more of the following: sodium polyacrylate solution, sodium polycarboxylate solution, Dow 731A, BYK-155, BYK-190, and BYK-192.

6. The anti-oxidation and color-changing ultra-white glass cooktop panel according to claim 1, characterized in that, The leveling agent is BYK-337.

7. The anti-oxidation and color-changing ultra-white glass cooktop panel according to claim 1, characterized in that, The defoamer is KS-604; The solvent is one or a mixture of several of propylene glycol methyl ether acetate and diethylene glycol butyl ether acetate.

8. The anti-oxidation and color-changing ultra-white glass cooktop panel according to claim 1, characterized in that, The antioxidant is any one of the compounds shown in the following structures: ； 。 9. An anti-oxidation and color-changing ultra-clear glass cooktop panel according to any one of claims 1-8, characterized in that, The coating preparation method includes the following steps: S1. Add the acrylic-modified silicone resin, silica sol, and 1 / 2 part by mass of solvent to a stirring tank, and stir and mix at a speed of 300-500 rpm for 20-40 minutes to obtain premix A; S2. Add the glass powder, high-temperature resistant pigment, dispersant, residual solvent and antioxidant to the premix A, increase the speed to 800-1200 rpm, and continue stirring for 30-60 minutes to obtain mixed slurry B; S3. Transfer the mixed slurry B to a sand mill for grinding and dispersion until the fineness is ≤15μm to obtain slurry C; S4. Add the leveling agent and defoamer to the slurry C, stir at a speed of 400-600 rpm for 20-40 minutes to make it evenly mixed, and after filtration, the antioxidant and color-changing ultra-white glass stove panel is obtained. S1 and S2 are performed under a nitrogen atmosphere.

10. A method for preparing an antioxidant and color-changing ultra-white glass cooktop panel, characterized in that, Includes the following steps: The coating is applied to the surface of the glass panel and cured to obtain a coating thickness of 50μm.

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