A high-temperature anti-adhesive agent, its preparation method, and its application in hot bending of automotive glass

Abstract

The present invention discloses a high-temperature anti-sticking agent, a preparation method, and an application thereof. The high-temperature anti-sticking agent comprises expanded graphite, wherein silicon dioxide is uniformly deposited in the expanded graphite, and the mass ratio of the expanded graphite to silicon dioxide is 10 to 30 parts:0.4 to 1.8 parts. The high-temperature anti-sticking agent exhibits excellent hydrophilicity under the current hot bending process used for automotive windshields, can be diluted completely with water, is easy to use, flame-retardant and safe to use, and is environmentally friendly with no VOC emissions. During the low-temperature period (below 500°C) of the hot bending process, the agent expands in volume, forming a barrier on the ink surface. The scaly structure forms a thin film covering the ink surface, which does not melt during the entire glass bending process, thereby effectively preventing adhesion between the A and B glass layers.

Description

Technical Field

[0001] The present invention relates to the field of high-temperature anti-sticking agents, and in particular to a high-temperature anti-sticking agent and a preparation method and application thereof. Background Art

[0002] As one of the important safety parts of a car, the windshield and sunroof glass have special performance requirements: moisture resistance, high temperature resistance, high pressure resistance, UV protection, infrared protection, impact resistance and high safety. At present, the preparation process of automobile windshield and sunroof glass is as follows: the original glass is trimmed, ground and cleaned according to the designed size. After the black edge ink is printed on the A piece of glass as the outer glass and dried, it is sintered at 600℃ for about 30 minutes. The ink is basically sintered, but the glass has not yet deformed. A layer of silicon powder is sprayed on the entire side of the printed ink, dried naturally, paired with B piece, compacted, and the paired glass is placed on the mold and hot bent at 400-700℃ for 30 minutes. The actual glass deformation temperature range is between 630-700℃. The glass is hot bent into shape using its own gravity. After separation, it is cleaned and then a PVB film is sandwiched between the A and B pieces of glass using a laminating machine for lamination. After preliminary rolling, the laminated glass is moved into an autoclave and pressurized and kept warm at 110-130℃ to bond the two pieces of glass together to obtain a finished automobile windshield. In this process, due to the instability of the hot bending furnace temperature, the different arch heights of different car models, and the different hot bending temperatures, the silicon powder anti-sticking agent currently used can easily cause the A and B glasses to stick together during the hot bending process, resulting in scrap, affecting the yield rate, and increasing production costs.

[0003] Chinese patent publication number CN111498841B discloses a method for preparing expanded graphite and its application in the adsorption of aromatic compounds. This method involves mixing one or more low-boiling-point alcohols with water and then adding them to natural flake graphite to produce pre-intercalated graphite. The pre-intercalated graphite is then mixed with a weakly or non-polar, low-boiling-point organic compound and sealed in an autoclave for heating and intercalation. After intercalation, the mixture is cooled to room temperature and then expanded using microwaves. The resulting FEG product exhibits significant advantages in adsorbing organic matter, particularly aromatic compounds. (This method is a method for producing expanded graphite. By infiltrating an organic solvent between graphite layers and then heating under high pressure, the volume expansion of the organic solvent increases the distance between the graphite layers, expanding the surface area and enhancing adsorption capacity. The present invention improves the hydrophilicity of the prepared expanded graphite through chemical modification, resulting in a high-temperature anti-sticking agent for expanded graphite with excellent water compatibility.) Summary of the Invention

[0004] The invention provides a high-temperature anti-adhesion agent and a preparation method thereof. The high-temperature anti-adhesion agent has good expansion performance and hydrophilicity at high temperature.

[0005] The present invention also discloses the application of a high-temperature anti-sticking agent in the hot bending of automobile glass, which can effectively prevent the adhesion of A and B glasses during the hot bending process without affecting the light transmittance of A and B glasses.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is:

[0007] A high-temperature anti-sticking agent comprises expanded graphite, wherein silicon dioxide is uniformly deposited in the expanded graphite, and the mass ratio of the expanded graphite to silicon dioxide is 10-30 parts:0.4-1.8 parts.

[0008] The present invention uniformly deposits silicon dioxide on the surface of expanded graphite, which not only increases the hydrophilicity of the expanded graphite, but also the interaction between the expanded graphite and silicon dioxide can synergistically improve the expansion performance at high temperatures, and has good high-temperature anti-stickiness.

[0009] The high temperature in the high temperature anti-sticking agent refers to 400-700° C. Expanded graphite is a loose, porous, worm-like substance obtained by intercalating natural graphite flakes, washing, drying, and high temperature expansion.

[0010] In one preferred embodiment, the D99 of the expanded graphite is below 8μ.

[0011] Based on the timeliness of vibration grinding and the subsequent usability, the D99 of expanded graphite after vibration grinding is controlled below 8μ. If the vibration grinding is too fine, the vibration grinding time will be longer, and if it is too coarse, it will easily clog the gun and cause unevenness during subsequent spraying.

[0012] Expanded graphite has a flake structure and its volume expands more than 100 times within the particle size range of 200-800 mesh.

[0013] In one preferred embodiment, the initial expansion temperature of the expanded graphite is between 180 and 300°C.

[0014] The initial expansion temperature of the expanded graphite is calculated based on the dehydration temperature of silicic acid and the initial melting temperature of the glass ink.

[0015] The present invention also discloses a method for preparing the high-temperature anti-sticking agent, comprising the following steps:

[0016] S1. Add low-boiling-point alcohol and expanded graphite and disperse them evenly, shake and grind them, and then discharge the material;

[0017] Add organic acid and deionized water to the materials discharged from S2 and S1, stir evenly, and then slowly add water-soluble silicate solution until the pH value reaches 4-6, which is the end point of the reaction. Filter and wash with distilled water several times until the washing liquid is neutral;

[0018] The filter cake obtained in S3 and S2 is baked to dehydrate the silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite and then taken out for use.

[0019] Low-boiling-point alcohol has good compatibility with expanded graphite. Expanded graphite can be quickly and evenly dispersed in it. It is easy to volatilize after synthesis, dries quickly, and can dissolve organic acids well.

[0020] Water-soluble silicates provide silicate radicals, which react with organic acids to form insoluble silicic acid, which deposits on the surface of the expanded graphite. The small amount of organic acid salt produced by the reaction between the organic acid and the water-soluble silicate can dissolve in a mixture of low-boiling alcohol and water. The silicic acid dehydrates and becomes silicon dioxide, which is completely adsorbed on the surface of the expanded graphite.

[0021] In one preferred embodiment, the mass parts of the raw materials in the preparation method are: 10-30 parts of low-boiling point alcohol, 10-30 parts of expanded graphite, 0.4-7.5 parts of organic acid, 35-430 parts of deionized water, and 2-8 parts of water-soluble silicate; preferably, 12-28 parts of low-boiling point alcohol, 12-28 parts of expanded graphite, 1.0-7.0 parts of organic acid, 2.5-7.5 parts of water-soluble silicate, and 44-403 parts of deionized water; further preferably, 15-26 parts of low-boiling point alcohol, 15-26 parts of expanded graphite, 1.2-6.6 parts of organic acid, 3-7 parts of water-soluble silicate, and 35-430 parts of deionized water.

[0022] If the silicate concentration is too low, the reaction time and deposition efficiency will be low. If the concentration is too high, silicate will be produced too quickly, which will lead to uneven deposition.

[0023] In one preferred embodiment, the boiling point of the organic acid is between 60-150° C.; preferably, the organic acid includes one or more of formic acid, acetic acid, trifluoroacetic acid, propionic acid and acrylic acid; further preferably, the organic acid includes one or more of formic acid, acetic acid and trifluoroacetic acid.

[0024] Ensure that the trace amount of acid remaining on the surface of the expanded graphite can be volatilized during the silicic acid dehydration process.

[0025] In one preferred embodiment, the water-soluble silicate includes one or more of sodium silicate, potassium silicate, ammonium silicate and lithium silicate; preferably, the water-soluble silicate includes one or more of sodium silicate, potassium silicate and ammonium silicate.

[0026] In one preferred embodiment, the low-boiling-point alcohol has a boiling point of 60-120°C and a carbon chain of no more than 4; preferably, the low-boiling-point alcohol includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol; more preferably, the low-boiling-point alcohol has a boiling point of 60-100°C, is miscible with water, and includes one or more of methanol, ethanol, n-propanol and isopropanol.

[0027] The longer the carbon chain and the worse the water compatibility, the more phase separation will be formed, and the soluble silicate will be difficult to precipitate on the surface of the expanded graphite.

[0028] The dispersion time in S1 is 1 to 1.5 hours.

[0029] Specifically, zirconium beads with a diameter of 0.8 to 1.0 mm are added to S1 and the mixture is shaken and ground for 24 to 30 hours. Preferably, the mass of the zirconium beads is 1.5 to 2 times the total mass of the expanded graphite and the low-boiling alcohol.

[0030] The baking temperature in S3 is 150-160°C and the baking time is 1-1.5 hours. The baking temperature is controlled at 150-160°C, which is the temperature at which silicic acid dehydrates to form silicon dioxide. Too high a temperature will result in high energy consumption and waste, and may also cause the intercalants between the expanded graphite layers to decompose, affecting the expansion effect.

[0031] The present invention also discloses an application of a high-temperature anti-adhesive agent in hot bending of automobile glass. The high-temperature anti-adhesive agent is evenly mixed with water, sprayed on the glass surface with printed ink, and dried; preferably, the high-temperature anti-adhesive agent and water are mixed at a ratio of 1:8 to 10.

[0032] The high-temperature anti-sticking agent prepared by the invention has good hydrophilicity and is easily dispersed in water. During use, it only needs to be diluted with water and shaken well before use.

[0033] In one preferred embodiment, in the preparation of automobile windshield and sunroof glass, sheet A is printed with ink, and after the surface is dried, a layer of high-temperature anti-sticking agent is sprayed on the glass surface of the printed ink. After air drying, it is paired with sheet B and fired once to form.

[0034] The mechanism of the present invention includes the following:

[0035] Graphite crystals are bidimensional macromolecular layered structures. The carbon atoms within each plane are bonded by carbon-carbon covalent bonds, and the layers are held together by weak van der Waals forces. Graphite's layered structure is very typical. Each sheet is a layer of carbon atoms, and the carbon atoms within the layer form strong covalent bonds through sp2 hybrid orbitals. This means that one 2s electron and two 2p electrons are hybridized in equivalent orbitals, located on the same plane, forming σ bonds with each other, while the two unhybridized 2p electrons are perpendicular to the plane, forming π bonds. This layered structure of graphite allows for the presence of certain gaps between the layers. Therefore, under certain conditions, atoms (or individual molecules) of certain reactants (such as acids, bases, and halogens) can enter the interlayer gaps and form intercalation compounds with the carbon network planes. Graphite with intercalation compounds is known as expandable graphite. The distances between carbon atoms are large, and the bonds between them are weak. This structure allows intercalation substances to enter the interlayers smoothly without disrupting the hexagonal network of carbon atoms within the layers. Therefore, natural graphite is an excellent matrix material for preparing graphite intercalation compounds. Expandable graphite is a crystalline compound that uses physical or chemical methods to insert non-carbonaceous reactants into the graphite interlayers, bonding to the hexagonal network planes while maintaining the graphite's layered structure. It not only retains the excellent physical and chemical properties of graphite, but also, due to the interaction between the intercalation substance and the graphite layers, exhibits new properties not possessed by native graphite or intercalation substances. When exposed to high temperatures, the intercalation compound in graphite decomposes, generating a thrust along the perpendicular axis of the graphite interlayers. This thrust is far greater than the interlayer bonding strength of the graphite particles. This thrust pushes the graphite interlayers apart, causing the graphite particles to expand significantly along the perpendicular axis, forming a worm-like structure called expanded graphite. Expanded graphite's high-temperature expansion properties make it an excellent interlayer anti-adhesion agent for hot bending of automotive glass. However, the low hydroxyl content on the graphite surface results in poor hydrophilicity, making it difficult to disperse in water. To improve the hydrophilicity of expanded graphite, it needs to be coated with a water-insoluble inorganic material. For automotive glass, which primarily contains soda-lime glass and trace amounts of aluminum oxide, suitable inorganic materials include calcium carbonate, aluminum oxide, and silicon dioxide. Calcium carbonate cannot form new chemical or hydrogen bonds with the expanded graphite surface, resulting in poor adhesion and easy separation from the expanded graphite, thus failing to achieve effective improvement. During the laminated glass production process, if the presence of aluminum oxide affects processing conditions such as temperature, pressure, and light transmittance, it can also reduce the adhesion between the PVB film and the glass. Instabilities during processing can damage the film's structure, compromising its adhesion to the glass. Therefore, aluminum oxide is not suitable. As the main component of glass, silicon dioxide does not produce the above-mentioned side effects. In addition, silicon dioxide can form O-Si-O chemical bonds with the hydroxyl groups on the surface to improve adhesion. When used, it is strongly dispersed in water and is not easily separated from the expanded graphite.

[0036] The present invention is further explained below:

[0037] 1. The present invention selects the initial expansion temperature of expanded graphite to be between 180 and 300°C. If the initial expansion temperature of expanded graphite is lower than 180°C, the oven temperature fluctuates slightly during the baking process after the reaction is completed, reaching the initial expansion temperature, causing premature expansion and increased particle size, which is unfavorable for subsequent spraying and affects the subsequent use effect. If the initial expansion temperature of expanded graphite is higher than 300°C, there is little expanded graphite between 300 and 500°C on the market, resulting in high cost and a narrow raw material selection range. If the initial expansion temperature exceeds 500°C, the ink begins to soften and begin to melt, and the expanded graphite has not yet begun to expand, and cannot achieve a good anti-sticking effect.

[0038] 2. The present invention uses low-boiling-point alcohols with a boiling point between 60 and 120°C, with methanol having the lowest boiling point, exceeding 60°C. Alcohols with a boiling point exceeding 120°C have more carbon atoms and poor compatibility with water, resulting in phase separation and making it difficult for soluble silicates to precipitate on the surface of expanded graphite.

[0039] The high-temperature anti-sticking agent is used to effectively prevent the glass ink on the A-glass (base glass) from adhering to the B-glass (cover glass) during the glass bending process, thereby improving the yield rate of automobile windshields.

[0040] Compared with the prior art, the present invention has the following beneficial effects:

[0041] 1. Good hydrophilicity and easy to disperse in water: During the use of the production line, just dilute it with water to 20%, shake it well and it can be used. It is easy to use, all diluted with water, has no VOC formula, is flame retardant and environmentally friendly.

[0042] 2. High temperature resistance of 500-700℃: It will not melt during the whole process of glass hot bending, causing the two pieces of glass to stick together.

[0043] 3. Flake structure: When sprayed on the ink surface, the fine structures are connected to each other to form a relatively dense structure, which protects the glass powder in the ink underneath from melting and causes the adhesion of A and B glasses.

[0044] 4. It will expand below 500℃: The glass powder in the ink will expand before it starts to melt, changing the distance between A and B glass, further preventing adhesion caused by high temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0046] Figure 1 This is the water drop angle measurement diagram of untreated expanded graphite;

[0047] Figure 2 This is a schematic diagram of water droplets on the surface of untreated expanded graphite after it is made into a film;

[0048] Figure 3 This is a schematic diagram of water droplets on the surface of a film made of treated expanded graphite;

[0049] Figure 4 This is a schematic diagram of the sticking after sintering at 630°C using silicon dioxide as a high-temperature anti-sticking agent in Comparative Example 1: one end of the glass is severely stuck and the two pieces of glass cannot be separated.

[0050] Figure 5 This is a schematic diagram of the sticking after sintering at 650°C using silicon dioxide as a high-temperature anti-sticking agent in Comparative Example 1: both ends of the glass are severely stuck and the two pieces of glass cannot be separated.

[0051] Figure 6 This is a schematic diagram of the adhesion after sintering at 630°C with sericite as a high-temperature anti-adhesive agent in Comparative Example 2: one end of the glass is severely adhered and the two pieces of glass cannot be separated.

[0052] Figure 7 This is a schematic diagram of the adhesion after sintering at 650°C with sericite as a high-temperature anti-adhesive agent in Comparative Example 2: both ends of the glass are severely adhered and the two pieces of glass cannot be separated.

[0053] Figure 8 This is a schematic diagram of the bonding of the sheets after sintering at 630°C using flaky aluminum oxide as a high-temperature anti-sticking agent in Comparative Example 3: The adhesion at both ends is very slight, and the two sheets of glass can be separated.

[0054] Figure 9 This is a schematic diagram of the adhesion after sintering at 650°C with flaky aluminum oxide as a high-temperature anti-adhesive agent in Comparative Example 3: both ends of the glass are severely adhered and the two pieces of glass cannot be separated.

[0055] Figure 10 This is a schematic diagram of the adhesion after sintering at 630℃ using ordinary graphite as a high-temperature anti-adhesive in Comparative Example 4: the adhesion at both ends is very slight, the two pieces of glass can be separated, but the high-temperature anti-adhesive remains on the glass and ink surfaces after washing with water.

[0056] Figure 11 This is a schematic diagram of the bonding after sintering at 650°C using ordinary graphite as a high-temperature anti-sticking agent in Comparative Example 4: one end is linearly bonded, and the other end is slightly bonded. The two pieces of glass can be separated, but the high-temperature anti-sticking agent on the glass and ink surfaces remains after being washed with water.

[0057] Figure 12This is a schematic diagram of the adhesion after sintering at 630℃ using flake graphite as a high-temperature anti-adhesive in Comparative Example 5: the adhesion at both ends is very slight, the two pieces of glass can be separated, but the high-temperature anti-adhesive remains on the glass and ink surfaces after washing with water.

[0058] Figure 13 This is a schematic diagram of the adhesion after sintering at 650℃ using flake graphite as a high-temperature anti-adhesive in Example 5: one end is linearly adhered and the other end is slightly adhered. The two pieces of glass can be separated, but the high-temperature anti-adhesive remains on the glass and ink surfaces after being washed with water.

[0059] Figure 14 This is a schematic diagram of the adhesion after sintering at 630℃ using expanded graphite as a high-temperature anti-adhesive in Comparative Example 6: There is no adhesion, the two pieces of glass can be separated, but the high-temperature anti-adhesive remains on the glass and ink surfaces after washing with water.

[0060] Figure 15 This is a schematic diagram of the adhesion after sintering at 650℃ using expanded graphite as a high-temperature anti-adhesive in Comparative Example 6: one end is slightly adhered, the two pieces of glass can be separated, but the high-temperature anti-adhesive remains on the glass and ink surfaces after being washed with water.

[0061] Figure 16 This is a schematic diagram of the bonding process after sintering at 630°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 1: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0062] Figure 17 This is a schematic diagram of the bonding process after sintering at 650°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 1: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0063] Figure 18 This is a schematic diagram of the bonding process after sintering at 630°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 2: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0064] Figure 19 This is a schematic diagram of the bonding process after sintering at 650°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 2: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0065] Figure 20 This is a schematic diagram of the bonding process after sintering at 630°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 3: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0066] Figure 21This is a schematic diagram of the bonding process after sintering at 650°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 3: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0067] Figure 22 This is a schematic diagram of the bonding process after sintering at 630°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 4: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0068] Figure 23 This is a schematic diagram of the bonding process after sintering at 650°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 4: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0069] Figure 24 This is a schematic diagram of the bonding process after sintering at 630°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 5: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0070] Figure 25 This is a schematic diagram of the bonding process after sintering at 650°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 5: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0071] Figure 26 This is a schematic diagram of the bonding process after sintering at 630°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 6: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water.

[0072] Figure 27 This is a schematic diagram of the bonding process after sintering at 650°C using modified expanded graphite as a high-temperature anti-sticking agent in Example 6: the entire panel is not sticky, the two glass sheets can be separated, and the high-temperature anti-sticking agent on the glass and ink surfaces is rinsed clean with water. DETAILED DESCRIPTION

[0073] The present invention will be described in detail below with reference to the accompanying drawings and in combination with embodiments. It should be noted that, in the absence of conflict, the embodiments and features of the embodiments of the present invention may be combined with each other.

[0074] Dry plate production:

[0075] Ink model: 1L6040-IR701A (Baifu)

[0076] Glass: 2mm float glass

[0077] Printing: 200-250 mesh polyester screen printing one layer

[0078] Surface drying: 180℃x2min

[0079] Pre-burning: 450-590℃x30min

[0080] Comparative Example 1

[0081] Table 1 Comparative Example 1 Group Distribution Ratio

[0082]

[0083]

[0084] Add distilled water to a 300g glue tank, stir, add silica, and disperse evenly. Take two pieces of glass that have been printed with ink, and use a 0.8-1.0mm diameter hand spray gun to spray the dispersed silica dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0085] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0086] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0087] Comparative Example 2

[0088] Table 2 Comparative Example 2 Group Allocation Ratio

[0089] Components Manufacturer Model Parts by weight distilled water self made 19 Sericite GD-4 / Chuzhou Ge Rui 1

[0090] Add distilled water to a 300g glue jar, stir, add sericite, and disperse evenly. Take two pieces of glass that have been printed with ink, and use a 0.8-1.0mm diameter hand spray gun to spray the dispersed sericite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0091] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0092] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0093] Comparative Example 3

[0094] Table 3 Comparative Example 3 Group Allocation Ratio

[0095]

[0096]

[0097] Add distilled water to a 300g glue tank, stir, add flake aluminum oxide, and disperse evenly. Take two pieces of glass that have been printed with ink, and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed flake aluminum oxide dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0098] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0099] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0100] Comparative Example 4

[0101] Table 4 Comparative Example 4 Group Allocation Ratio

[0102] Components Manufacturer Model Parts by weight distilled water self made 19 Ordinary graphite 2800 / Shandong Henglin 1

[0103] Add distilled water to a 300g glue jar and stir. Add ordinary graphite. The graphite floats on the water surface and is difficult to disperse evenly. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed ordinary graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0104] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0105] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0106] Comparative Example 5

[0107] Table 5 Comparative Example 5 Group Allocation Ratio

[0108]

[0109]

[0110] Add distilled water to a 300g glue jar and stir. Add flake graphite. The graphite floats on the water and is difficult to disperse evenly. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed flake graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0111] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0112] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0113] Comparative Example 6

[0114] Table 6 Comparative Example 6 Group Allocation Ratio

[0115] Components Manufacturer Model Parts by weight distilled water self made 19 Expanded graphite EG-150 / Qingdao Yanhai 1

[0116] Add distilled water to a 300g glue jar and stir. Add expanded graphite. The graphite floats on the water surface and is difficult to disperse evenly. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed expanded graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0117] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0118] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0119] Example 1

[0120] Table 7 Example 1 group distribution ratio

[0121]

[0122]

[0123] Take 5 parts of sodium silicate and add it to a beaker, add 125 parts of water, stir and dissolve completely.

[0124] Add methanol to a three-necked flask and stir. Add expanded graphite and mix evenly. Disperse at high speed for 1 hour. Pour the mixture into a glass bottle dedicated for shaking. Add 60 parts of 0.8-1.0mm zirconium beads and shake and grind for 24 hours. Detect the particle size distribution until D99 is below 8μ. Discharge the material and introduce it into a three-necked flask and stir. Add 1.9 parts of formic acid and 20 parts of deionized water and stir evenly. Pour the dissolved sodium silicate solution into a constant pressure funnel and slowly add it dropwise to the three-necked flask while stirring rapidly. After the addition is complete, continue stirring to react. Measure the pH value of the mixed system until the pH reaches between 4-6, which is the reaction end point. Filter and wash with distilled water several times until the pH is 6-7. Place the filter cake in a 150°C oven and bake for 1 hour to dehydrate the produced silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite. Remove and set aside.

[0125] Add distilled water to a 300g plastic jar and stir. Add the modified expanded graphite. The graphite will not float on the water surface and should be evenly dispersed. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed modified expanded graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0126] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0127] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0128] Example 2

[0129] Table 8 Implementation of 2 group allocation ratios

[0130]

[0131]

[0132] Take 4.4 parts of sodium silicate and add it to a beaker. Add 138 parts of water and stir until completely dissolved.

[0133] Add ethanol to a three-necked flask and stir. Add expanded graphite and mix evenly. Disperse at high speed for 1 hour. Pour the mixture into a glass bottle dedicated for shaking. Add 66 parts of 0.8-1.0mm zirconium beads and grind them for 24 hours. Detect the particle size distribution until D99 is below 8μ. Discharge the material and introduce it into a three-necked flask and stir. Add 2.2 parts of acetic acid and 22 parts of deionized water and stir evenly. Pour the dissolved sodium silicate solution into a constant pressure funnel and slowly add it dropwise to the three-necked flask while stirring rapidly. After the addition is complete, continue stirring the reaction and measure the pH value of the mixed system until the pH reaches between 4-6, which is the reaction end point. Filter and wash with distilled water several times until the pH is 6-7. Place the filter cake in a 150°C oven and bake for 1 hour to dehydrate the produced silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite and removed for use.

[0134] Add distilled water to a 300g plastic jar and stir. Add the modified expanded graphite. The graphite will not float on the water surface and should be evenly dispersed. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed modified expanded graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0135] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0136] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0137] Example 3

[0138] Table 9 Example 3 group distribution ratio

[0139] High temperature anti-stick agent Manufacturer Model Parts by weight Expanded graphite EG-150 / Qingdao Yanhai 18 n-Propanol Aladdin 18 Formic acid Aladdin 1.4 Potassium silicate Aladdin 4.5 Deionized water self made 168

[0140] Take 4.5 parts of potassium silicate and add it to a beaker, add 150 parts of water, stir and dissolve completely for use.

[0141] Add n-propanol to a three-necked flask and stir. Add expanded graphite and mix evenly. Disperse at high speed for 1 hour. Pour the mixture into a glass bottle dedicated for shaking. Add 54 parts of 0.8-1.0mm zirconium beads and grind them for 24 hours. Detect the particle size distribution until D99 is below 8μ. Discharge the material and introduce it into a three-necked flask and stir. Add 1.4 parts of formic acid and 18 parts of deionized water and stir evenly. Pour the dissolved potassium silicate solution into a constant pressure funnel and slowly add it dropwise to the three-necked flask while stirring rapidly. After the addition is complete, continue stirring the reaction and measure the pH value of the mixed system until the pH reaches between 4-6, which is the reaction end point. Filter and wash with distilled water several times until the pH is 6-7. Place the filter cake in a 150°C oven and bake it for 1 hour to dehydrate the produced silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite and removed for use.

[0142] Add distilled water to a 300g plastic jar and stir. Add the modified expanded graphite. The graphite will not float on the water surface and should be evenly dispersed. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed modified expanded graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0143] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0144] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0145] Example 4

[0146] Table 10 Example 4 group distribution ratio

[0147] High temperature anti-stick agent Manufacturer Model Parts by weight Expanded graphite EG-150 / Qingdao Yanhai 24 Isopropyl alcohol Aladdin 24 Trifluoroacetic acid Aladdin 4.3 Ammonium silicate Aladdin 4.8 Deionized water self made 184

[0148] Take 4.8 parts of ammonium silicate and add it to a beaker. Add 160 parts of water and stir until completely dissolved.

[0149] Add isopropyl alcohol to a three-necked flask and stir. Add expanded graphite and mix evenly. Disperse at high speed for 1 hour. Pour the mixture into a glass bottle dedicated for shaking. Add 72 parts of 0.8-1.0mm zirconium beads and grind them for 24 hours. Detect the particle size distribution until D99 is below 8μ. Discharge the material and introduce it into a three-necked flask and stir. Add 4.3 parts of trifluoroacetic acid and 24 parts of deionized water and stir evenly. Pour the dissolved ammonium silicate solution into a constant pressure funnel and slowly add it dropwise to the three-necked flask while stirring rapidly. After the addition is complete, continue stirring to react. Measure the pH value of the mixed system until the pH reaches between 4-6, which is the reaction end point. Filter and wash with distilled water several times until the pH is 6-7. Place the filter cake in a 150°C oven and bake for 1 hour to dehydrate the produced silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite. Remove and set aside.

[0150] Add distilled water to a 300g plastic jar and stir. Add the modified expanded graphite. The graphite will not float on the water surface and should be evenly dispersed. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed modified expanded graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0151] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0152] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0153] Example 5

[0154] Table 11 Example 5 group distribution ratio

[0155] High temperature anti-stick agent Manufacturer Model Parts by weight Expanded graphite EG-150 / Qingdao Yanhai 16 ethanol Aladdin 16 Trifluoroacetic acid Aladdin 2.4 Potassium silicate Aladdin 3.2 Deionized water self made 144

[0156] Take 3.2 parts of potassium silicate and add it to a beaker. Add 128 parts of water and stir until completely dissolved.

[0157] Add ethanol to a three-necked flask and stir. Add expanded graphite and mix evenly. Disperse at high speed for 1 hour. Pour the mixture into a glass bottle dedicated for shaking. Add 48 parts of 0.8-1.0mm zirconium beads and shake and grind for 24 hours. Detect the particle size distribution until D99 is below 8μ. Discharge the material and introduce it into a three-necked flask and stir. Add 2.4 parts of trifluoroacetic acid and 16 parts of deionized water and stir evenly. Pour the dissolved potassium silicate solution into a constant pressure funnel and slowly add it dropwise to the three-necked flask while stirring rapidly. After the addition is complete, continue stirring to react. Measure the pH value of the mixed system until the pH reaches between 4-6, which is the reaction end point. Filter and wash with distilled water several times until the pH is 6-7. Place the filter cake in a 150°C oven and bake for 1 hour to dehydrate the produced silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite. Remove and set aside.

[0158] Add distilled water to a 300g plastic jar and stir. Add the modified expanded graphite. The graphite will not float on the water surface and should be evenly dispersed. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed modified expanded graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0159] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0160] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0161] Example 6

[0162] Table 12 Example 6 group distribution ratio

[0163] High temperature anti-stick agent Manufacturer Model Parts by weight Expanded graphite EG-150 / Qingdao Yanhai 26 Methanol Aladdin 26 Formic acid Aladdin 1.9 Ammonium silicate Aladdin 5.2 Deionized water self made 200

[0164] Take 5.2 parts of ammonium silicate and add it to a beaker. Add 174 parts of water and stir until completely dissolved.

[0165] Add methanol to a three-necked flask and stir. Add expanded graphite and mix evenly. Disperse at high speed for 1 hour. Pour the mixture into a glass bottle dedicated for shaking. Add 78 parts of 0.8-1.0mm zirconium beads and grind them for 24 hours. Detect the particle size distribution until D99 is below 8μ. Discharge the material and introduce it into a three-necked flask and stir. Add 1.9 parts of formic acid and 26 parts of deionized water and stir evenly. Pour the dissolved ammonium silicate solution into a constant pressure funnel and slowly add it dropwise to the three-necked flask while stirring rapidly. After the addition is complete, continue stirring the reaction and measure the pH value of the mixed system until the pH reaches between 4-6, which is the reaction end point. Filter and wash with distilled water several times until the pH is 6-7. Place the filter cake in a 150°C oven and bake it for 1 hour to dehydrate the produced silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite. Remove and set aside.

[0166] Add distilled water to a 300g plastic jar and stir. Add the modified expanded graphite. The graphite will not float on the water surface and should be evenly dispersed. Take two pieces of glass that have been printed with ink and use a 0.8-1.0mm caliber hand spray gun to spray the dispersed modified expanded graphite dispersion on the ink surface. The spraying pressure is 1.5kg / cm 2 , keep the gun at about 25cm, spray 2 "cross" shapes, let it dry and set aside.

[0167] Cover with glass B, take a pair and place them in a muffle furnace at 400-630℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0168] Cover with glass B, take another pair and place them in a muffle furnace at 400-650℃ for 30 minutes, take them out and observe the adhesion of the two pieces of glass.

[0169] The glasses of Comparative Examples 1-6 and Examples 1-6 fired at 630°C and 650°C were observed for sticking, then separated and rinsed, and the high-temperature anti-sticking agent residue on the surface of glass B was observed. The transmittance in the visible light band was tested.

[0170] The performance test results of the high-temperature anti-adhesives prepared in Comparative Examples 1-6 and Examples 1-6 are listed in Tables 13 and 14. The transmittance test standard refers to GB / T 40415-2021; the architectural glass safety standard GB15763.2-2005; and the softening point test standard GB / T 28195-2011.

[0171] Table 13 Performance test results of inks prepared in Comparative Examples 1 to 6

[0172]

[0173]

[0174] Table 14 Test results of ink properties prepared in Examples 1 to 6

[0175]

[0176]

[0177] Table 15 Test results of light transmittance performance of unfired B glass

[0178]

[0179] Analysis of the ink properties after sintering in Comparative Examples 1, 2, 3 and Comparative Examples 4, 5, and 6 reveals that the inks used in Comparative Examples 1, 2, and 3 are highly hydrophilic inorganic materials. The high-temperature anti-sticking agent remaining on the surface after sintering at 630°C and 650°C is easily washed away with water, which has little effect on the transmittance of the fired sheet B. In Comparative Examples 1, 2, and 3, sheet 3 is a flaky structure, and its anti-sticking effect is slightly better than that of sheets 1 and 2. In Comparative Examples 4, 5, and 6, graphite is used, which has very poor hydrophilicity. The high-temperature anti-sticking agent remaining on the surface after sintering at 630°C and 650°C is easily washed away with water, resulting in a large amount of residue, which affects the transmittance of the fired sheet B. Furthermore, in Comparative Examples 4, 5, and 6, expanded graphite is used in sheet 6, which has excellent anti-sticking effect after sintering at 630°C and 650°C.

[0180] Compared with Comparative Example 6, Examples 1 to 6 use modified expanded graphite, and exhibit excellent anti-stick properties after firing at 630°C and 650°C. Surface treatment with silica significantly enhances hydrophilicity, as evidenced by the shapes of water droplets formed on the surface before and after treatment. Firing at 630°C and 650°C allows for clean rinsing with water, with minimal effect on the transmittance of the fired B sheet. Compared to the transmittance of the unfired B sheet, the transmittance is essentially unaffected, particularly in the green range of 500-600nm and the red range of 600-700nm. The fired glass, when installed on a car's windshield, does not affect the driver's and passenger's reaction to traffic lights, thereby ensuring their safety.

Claims

1. A method for preparing a high-temperature anti-sticking agent, characterized in that The method comprises the following preparation steps: S1, add low boiling point alcohol and expanded graphite and disperse them evenly, shake and grind them, and then discharge; Add organic acid and deionized water to the materials discharged from S2 and S1, stir evenly, and then slowly add water-soluble silicate solution until the pH value reaches 4-6, which is the end point of the reaction. Filter and wash with distilled water several times until the washing liquid is neutral; The filter cake obtained in S3 and S2 is baked to dehydrate the silicic acid into silicon dioxide, which is completely adsorbed on the surface of the expanded graphite and then taken out for use; The raw materials in the preparation method are as follows: 10-30 parts by weight of low-boiling-point alcohol, 10-30 parts by weight of expanded graphite, 0.4-7.5 parts by weight of organic acid, 35-430 parts by weight of deionized water, and 2-8 parts by weight of water-soluble silicate; The boiling point of the organic acid is between 60-150°C; The low-boiling-point alcohol has a boiling point of 60-120°C and a carbon chain of no more than 4; The baking temperature in S3 is 150-160°C and the baking time is 1-1.5 hours; The initial expansion temperature of the expanded graphite is between 180°C and 300°C.

2. The method for preparing a high-temperature anti-sticking agent according to claim 1, wherein: The raw materials in the preparation method are respectively as follows: 12-28 parts by weight of low-boiling-point alcohol, 12-28 parts by weight of expanded graphite, 1.0-7.0 parts by weight of organic acid, 2.5-7.5 parts by weight of water-soluble silicate and 44-403 parts by weight of deionized water.

3. The method for preparing a high-temperature anti-sticking agent according to claim 1, wherein: The raw materials in the preparation method are respectively as follows: 15-26 parts by weight of low-boiling-point alcohol, 15-26 parts by weight of expanded graphite, 1.2-6.6 parts by weight of organic acid, 3-7 parts by weight of water-soluble silicate and 35-430 parts by weight of deionized water.

4. The method for preparing a high-temperature anti-sticking agent according to claim 1, wherein: The organic acid includes one or more of formic acid, acetic acid, trifluoroacetic acid, propionic acid and acrylic acid.

5. The method for preparing a high-temperature anti-sticking agent according to claim 1, wherein: The organic acid includes one or more of formic acid, acetic acid and trifluoroacetic acid.

6. The method for preparing a high-temperature anti-sticking agent according to claim 1, characterized in that: The water-soluble silicate includes one or more of sodium silicate, potassium silicate, ammonium silicate and lithium silicate.

7. The method for preparing a high-temperature anti-sticking agent according to claim 1, characterized in that: The water-soluble silicate includes one or more of sodium silicate, potassium silicate and ammonium silicate.

8. The method for preparing a high-temperature anti-sticking agent according to claim 1, characterized in that: The low boiling point alcohol includes one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol.

9. The method for preparing a high-temperature anti-sticking agent according to claim 1, characterized in that: The low-boiling-point alcohol has a boiling point of 60-100° C., is miscible with water, and includes one or more of methanol, ethanol, n-propanol, and isopropanol.

10. Application of a high-temperature anti-adhesive agent prepared by the preparation method according to any one of claims 1 to 9 in hot bending of automobile glass, characterized in that: The high-temperature anti-sticking agent is mixed evenly with water, sprayed on the glass surface of the printing ink, and dried.

11. Application of the high-temperature anti-adhesive agent according to claim 10 in hot bending of automobile glass, characterized in that: The high-temperature anti-sticking agent is mixed with water in a weight ratio of 1:8-10.

12. Use of the high-temperature anti-adhesive agent according to claim 10 in hot bending of automobile glass, characterized in that: In the preparation of automobile windshield and sunroof glass, sheet A is printed with ink, and after the surface is dried, a layer of high-temperature anti-sticking agent is sprayed on the glass surface of the printed ink. After air drying, it is paired with sheet B and fired once to form.

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