A paste for automotive laminated glass and a method for preparing the same

Abstract

The application discloses a kind of slurry for automobile laminated glass and its preparation method, belong to glass slurry technical field, the slurry is composed of solid powder and organic carrier;The solid powder includes the following composition and its mass fraction: first inorganic glass powder 60~80%, second inorganic glass 4~15%, black pigment 15~30%.The slurry of the application is suitable for the baking process of all laminated glass, and has excellent blackness value and safety performance, etc., and the preparation method is simple.

Description

Technical Field

[0001] This invention relates to a slurry for automotive laminated glass and its preparation method, belonging to the field of glass slurry technology. Background Technology

[0002] Automotive laminated glass is formed by bonding a polymer film between two layers of glass, providing a certain degree of penetration resistance and protecting the safety of vehicle occupants. The paste used in laminated glass printing, after being baked on the glass, serves decorative and UV-blocking purposes. Laminated glass is baked at temperatures below 650℃, which differs from the molding process of tempered glass. The baking process for laminated glass is complex, requiring high standards for the color stability, anti-sticking properties, and sintering performance of the glass paste. In particular, the glass paste used on the second layer must possess excellent anti-sticking properties to prevent it from adhering to the upper glass layer during molding, which could lead to deformation, affect the lamination process, and reduce strength. Simultaneously, while ensuring anti-sticking properties, it must also have a suitable sintering temperature range and color stability to guarantee product quality. Currently, there are many types of laminated glass pastes on the market, each with limited performance characteristics, and each product is limited to a relatively single process, significantly increasing the cost of automotive glass manufacturing. Therefore, developing a glass paste suitable for the specific lamination glass baking process is essential. Summary of the Invention

[0003] To address the problems existing in the prior art, the present invention provides a slurry for automotive laminated glass and its preparation method. The slurry is suitable for all laminar glass baking processes and has excellent blackness and safety performance.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: a slurry for automotive laminated glass, the slurry being composed of solid powder and an organic carrier; the solid powder comprising the following components and their mass fractions: 60-80% first inorganic glass powder, 4-15% second inorganic glass, and 15-30% black pigment, wherein the particle size of the first inorganic glass powder and the second inorganic glass powder is 1-10 μm.

[0005] Preferably, the first inorganic glass powder comprises the following components and their mass fractions: Bi2O3 28-61%, SiO2 15-33%, TiO2 0.5-5%, B2O3 2-14%, Al2O3 0.5-4%, La2O3 0.5-2%, ZnO 2-14%, BaO 1-5%, and alkali gold oxides 3-7%.

[0006] Preferably, the specific steps of the preparation method of the first inorganic glass powder are as follows: take Bi2O3, SiO2, TiO2, B2O3, Al2O3, La2O3, ZnO, BaO and alkali gold oxide raw materials according to the above mass fractions and mix them evenly, then melt them at high temperature and fire them, then quench them with water to form glass slag, and then grind them to 1-10μm to obtain the first inorganic glass powder.

[0007] The firing temperature is 900–1300℃, and the firing time is 0.5–2 hours.

[0008] Preferably, the second inorganic glass powder comprises the following components and their mass fractions: Bi2O3 15-55%, SiO2 15-33%, B2O3 10-44%, ZnO 14-17%, and alkali gold oxides 1-8%.

[0009] Preferably, the preparation method of the second inorganic glass powder is as follows: Bi2O3, SiO2, B2O3, ZnO and alkali gold oxide raw materials are taken according to the above mass fractions and mixed evenly, then melted at high temperature and fired, then water-cooled and quenched to form glass slag, and then ground to 1-10μm to obtain the second inorganic glass powder.

[0010] The firing temperature is 950–1350℃, and the firing time is 0.5–3 hours.

[0011] Preferably, the black pigment is one or more of copper chromium black, iron chromium black, manganese iron black, and cobalt black.

[0012] Preferably, the mass ratio of the solid powder to the organic carrier is 1:0.15 to 1:0.3.

[0013] This invention also provides a slurry for automotive laminated glass and a method for preparing the same, comprising the following steps:

[0014] S1. Take the first inorganic glass powder, the second inorganic glass powder and the black pigment according to the above mass fraction, and ball mill them together for 1 to 6 hours to obtain a solid powder.

[0015] S2. Mix the solid powder obtained in S1 with the organic carrier evenly to obtain a paste-like material;

[0016] S3. Grind the paste obtained in step S2 3 to 5 times to obtain a slurry for automotive glass.

[0017] The beneficial effects of this invention are:

[0018] (1) The automotive laminated glass paste of the present invention is applicable to the baking process of all laminated windshields and has excellent anti-sticking properties, excellent blackness value and safety performance.

[0019] (2) By controlling the relative contents of bismuth oxide, aluminum oxide and lanthanum oxide in the first inorganic glass powder, this invention ensures that the glass powder spontaneously crystallizes during the sintering process, forming various crystals such as bismuth silicate and bismuth titanate in the system. When applied to the second laminated windshield glass, it has excellent anti-adhesion properties, ensuring the regular shape of the glass and not affecting the subsequent lamination process and the safety performance of the glass. Bismuth oxide is the main component for crystallization. Lanthanum oxide is usually used as a colorant or clarifying agent in glass. In the presence of aluminum oxide in this system, its crystallization range is wide, which can promote the formation of smaller grains of itself and bismuth oxide.

[0020] (3) By controlling the relative content of each component in the second inorganic glass powder and the relative content of the second inorganic glass powder introduced into the glass slurry, the second inorganic glass powder can play a regulatory role in the degree of spontaneous crystallization of the first inorganic glass powder, ensuring that the first inorganic glass powder has an appropriate degree of crystallization in the sintering process, without reducing the blackness of the glass slurry, and ensuring excellent anti-sticking and safety performance. Detailed Implementation

[0021] To provide a clearer and more complete description of the present invention, specific embodiments are described below, but these are not intended to limit the invention.

[0022] Unless otherwise specified, the experimental methods in the following examples are conventional methods, and the experimental reagents and materials involved are conventional chemical reagents and materials unless otherwise specified.

[0023] The present invention provides a slurry for automotive laminated glass, which is composed of solid powder and an organic carrier. The organic carrier is generally composed of solvent, resin, dispersant, leveling agent, etc., and is commercially available. Its composition is not the focus of this invention and will not be specifically described in this invention.

[0024] A further technical solution of the present invention is that the solid powder comprises the following components and their mass fractions: 60-80% first inorganic glass powder, 4-15% second inorganic glass, and 15-30% black pigment.

[0025] A further technical solution of the present invention comprises the following components and their mass fractions: Bi2O3 28-61%, SiO2 15-33%, TiO2 0.5-5%, B2O3 2-14%, Al2O3 0.5-4%, La2O3 0.5-2%, ZnO 2-14%, BaO 1-5%, and alkali gold oxides 3-7%; the second inorganic glass powder comprises the following components and their mass fractions: Bi2O3 15-55%, SiO2 15-33%, B2O3 10-44%, ZnO 14-17%, and alkali gold oxides 1-8%; the black pigment is one or more of copper chromium black, iron chromium black, manganese iron black, and cobalt black; and the alkali gold oxide is one or more of common Na2O, K2O, Li2O, etc.

[0026] This invention provides a method for preparing a slurry for automotive laminated glass, the specific steps of which are as follows:

[0027] (1) Weigh out Bi2O3, SiO2, TiO2, B2O3, Al2O3, La2O3, ZnO, BaO and alkali gold oxide raw materials according to the mass fraction of the first inorganic glass powder raw materials and mix them evenly. Then place them in a high-temperature furnace and melt them at a temperature of 900 to 1300℃ for 0.5 to 2 hours. After that, water-cooled quenching is performed to form glass slag. Then place it in a planetary ball mill and grind it to 1 to 10 μm to obtain the first inorganic glass powder.

[0028] (2) Weigh out Bi2O3, SiO2, B2O3, ZnO and alkali gold oxide raw materials according to the mass fraction of the second inorganic glass powder raw materials and mix them evenly. Then place them in a high-temperature furnace and melt them at a temperature of 950 to 1350℃ for 0.5 to 3 hours. After that, water-cooled quenching is performed to form glass slag. Then place it in a planetary ball mill and grind it to 1 to 10 μm to obtain the second inorganic glass powder.

[0029] (3) Weigh the first inorganic glass powder, the second inorganic glass powder and the black pigment according to the mass fraction of the above solid powder raw materials, and place them in a horizontal ball mill and mix for 1 to 6 hours to obtain solid powder.

[0030] (4) The solid powder obtained in S1 and the organic carrier are mixed evenly in a kneader at a mass ratio of 1:0.15 to 1:0.3 to obtain a paste-like material;

[0031] (5) Place the paste material obtained in step S2 into a three-roll mill for grinding 3 to 5 times to obtain a slurry for automotive glass.

[0032] Examples 1 to 9

[0033] Examples 1 to 9 obtained automotive laminated glass slurry using the preparation method of the present invention. The mass ratio of solid powder to organic carrier, the mass content of the first inorganic glass powder, the second inorganic glass powder and the black pigment in the solid powder, and the sum of the contents of each raw material in the solid powder are 100%. The results of the addition content of each raw material are shown in Table 1.

[0034] Comparative Examples 1 to 6

[0035] Comparative Examples 1 to 6 obtained automotive laminated glass slurries using the preparation method of the present invention. The mass ratio of solid powder to organic carrier in Comparative Examples 1 to 6, as well as the mass content of the first inorganic glass powder, the second inorganic glass powder, and the black pigment in the solid powder, and the sum of the contents of each raw material in the solid powder are 100%. The results of each raw material and its content are shown in Table 1.

[0036] The raw materials and content results of the first inorganic glass powder in Examples 1 to 9 and Comparative Examples 1 to 5 are shown in Table 3, and the raw materials and content results of the second inorganic glass powder are shown in Table 4.

[0037] Table 1. Raw materials and content of slurries from Examples 1 to 9

[0038]

[0039] Table 2. Raw materials and content of slurries from Comparative Examples 1 to 5

[0040]

[0041] Table 3. Raw materials and content of the first inorganic glass powder

[0042]

[0043] Table 4. Raw materials and content of the second inorganic glass powder

[0044]

[0045] Effect Example

[0046] The automotive laminated glass pastes prepared in Examples 1 to 9 and Comparative Examples 1 to 6 were printed on flat glass, and their various properties were tested at 520–650°C. The coefficient of thermal expansion (25–300°C) of the corresponding solid powder samples was also tested. The performance results of Examples 1 to 9 are shown in Table 5, and the performance results of Comparative Examples 1 to 6 are shown in Table 6.

[0047] Table 5 Performance of Examples 1 to 9

[0048]

[0049] Table 6 Performance of Comparative Examples 1 to 6

[0050]

[0051] As can be seen from Tables 1 to 6, the automotive laminated glass slurry prepared by this invention exhibits excellent blackness and a small coefficient of thermal expansion after sintering, ensuring its color stability and safety performance.

[0052] Compared with Example 3, the first inorganic glass powder in Comparative Example 1 does not contain La2O3. The surface roughness value of Comparative Example 1 is much smaller than that of Example 3. At the same time, the surface roughness value of Comparative Example 1 is also much smaller than that of other examples. This indicates that the presence of La2O3 is beneficial to promoting the spontaneous crystallization of the first inorganic glass powder and improving its anti-sticking performance. In addition, the coefficient of thermal expansion of Comparative Example 1 is also larger than that of Example 3. At the same time, the surface roughness value of Comparative Example 1 is also larger than that of other examples. This indicates that the presence of La2O3 also affects the coefficient of thermal expansion of the glass slurry to a certain extent.

[0053] Compared with Examples 1 to 9, the first inorganic glass powder in Comparative Example 2 has a higher Al2O3 content, a significantly higher minimum sintering temperature, and more Al2O3 can increase the size of the precipitated crystals, resulting in a significant increase in roughness and a significant decrease in blackness.

[0054] Compared with Examples 1 to 9, the first inorganic glass powder in Comparative Example 3 has a higher Bi2O3 content. Compared with Example 6, the first inorganic glass powder in Comparative Example 3 has a higher bismuth oxide content, which leads to a slightly higher degree of crystallization and a greater impact on blackness. In addition, Bi2O3 has a greater impact on the coefficient of thermal expansion of the glass slurry.

[0055] Compared with Example 3, the content of the second inorganic glass powder in Comparative Examples 4 and 5 changed. In Comparative Example 4, when the amount of the second inorganic glass powder introduced was slightly more, it had a greater inhibitory effect on the crystallization tendency of the first inorganic glass powder, resulting in a smaller glaze roughness value. In Comparative Example 5, when the amount of the second inorganic glass powder introduced was slightly less, it had a greater inhibitory effect on the crystallization tendency of the first inorganic glass powder, resulting in a slightly larger coefficient of expansion, which affected its safety performance.

[0056] Compared with Example 3, the content of the first inorganic glass powder in Comparative Example 6 changed. When a slightly larger amount of the first inorganic glass powder was introduced, the second glass powder was insufficient to suppress the crystallization tendency of the first inorganic glass powder, resulting in a significant increase in its crystallization tendency, a larger roughness of the glaze surface, and a significant decrease in blackness.

[0057] In Examples 1 to 9 and Comparative Examples 1 to 6 above, copper chromate black was used as the black pigment, and Na2O was used as the alkali metal oxide. Moreover, through extensive experiments, this invention has found that the use of a single black pigment, or the use of a mixture of multiple black pigments, as well as the mixing ratio of multiple black pigments, has little impact on the performance of the slurry; the use of a single alkali metal oxide, or the use of a mixture of multiple alkali metal oxides, as well as the mixing ratio of multiple alkali metal oxides, has little impact on the performance of the slurry.

[0058] In summary, the glass slurry for automotive laminated glass prepared by this invention, by introducing substances such as bismuth oxide, aluminum oxide, and lanthanum oxide into the first glass powder, can give the first inorganic glass powder an excellent degree of crystallization. Introducing a second inorganic glass powder into the system, and by adjusting the amount added, can further control its crystallization potential energy, ensuring that the glaze surface of the glass slurry has a suitable roughness after sintering. Therefore, it can prevent the slurry from bonding to the upper glass layer during sintering, without affecting the lamination process.

[0059] Finally, it should be noted that the above embodiments are only used to illustrate and not limit the technical solutions of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention without departing from the spirit and scope of the present invention. Any modifications or partial substitutions should be covered within the scope of the claims of the present invention.

Claims

1. A paste for automotive laminated glass, characterized by comprising, The slurry is composed of solid powder and organic carrier; The solid powder is composed of the following components and mass fractions: 60-80% of first inorganic glass powder, 4-15% of second inorganic glass, and 15-30% of black pigment; The first inorganic glass powder comprises the following components and mass fractions: Bi2O3 28-61%, SiO2 15-33%, TiO2 0.5-5%, B2O3 2-14%, Al2O3 0.5-4%, La2O3 0.5-2%, ZnO 2-14%, BaO 1-5%, and alkali metal oxide 3-7%; the particle size of the first inorganic glass powder is 1-10 μm; The second inorganic glass powder comprises the following components and mass fractions: Bi2O3 15-55%, SiO2 15-33%, B2O3 10-44%, ZnO 14-17%, and alkali metal oxide 1-8%; the particle size of the second inorganic glass powder is 1-10 μm.

2. The paste for automotive laminated glass according to claim 1, wherein The preparation method of the first inorganic glass powder comprises the following steps: taking Bi2O3, SiO2, TiO2, B2O3, Al2O3, La2O3, ZnO, BaO, and alkali metal oxide raw materials according to the above mass fractions, mixing them uniformly, high-temperature melting, firing, water quenching to form glass slag, and grinding to 1-10 μm to obtain the first inorganic glass powder.

3. The paste for automotive laminated glass according to claim 2, wherein The firing temperature is 900-1300 °C, and the firing time is 0.5-2 h.

4. The paste for automotive laminated glass according to claim 1, wherein The preparation method of the second inorganic glass powder comprises the following steps: taking Bi2O3, SiO2, B2O3, ZnO, and alkali metal oxide raw materials according to the above mass fractions, mixing them uniformly, high-temperature melting, firing, water quenching to form glass slag, and grinding to 1-10 μm to obtain the second inorganic glass powder.

5. The paste for automotive laminated glass according to claim 4, wherein The firing temperature is 950-1350 °C, and the firing time is 0.5-3 h.

6. The paste for automotive laminated glass according to claim 1, wherein The black pigment is one or more of copper-chromium black, iron-chromium black, manganese-iron black, and cobalt black.

7. The paste according to claim 1, wherein The mass ratio of the solid powder to the organic carrier is 1:0.15-1:0.

3.

8. A method for preparing the paste for the automotive laminated glass according to any one of claims 1 to 7, characterized by, The method comprises the following steps: S1, taking the first inorganic glass powder, the second inorganic glass powder, and the black pigment according to the above mass fractions, ball-milling and mixing for 1-6 h to obtain the solid powder; S2, mixing the solid powder obtained in S1 with the organic carrier uniformly to obtain the paste material; S3, grinding the paste material obtained in step S2 for 3-5 times to obtain the slurry for automobile glass.

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