A colored enamel glass and a method for making the same

Abstract

The present application belongs to the technical field of colored glaze glass, and particularly relates to a colored glaze glass and a preparation method thereof. The preparation method of the colored glaze glass comprises the following steps: (1) selecting a glass original piece, cleaning, cutting and edge grinding, and then reserving; (2) printing glaze on the outer surface of the glass treated in step (1) by using a silk screen printing process, and drying; (3) performing a tempering treatment on the glass treated in step (2); (4) immersing the glass treated in step (3) in an ethanol aqueous solution containing a silane coupling agent, and then washing and drying, and reserving; (5) taking two pieces of the glass treated in step (4), coating glue on the inner surfaces of the two pieces of glass, and curing to obtain a colored glaze glass. The glue film of the colored glaze glass has good bonding performance and mechanical properties, prevents glass from splashing when breaking, and can resist the erosion of the external environment, maintain the bonding performance and mechanical strength of the glue film, and prolong the service life of the colored glaze glass.

Description

Technical Field

[0001] This invention belongs to the field of colored glaze glass technology, specifically relating to a colored glaze glass and its preparation method. Background Technology

[0002] Glass is an amorphous inorganic non-metallic material. Due to its excellent light transmittance, it is one of the most commonly used conventional materials and has a wide range of applications in daily life, construction, medical and other fields.

[0003] Traditional enamel glass, due to its inherent brittleness and low strength, poses certain safety hazards, limiting its application. It also has limitations, such as being easily scratched during transportation, installation, and use; and the potential for sharp fragments when broken, posing a safety risk.

[0004] Currently, an adhesive film layer is commonly applied to the surface of enamel glass, primarily serving to bond and protect the glass, enhancing its durability, safety, and practicality, while simultaneously meeting the dual demands of modern architecture for aesthetics and performance. The mainstream adhesive films are mainly divided into two categories: organic adhesive interlayers and epoxy resin-based adhesives. However, many limitations remain. For example, films made from ordinary epoxy resin have poor mechanical properties and poor resistance to damp heat aging. Long-term exposure to outdoor environments may cause micro-cracks in the enamel surface due to changes in external temperature and humidity, thus shortening the lifespan of the enamel glass.

[0005] To solve the above-mentioned technical problems, the present invention provides an adhesive film layer on the surface of colored glaze glass, overcoming the limitations of traditional colored glaze glass. Summary of the Invention

[0006] The primary objective of this invention is to provide a method for preparing colored glaze glass, which involves screen printing glaze onto the glass surface, followed by tempering, adhesive coating, and curing to obtain colored glaze glass. This preparation process is simple and efficient.

[0007] The second objective of this invention is to provide a colored enamel glass, wherein the enamel glass film has good adhesive and mechanical properties, prevents the glass from shattering and splashing, and the enamel film can resist the erosion of the external environment, maintain the adhesive properties and mechanical strength of the enamel film, and extend the service life of the colored enamel glass.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] A method for preparing colored glaze glass includes the following steps:

[0010] (1) Select glass sheets, clean, cut, and grind the edges for later use;

[0011] (2) The glaze is printed onto the outer surface of the glass after step (1) using screen printing technology, and then dried.

[0012] (3) Temper the glass after step (2);

[0013] (4) Immerse the glass treated in step (3) in an ethanol aqueous solution containing silane coupling agent, and wash and dry it for later use;

[0014] (5) Take two pieces of glass after the treatment in step (4), apply adhesive to the inner surface of the two pieces of glass and cure to obtain colored glaze glass.

[0015] Furthermore, the adhesive comprises the following raw materials in parts by weight: 50-60 parts epoxy resin, 5-10 parts 5-hydroxypentanal, 8-14 parts modified calcium carbonate, and 0.3-0.5 parts photoinitiator.

[0016] Furthermore, the preparation process of the modified calcium carbonate is as follows:

[0017] a. Add calcium carbonate to water, then add chitosan, stir evenly, and then ball mill. After drying the ball milling product, pretreated calcium carbonate is obtained.

[0018] b. Add phytic acid and ethylenediamine to water for a first heating reaction, then add the pretreated calcium carbonate for a second heating reaction to obtain modified calcium carbonate.

[0019] Further, in step a, the mass ratio of chitosan, calcium carbonate, and water is 1:(2-4):(150-300); the ball milling speed is 300-500 rpm, and the time is 10-15 h.

[0020] Furthermore, the calcium carbonate is heavy calcium carbonate with a particle size of 0.5–5 μm.

[0021] Further, in step b, the ratio of phytic acid, ethylenediamine, and water is 1 mL: 1-2 g: 100-300 mL; the temperature of the first heating reaction is 70-80℃, and the time is 40-60 min; the mass ratio of the pretreated calcium carbonate to ethylenediamine is 1: (2-5); and the temperature of the second heating reaction is 80-90℃, and the time is 2-4 h.

[0022] Furthermore, the epoxy resin is bisphenol A epoxy resin with an epoxy equivalent of 150-600; the photoinitiator is benzophenone.

[0023] Furthermore, in the screen printing process described in step (2), the printing temperature is 16-25℃; the screen mesh size is 150-250 mesh; and the drying temperature is 95-125℃.

[0024] Further, in the tempering process described in step (3), the tempering temperature is 600-700℃ and the time is 70-80s / mm; after the tempering process in step (3), the following process is also included: immersing the tempered glass in acid solution at 70-90℃ for 1-3 hours; after taking it out, blow it dry, wash it with water until it is neutral, and then dry it.

[0025] Further, in step (4), the concentration of the ethanol aqueous solution is 90-95 wt%; the mass ratio of the silane coupling agent to the ethanol aqueous solution is (3-10):(90-100); the mass ratio of the glass treated in step (3) to the ethanol aqueous solution is 1:10-500; the soaking temperature is 50-60℃ and the time is 1-2h; the silane coupling agent is γ-aminopropyltriethoxysilane; and the curing temperature in step (5) is 70-90℃ and the time is 3-8h.

[0026] A colored glaze glass is prepared according to the preparation method described above.

[0027] Compared with the prior art, the main advantages of the present invention are as follows:

[0028] 1. This invention provides a colored glaze glass. The adhesive film formed on the surface of the colored glaze glass by curing an adhesive has good bonding and mechanical properties, preventing the glass from shattering and splashing. Furthermore, the adhesive film can resist the erosion of the external environment, maintain the bonding performance and mechanical strength of the adhesive film, and extend the service life of the colored glaze glass.

[0029] (1) In the preparation process of colored enamel glass, the glass surface is first treated with a silane coupling agent to activate the glass. At the same time, 5-hydroxypentanal is added to the adhesive to react with the amino groups of the silane coupling agent on the pretreated glass to form a Schiff base reaction, thereby improving the bonding tightness between the adhesive and the glass and enhancing corrosion resistance. Furthermore, the epoxy resin in the adhesive has excellent chemical stability. The addition of 5-hydroxypentanal to the adhesive can react with the epoxy groups of the epoxy resin to form a ring-opening addition reaction. After curing, a highly cross-linked three-dimensional network structure is formed. The structure is dense and can effectively block the penetration and diffusion of water molecules, oxygen and other media.

[0030] (2) Modified calcium carbonate is also added to the adhesive of the present invention. Compared with calcium carbonate, phytic acid and ethylenediamine form a cross-linked network structure on the surface of calcium carbonate. The phosphate groups in phytic acid and the epoxy groups in epoxy resin interact, making the modified calcium carbonate and the resin matrix more compatible, improving the density of the glaze film, avoiding defects such as cracks in the film, and improving the mechanical properties of the film.

[0031] 2. The method for preparing colored glaze glass provided by the present invention uses screen printing technology to print glaze onto the glass surface, followed by tempering, adhesive coating, and curing to obtain colored glaze glass. This preparation process is simple and efficient. Attached Figure Description

[0032] Figure 1 This is a scanning electron microscope image of the modified calcium carbonate obtained in Example 1 of the present invention. Detailed Implementation

[0033] The technical solution of the present invention will be further described below with reference to specific embodiments. However, those skilled in the art should understand that the following embodiments are only for illustrating the present invention and should not be regarded as limiting the present invention. Specific conditions not specified in the embodiments are performed according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the reagents or instruments used are all conventional products obtained through commercial channels.

[0034] Example 1

[0035] A method for preparing colored glaze glass includes the following steps:

[0036] (1) Select glass sheets, clean and cut them, grind the edges and set them aside;

[0037] (2) The glaze (ink) is printed onto the outer surface of the glass after step (1) using screen printing technology. The printing temperature is 20°C and the screen mesh is 200 mesh. The glass is dried at 110°C.

[0038] (3) Clean the glass surface from step (2), dry it, and send it into a tempering furnace for tempering treatment. The tempering temperature is 650℃ and the time is 75s / mm; obtain tempered glass; then immerse the tempered glass in concentrated sulfuric acid at 80℃ for 2 hours; take it out, blow it dry, wash it with water until neutral, and then dry it again for later use;

[0039] (4) Immerse the glass treated in step (3) in an ethanol aqueous solution containing γ-aminopropyltriethoxysilane, wherein the concentration of the ethanol aqueous solution is 95 wt%, and the mass ratio of γ-aminopropyltriethoxysilane to the ethanol aqueous solution is 5:95; the mass ratio of the glass treated in step (3) to the ethanol aqueous solution is 1:300; the immersion temperature is 55℃ and the time is 1.5h; after the reaction is completed, the reaction solution is washed and dried for later use.

[0040] (5) Take two pieces of glass after the treatment in step (4), apply adhesive to the inner surface of the two pieces of glass, cure at 80°C for 5 hours to form an adhesive film on the glass surface, and obtain colored glaze glass. Control the thickness of the adhesive film to 0.3 mm.

[0041] The adhesive comprises the following raw materials in parts by weight: 55 parts epoxy resin (bisphenol A epoxy resin, epoxy equivalent between 150 and 600), 8 parts 5-hydroxypentanal, 12 parts modified calcium carbonate, and 0.4 parts photoinitiator (benzophenone); the above components are mixed evenly to obtain the adhesive.

[0042] The preparation process of modified calcium carbonate is as follows:

[0043] a. Take calcium carbonate (heavy calcium carbonate with a particle size of 0.5-5 μm) and add it to water, then add chitosan, wherein the mass ratio of chitosan, calcium carbonate and water is 1:3:200; after stirring evenly, ball milling is performed at a speed of 400 rpm for 12 hours; after drying the ball milling product, pretreated calcium carbonate is obtained.

[0044] b. Phytic acid and ethylenediamine were added to deionized water, with a phytic acid:ethylenediamine:water ratio of 1 mL:1.5 g:200 mL. The mixture was heated at 75°C for 50 min. Then, the pretreated calcium carbonate was added, with a pretreated calcium carbonate:ethylenediamine mass ratio of 1:3. The mixture was heated at 85°C for 3 h to obtain modified calcium carbonate. An electron micrograph of the modified calcium carbonate is shown below. Figure 1 As shown.

[0045] This embodiment also provides a colored glaze glass, which is prepared using the aforementioned preparation method.

[0046] Example 2

[0047] A method for preparing colored glaze glass includes the following steps:

[0048] (1) Select glass sheets, clean, cut, and grind the edges for later use;

[0049] (2) The glaze (ink) is printed onto the outer surface of the glass after step (1) using screen printing technology. The printing temperature is 16℃ and the screen mesh is 150 mesh. The glass is dried at 95℃.

[0050] (3) Clean the glass surface from step (2), dry it, and send it into a tempering furnace for tempering treatment. The tempering temperature is 600℃ and the heating time is 70s / mm. Tempered glass is obtained. Then, the tempered glass is immersed in concentrated sulfuric acid at 70℃ for 3 hours. After taking it out, it is dried, washed with water until neutral, and then dried again for later use.

[0051] (4) Immerse the glass treated in step (3) in an ethanol aqueous solution containing γ-aminopropyltriethoxysilane, wherein the concentration of the ethanol aqueous solution is 90 wt%, and the mass ratio of γ-aminopropyltriethoxysilane to 90 wt% ethanol aqueous solution is 3:90; the mass ratio of the treated glass to the ethanol aqueous solution is 1:100; the immersion temperature is 50℃ and the time is 2h; after the reaction is completed, the reaction solution is washed and dried for later use.

[0052] (5) Take two pieces of glass after the treatment in step (4), apply adhesive to the inner surface of the two pieces of glass, cure at 70°C for 8 hours to form an adhesive film on the glass surface, and obtain colored glaze glass. Control the thickness of the adhesive film to be 0.3 mm.

[0053] The adhesive comprises the following raw materials in parts by weight: 50 parts epoxy resin (bisphenol A epoxy resin, epoxy equivalent between 150 and 600), 5 parts 5-hydroxypentanal, 8 parts modified calcium carbonate, and 0.3 parts photoinitiator (benzophenone); the above components are mixed evenly to obtain the adhesive.

[0054] The preparation process of modified calcium carbonate is as follows:

[0055] a. Take calcium carbonate (heavy calcium carbonate with a particle size of 0.5-5 μm) and add it to water, then add chitosan, wherein the mass ratio of chitosan, calcium carbonate and water is 1:2:150; after stirring evenly, ball milling is performed at a speed of 500 rpm for 10 hours; after drying the ball milling product, pretreated calcium carbonate is obtained.

[0056] b. Add phytic acid and ethylenediamine to deionized water, wherein the ratio of phytic acid, ethylenediamine and water is 1 mL: 1 g: 100 mL; heat at 70°C for 60 min; then add the pretreated calcium carbonate, wherein the mass ratio of pretreated calcium carbonate and ethylenediamine is 1:2, and heat at 80°C for 4 h to obtain modified calcium carbonate.

[0057] This embodiment also provides a colored glaze glass, which is prepared using the aforementioned preparation method.

[0058] Example 3

[0059] A method for preparing colored glaze glass includes the following steps:

[0060] (1) Select glass sheets, clean, cut, and grind the edges for later use;

[0061] (2) The glaze (ink) is printed onto the outer surface of the glass after step (1) using screen printing technology. The printing temperature is 25°C and the screen mesh is 250 mesh. The glass is dried at 125°C.

[0062] (3) Clean the glass surface from step (2), dry it, and send it into a tempering furnace for tempering treatment. The tempering temperature is 700℃ and the time is 80s / mm; obtain tempered glass; then immerse the tempered glass in concentrated sulfuric acid at 90℃ for 1h; take it out, blow it dry, wash it with water until neutral, and then dry it again for later use;

[0063] (4) Immerse the glass treated in step (3) in an ethanol aqueous solution containing γ-aminopropyltriethoxysilane, wherein the concentration of the ethanol aqueous solution is 95 wt%, and the mass ratio of γ-aminopropyltriethoxysilane to the ethanol aqueous solution is 10:100; the mass ratio of the glass treated in step (3) to the ethanol aqueous solution is 1:500; the immersion temperature is 60℃ and the time is 1h; after the reaction is completed, the reaction solution is washed and dried for later use.

[0064] (5) Take two pieces of glass after the treatment in step (4), apply adhesive to the inner surface of the two pieces of glass, cure at 90°C for 3 hours to form an adhesive film on the glass surface, and obtain colored glaze glass. Control the thickness of the adhesive film to be 0.3 mm.

[0065] The adhesive comprises the following raw materials in parts by weight: 60 parts epoxy resin (bisphenol A epoxy resin, epoxy equivalent between 150 and 600), 10 parts 5-hydroxypentanal, 14 parts modified calcium carbonate, and 0.5 parts photoinitiator (benzophenone); the above components are mixed evenly to obtain the adhesive.

[0066] The preparation process of modified calcium carbonate is as follows:

[0067] a. Take calcium carbonate (heavy calcium carbonate with a particle size of 0.5-5 μm) and add it to water, then add chitosan, wherein the mass ratio of chitosan, calcium carbonate and water is 1:4:300; after stirring evenly, ball milling is performed at a speed of 300 rpm for 15 hours; after drying the ball milling product, pretreated calcium carbonate is obtained.

[0068] b. Add phytic acid and ethylenediamine to deionized water, wherein the ratio of phytic acid, ethylenediamine and water is 1 mL: 2 g: 300 mL; heat at 80°C for 40 min; then add the pretreated calcium carbonate, wherein the mass ratio of pretreated calcium carbonate and ethylenediamine is 1: 5, and heat at 90°C for 2 h to obtain modified calcium carbonate.

[0069] This embodiment also provides a colored glaze glass, which is prepared using the aforementioned preparation method.

[0070] Comparative Example 1

[0071] Comparative Example 1 is basically the same as Example 1, except that step (4) is omitted in the preparation of colored glaze glass.

[0072] Comparative Example 2

[0073] Comparative Example 2 is basically the same as Example 1, except that 5-hydroxypentanal is omitted from the adhesive.

[0074] Comparative Example 3

[0075] Comparative Example 3 is basically the same as Example 1, except that modified calcium carbonate is replaced with calcium carbonate.

[0076] Experimental Example 1

[0077] (1) 180° peel strength test: The peel strength between the film and glass in Examples 1-3 and Comparative Examples 1-3 was determined using a universal tensile testing machine. The peel speed was set to 100±10mm / min, and the peel strength (N / mm) was measured.

[0078] (2) Apply a 5×10 mm coating to the enamel-coated surface of the glass using a scraper. 2 The pressure was applied to the film, and the film was scraped back and forth 20 times. The results of the test are shown in Table 1.

[0079] Table 1

[0080]

[0081] As can be seen from the test results in Table 1, the adhesive films obtained in Examples 1-3 of this invention have excellent peel strength, and the surface integrity of the adhesive film is good after scratching. Compared with Example 1, Comparative Example 1 omits step (4); Comparative Example 2 omits 5-hydroxypentanal in the adhesive; and Comparative Example 3 replaces modified calcium carbonate with calcium carbonate. The peel strength of all three decreased to varying degrees, and a small number of scratches appeared on the surface of the adhesive film. This is because 5-hydroxypentanal in the adhesive can react with the amino group of the silane coupling agent on the glass, improving the bonding tightness between the adhesive and the glass. In addition, the modified calcium carbonate introduced into the adhesive has better compatibility with the epoxy resin matrix, which also improves the density of the glaze adhesive film and improves the mechanical properties of the adhesive film.

[0082] Experimental Example 2

[0083] The colored enamel glass samples from Examples 1-3 and Comparative Examples 1-3 were placed at 85°C and 90% relative humidity for 24 hours to observe for phenomena such as delamination and cracks. A 180° peel strength test was also performed according to the method described in Experimental Example 1, and the test results are shown in Table 2.

[0084] Table 2

[0085]

[0086] As can be seen from the test results in Table 2, the adhesive film on the colored enamel glass of Examples 1-3 of the present invention has good high temperature and high humidity resistance. After treatment in a high temperature and high humidity environment, it still maintains good peel strength and no delamination or cracks appear. The peel strength of Comparative Examples 2 and 3 is reduced, and delamination occurs at the edges under high temperature and high humidity conditions. In addition, Comparative Example 3 also shows cracks.

[0087] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them. The basic principles and main features of the present invention have been described above with specific implementation schemes. Based on the present invention, some modifications or substitutions can be made, but these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of protection claimed by the present invention.

Claims

1. A method of making a colored enamel glass, characterized in that, The preparation method comprises the following steps: (1) selecting a glass sheet, cleaning, cutting and grinding the glass sheet, and then preparing the glass sheet; (2) printing glaze on the outer surface of the glass sheet prepared in step (1) by using a silk screen printing process, and drying the glass sheet; (3) performing a tempering treatment on the glass sheet prepared in step (2); (4) immersing the glass sheet prepared in step (3) in an ethanol aqueous solution containing a silane coupling agent, and then washing and drying the glass sheet to obtain a glass sheet for use; (5) taking two glass sheets prepared in step (4), coating a glue on the inner surfaces of the two glass sheets, and curing the glue to obtain a colored glaze glass. The glue comprises the following raw materials in parts by weight: 50-60 parts of epoxy resin, 5-10 parts of 5-hydroxyvaleraldehyde, 8-14 parts of modified calcium carbonate, and 0.3-0.5 parts of a photoinitiator. The modified calcium carbonate is prepared by the following process: a. adding calcium carbonate into water, adding chitosan, stirring uniformly, performing ball milling, drying the ball-milled product to obtain pretreated calcium carbonate; b. adding phytic acid and ethylenediamine into water, performing a first heating reaction, adding the pretreated calcium carbonate to perform a second heating reaction, and obtaining modified calcium carbonate.

2. The method of claim 1, wherein the colored enamel glass is prepared by the steps of: In step a, the mass ratio of the chitosan, calcium carbonate and water is 1:(2-4):(150-300); the rotation speed of the ball milling is 300-500 rpm, and the time is 10-15 h.

3. The method of claim 1, wherein the colored enamel glass is prepared by the steps of: In step b, the amount ratio of the phytic acid, ethylenediamine and water is 1 mL:1-2 g:100-300 mL; the temperature of the first heating reaction is 70-80℃, and the time is 40-60 min; the mass ratio of the pretreated calcium carbonate and ethylenediamine is 1:(2-5), and the temperature of the second heating reaction is 80-90℃, and the time is 2-4 h.

4. The method of claim 1, wherein the colored enamel glass is prepared by the steps of: The epoxy resin is bisphenol A epoxy resin with an epoxy equivalent weight of 150-600; and the photoinitiator is benzophenone.

5. The method of claim 1, wherein the colored enamel glass is prepared by the steps of: In the silk screen printing process in step (2), the printing temperature is 16-25℃, the mesh number of the screen plate is 150-250 meshes, and the drying temperature is 95-125℃.

6. The method of claim 1, wherein the colored enamel glass is prepared by the steps of: In the tempering treatment in step (3), the tempering temperature is 600-700℃, and the time is 70-80 s / mm; after the tempering treatment in step (3), the glass is further immersed in an acid solution at 70-90℃ for 1-3 h, and then is blown dry, washed with water to neutral, and dried.

7. The method of claim 1, wherein the colored enamel glass is prepared by the steps of: In step (4), the concentration of the ethanol aqueous solution is 90-95 wt%, the mass ratio of the silane coupling agent and the ethanol aqueous solution is (3-10):(90-100), the mass ratio of the glass sheet prepared in step (3) and the ethanol aqueous solution is 1:10-500, the immersion temperature is 50-60℃, and the immersion time is 1-2 h; the silane coupling agent is γ-aminopropyltriethoxysilane; and in step (5), the curing temperature is 70-90℃, and the curing time is 3-8 h.

8. A colored enamel glass characterized by, The colored glaze glass is prepared by the preparation method according to any one of claims 1-7.

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