CN115925278A - A kind of wear-resistant coated glass and preparation method thereof - Google Patents

Abstract

The invention discloses wear-resistant coated glass and a preparation method thereof, belonging to the technical field of coated glass and comprising a glass main body, wherein the surface of the glass main body is sequentially provided with a silicon nitride priming layer, a silver coating layer, a wear-resistant layer and a protective layer; the wear-resistant layer is made of wear-resistant paint; the protective layer is made of erosion-resistant paint; the wear-resistant coating comprises the following raw materials in parts by weight: 9.4-15 parts of deionized water, 1-8 parts of silica sol, 1-1.2 parts of sulfuryl chloride, 5-8 parts of modified nano zinc oxide, 10-14 parts of mixed solution A, 2.8-3.3 parts of silane coupling agent KH-560 and 14-20 parts of isopropanol. The wear-resistant layer is arranged on the outer side of the silver coating, so that the wear resistance of the glass is improved, the light transmittance of the wear-resistant layer is improved, the high light transmittance of the silver coating is ensured, the erosion resistance and the wear resistance of the wear-resistant layer are improved by arranging the protective layer, and the light transmittance of the glass is further ensured.

Description

A kind of wear-resistant coated glass and preparation method thereof

technical field

The invention belongs to the technical field of coated glass, and in particular relates to wear-resistant coated glass and a preparation method thereof.

Background technique

Coated glass is coated with one or more transparent films of metals, metal compounds or non-metal compounds on the glass surface by methods such as chemical vapor deposition, physical vapor deposition, plasma sputtering deposition, metal organic deposition and sol-gel method , so that the glass can have the functions of conductivity and antistatic, but the corrosion resistance of this layer of coating is poor, and it is easy to be eroded by the external environment, resulting in a decrease in the light transmittance of the glass; The role of light, due to the soft texture of silver, is susceptible to friction and scratches during transportation and installation, resulting in rough glass surfaces and a decrease in the light transmittance of the glass.

Contents of the invention

The purpose of the present invention is to provide a wear-resistant coated glass and its preparation method to solve the problems in the background technology.

The purpose of the present invention can be achieved through the following technical solutions:

A wear-resistant coated glass, comprising a glass body, the surface of the glass body is sequentially provided with a silicon nitride primer layer, a silver-plated layer, a wear-resistant layer and a protective layer; the material of the wear-resistant layer is a wear-resistant paint; the The material of the protective layer is an erosion-resistant coating; the wear-resistant coating includes the following raw materials in parts by weight: 9.4-15 parts of deionized water, 1-8 parts of silica sol, 1-1.2 parts of sulfuryl chloride, 5-8 parts of modified nano Zinc oxide, 10-14 parts of mixed solution A, 2.8-3.3 parts of silane coupling agent KH-560, 14-20 parts of isopropanol.

As a further solution of the present invention, the particle size of the silica sol is 12-15 nm.

As a further solution of the present invention, the modified nano zinc oxide includes the following preparation steps:

Mix and stir 10-12mL stearic acid and 20-30mL isopropanol evenly, then add 1-1.5g nanometer zinc oxide, continue stirring at 18-20°C for 1-1.2h, let stand for 30-40min, and remove clear solution to obtain modified nano-zinc oxide. The modified nano-zinc oxide has modified the surface of nano-zinc oxide with stearic acid, which reduces the surface activation energy of nano-zinc oxide and improves its dispersibility in wear-resistant coatings; modified nano-zinc oxide has high transparency and The characteristics of small refractive index, easy doping, can change the porosity and surface roughness of the coating film system, and improve the light transmittance of the coating.

As a further solution of the present invention, the mixed solution A is prepared by mixing 3-isocyanatopropyltriethoxysilane and methyl orthosilicate in a mass ratio of 5-6.5:1-1.3.

As a further solution of the present invention, the wear-resistant coating includes the following preparation steps:

Weigh the raw materials according to the formula, add deionized water, silica sol, sulfuryl chloride, and modified nano-zinc oxide into the reaction vessel, add the mixed solution A dropwise, react at 80-85°C for 30-45min, and then cool down to 25±1.5 ℃, add silane coupling agent KH-560 and isopropanol, and stir for 1-2 hours to obtain a wear-resistant coating. Silanol is generated by the hydrolysis of 3-isocyanatopropyltriethoxysilane, and the silanol of the silica sol particles and the silanol are further dehydrated and condensed to form a silicon oxide silicon (Si-O-Si) covalent bond. Through the curing process, a high The cross-linked dense network or body structure, as the coating of the wear-resistant layer, is beneficial to improve the wear resistance of the coating.

As a further solution of the present invention, the erosion-resistant coating includes the following preparation steps:

Step S1. Dissolve epoxy resin E-44 in acetone, add silicone resin TSR-144, silane coupling agent KH560, dibutyltin dilaurate, heat up to 80-90°C, reflux and stir for 1.5-2h, and mix well Uniform, cooled after the reaction, to obtain epoxy-modified silicone resin;

Step S2. Mix and grind epoxy-modified silicone resin, polytetrafluoroethylene micropowder and defoamer BYK-141 to a fineness of 25-30 μm, then add curing agent T-31 and stir evenly to obtain an erosion-resistant coating. PTFE has structural characteristics such as high crystallinity, large relative molecular mass, no branched chain in the molecule, high C-F bond energy and F atoms shielding the main chain, which improves the corrosion resistance and wear resistance of the coating.

As a further scheme of the present invention, the mass ratio of epoxy resin E-44, acetone, organosilicon resin TSR-144, silane coupling agent KH560, dibutyltin dilaurate described in step S1 is 40-50:40-50: 20-30:2-3:1-1.2.

As a further solution of the present invention, the mass ratio of epoxy-modified silicone resin, polytetrafluoroethylene micropowder, defoamer BYK-141, and curing agent T-31 in step S2 is 20-30:20-30:20 -30:1-5.

As a further solution of the present invention, the preparation method of the wear-resistant coated glass includes the following preparation steps:

Step 1, using DC magnetron sputtering technology to prepare a silicon nitride primer layer on the surface of the glass body;

Step 2, using DC magnetron sputtering technology to prepare a silver-coated layer on the surface of the glass body;

Step 3. Filter the wear-resistant paint with a 3μm microporous membrane, add the wetting and leveling agent BYK-333 to mix, and apply it on the surface of the silver-plated layer by flow coating. After the surface is dry, dry it at a constant temperature of 40-50°C 1-2h, the coating is cured, and the preparation of the wear-resistant layer is completed;

Step 4: Spray the erosion-resistant coating on the outside of the wear-resistant layer, and dry it at 25±1.5°C for 24-30 hours to cure the coating and complete the preparation of the protective layer to obtain a wear-resistant coated glass.

As a further solution of the present invention, the target material of the DC magnetron sputtering technology described in step 1 is a silicon target, the functional gases are argon and nitrogen, the volume ratio of argon and nitrogen is 1-3:1-8, and the degree of vacuum It is 0.1-1.33Pa.

As a further solution of the present invention, the target material of the DC magnetron sputtering technique described in step 2 is a silver target.

As a further solution of the present invention, the mass ratio of the wear-resistant coating to the wetting and leveling agent BYK-333 in Step 3 is 100:0.3-0.4.

Beneficial effects of the present invention:

In the present invention, silanol is generated by hydrolysis of 3-isocyanatopropyltriethoxysilane, and the silanol and silanol of the silica sol particles are further dehydrated and condensed to form a silicon-oxygen-silicon (Si-O-Si) covalent bond. Through the curing process, Finally, a highly cross-linked and dense network or body structure is formed. The material of the wear-resistant layer is conducive to improving the wear resistance of the glass, preventing the silver-coated layer from being scratched by friction, and ensuring the high light transmission of the silver-coated layer of the coated glass. Rate;

The present invention modifies the surface of nano-zinc oxide through stearic acid, reduces the surface activation energy of nano-zinc oxide, and improves its dispersibility in wear-resistant coatings; the modified nano-zinc oxide has high transparency and low refractive index The characteristics of easy doping, can change the porosity and surface roughness of the coating system, and further improve the light transmittance of the glass;

The present invention mixes and grinds epoxy-modified organic silicon resin, polytetrafluoroethylene micropowder and defoamer BYK-141, and mixes curing agent T-31 to obtain an erosion-resistant coating. Polytetrafluoroethylene has high crystallinity, large relative molecular mass, There are no branched chains in the molecule, high C-F bond energy, and F atoms have a shielding effect on the main chain. The prepared protective layer material can improve the corrosion resistance of the wear-resistant layer and further improve the wear resistance of the wear-resistant layer. , to ensure the high light transmittance of the glass.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1

A modified nano-zinc oxide, comprising the following preparation steps:

Mix 10mL of stearic acid and 20mL of isopropanol and stir evenly, then add 1g of nano-zinc oxide, continue stirring at 18-20°C for 1 hour, let stand for 30min, and remove the supernatant to obtain modified nano-zinc oxide.

Example 2

A modified nano-zinc oxide, comprising the following preparation steps:

Mix and stir 12mL stearic acid and 30mL isopropanol evenly, then add 1.5g nano-zinc oxide, continue stirring at 18-20°C for 1.2h, let stand for 40min, and remove the supernatant to obtain modified nano-zinc oxide.

Example 3

A wear-resistant coating comprises the following preparation steps:

Weigh the raw materials according to the formula, add 9.4g deionized water, 1g silica sol, 1g sulfuryl chloride, 5g modified nano-zinc oxide prepared in Example 1 into the reaction vessel, add dropwise 10g mixed solution A (by 3-isocyanate Propyltriethoxysilane and methyl orthosilicate are mixed according to the mass ratio of 5:1.3), react at 80-85°C for 30min, cool down to 25±1.5°C, and add 2.8g of silane coupling agent KH -560, 14g of isopropanol, stirred for 1 hour to obtain a wear-resistant coating.

Comparative example 1

Compared with Example 3 in this comparative example, only "5g of the modified nano-zinc oxide prepared in Example 1" was replaced with "5g of nano-zinc oxide", and the rest of the steps and parameters were the same.

Example 4

A wear-resistant coating comprises the following preparation steps:

Weigh the raw materials according to the formula, add 15g deionized water, 8g silica sol, 1.2g sulfuryl chloride, 8g modified nano-zinc oxide obtained in Example 2 into the reaction vessel, add dropwise 14g mixed solution A (by 3-isocyanate Propyltriethoxysilane and methyl orthosilicate are mixed according to the mass ratio of 6.5:1), react at 80-85°C for 45min, cool down to 25±1.5°C, and add 3.3g of silane coupling agent KH -560, 20g of isopropanol, stirred for 2 hours to obtain a wear-resistant coating.

Example 5

A kind of erosion-resistant coating comprises following preparation steps:

Step S1. Dissolve 40g of epoxy resin E-44 in 40g of acetone, add 20g of silicone resin TSR-144, 2g of silane coupling agent KH560, and 1g of dibutyltin dilaurate, heat up to 80°C, and stir at reflux for 1.5h. Mix well and cool after reaction to obtain epoxy-modified silicone resin;

Step S2: Mix and grind 20g of epoxy-modified silicone resin, 20g of polytetrafluoroethylene micropowder and 20g of defoamer BYK-141 until the fineness is 25-30μm, then add 1g of curing agent T-31, and stir evenly to obtain Erosion resistant coatings.

Comparative example 2

Compared with Example 5, this comparative example only does not add "20g polytetrafluoroethylene micropowder", and the rest of the steps and parameters are the same.

Example 6

A kind of erosion-resistant coating comprises following preparation steps:

Step S1. Dissolve 50g of epoxy resin E-44 in 50g of acetone, add 30g of silicone resin TSR-144, 3g of silane coupling agent KH560, 1.2g of dibutyltin dilaurate, heat up to 90°C, and stir at reflux for 2h. Mix well and cool after reaction to obtain epoxy-modified silicone resin;

Step S2, mix and grind 30g of epoxy-modified silicone resin, 30g of polytetrafluoroethylene micropowder and 30g of defoamer BYK-141 to a fineness of 25-30 μm, then add 5g of curing agent T-31, and stir evenly to obtain Erosion resistant coatings.

Example 7

A preparation method of wear-resistant coated glass, comprising the following preparation steps:

Step 1. Using DC magnetron sputtering technology (the target is a silicon target, the functional gases are argon and nitrogen, the volume ratio of argon and nitrogen is 1:1, and the vacuum is 0.1Pa) to prepare nitrogen on the surface of the glass body Silicon base layer;

Step 2, using DC magnetron sputtering technology (the target material is a silver target) to prepare a silver-coated layer on the surface of the glass body;

Step 3, filter the wear-resistant coating obtained in Example 3 with a 3 μm microporous membrane, add wetting and leveling agent BYK-333 (the mass ratio of wear-resistant coating and wetting and leveling agent BYK-333 is 100:0.3 ) mixed, and coated on the surface of the glass body by flow coating, after the surface is dry, dry at a constant temperature of 40-50°C for 1-2h to cure the coating and complete the preparation of the wear-resistant layer;

Step 4: Spray the erosion-resistant coating prepared in Example 5 on the outside of the wear-resistant layer, and dry at 25±1.5°C for 24-30 hours to cure the coating and complete the preparation of the protective layer to obtain a wear-resistant coated glass.

Example 8

A preparation method of wear-resistant coated glass, comprising the following preparation steps:

Step 1. Using DC magnetron sputtering technology (the target is a silicon target, the functional gases are argon and nitrogen, the volume ratio of argon and nitrogen is 2:4.5, and the vacuum is 0.1Pa) to prepare nitrogen on the surface of the glass body Silicon base layer;

Step 2, using DC magnetron sputtering technology (the target material is a silver target) to prepare a silver-coated layer on the surface of the glass body;

Step 3, filter the wear-resistant coating obtained in Example 4 with a 3 μm microporous membrane, add wetting and leveling agent BYK-333 (the mass ratio of the wear-resistant coating to the wetting and leveling agent BYK-333 is 100:0.4 ) mixed, and coated on the surface of the glass body by flow coating, after the surface is dry, dry at a constant temperature of 40-50°C for 1-2h to cure the coating and complete the preparation of the wear-resistant layer;

Step 4. Spray the erosion-resistant coating prepared in Example 6 on the outside of the wear-resistant layer, and dry at 25±1.5°C for 24-30 hours to cure the coating and complete the preparation of the protective layer to obtain a wear-resistant coated glass.

Example 9

A preparation method of wear-resistant coated glass, comprising the following preparation steps:

Step 1. Using DC magnetron sputtering technology (the target is a silicon target, the functional gases are argon and nitrogen, the volume ratio of argon and nitrogen is 3:8, and the vacuum degree is 1.33Pa) to prepare nitrogen on the surface of the glass body Silicon base layer;

Step 2, using DC magnetron sputtering technology (the target material is a silver target) to prepare a silver-coated layer on the surface of the glass body;

Step 3, filter the wear-resistant coating obtained in Example 4 with a 3 μm microporous membrane, add wetting and leveling agent BYK-333 (the mass ratio of the wear-resistant coating to the wetting and leveling agent BYK-333 is 100:0.35 ) mixed, and coated on the surface of the glass body by flow coating, after the surface is dry, dry at a constant temperature of 40-50°C for 1-2h to cure the coating and complete the preparation of the wear-resistant layer;

Step 4: Spray the erosion-resistant coating prepared in Example 5 on the outside of the wear-resistant layer, and dry at 25±1.5°C for 24-30 hours to cure the coating and complete the preparation of the protective layer to obtain a wear-resistant coated glass.

Comparative example 3

Compared with Example 7, this comparative example only replaces "the wear-resistant coating prepared in Example 3" with "the wear-resistant coating prepared in Comparative Example 1", and the rest of the steps and parameters are the same.

Comparative example 4

Compared with Example 7, this comparative example only replaces "the erosion-resistant coating prepared in Example 5" with "the erosion-resistant coating prepared in Comparative Example 2", and the rest of the steps and parameters are the same.

Carry out following performance test to the coated glass that embodiment 7-9 and comparative example 3-4 make:

Light transmittance test: Use OU4220 visible/infrared/ultraviolet light transmittance meter to test the light transmittance of the coated glass to be tested, and record the measured data;

Wear resistance test: According to GB/T 18915.2-2013, test the wear resistance of the coated glass to be tested, and calculate the absolute value of the difference in visible light transmittance of the sample before and after the test;

Corrosion resistance test: test the acid resistance and alkali resistance of the coated glass to be tested according to GB/T 18915.2-2013, and calculate the absolute value of the difference in visible light transmittance before and after the test.

The test results are shown in Table 1.

Table 1

As can be seen from Table 1, the coated glass prepared in Examples 7-9 has better light transmittance and wear resistance than the coated glass prepared in Comparative Example 3, and has better light transmittance and abrasion resistance than the coated glass prepared in Comparative Example 4. Better wear and erosion resistance.

It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply that there is a relationship between these entities or operations. There is no such actual relationship or order between them. Furthermore, the term "comprises", "comprises" or any other variation thereof is intended to cover a non-exclusive inclusion such that a process, method, article, or apparatus comprising a set of elements includes not only those elements, but also includes elements not expressly listed. other elements of or also include elements inherent in such a process, method, article, or device.

Although the embodiments of the present invention have been shown and described, those skilled in the art can understand that various changes, modifications and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. and modifications, the scope of the invention is defined by the appended claims and their equivalents.

Claims (10)

1. a kind of wear-resistant coated glass, it is characterized in that, comprise glass main body, described glass main body surface is provided with silicon nitride primer layer, silver-plated layer, wear-resistant layer and protective layer successively; The material of described wear-resistant layer is wear-resistant coating; the material of the protective layer is an erosion-resistant coating; the wear-resistant coating includes the following raw materials in parts by weight: 9.4-15 parts of deionized water, 1-8 parts of silica sol, 1-1.2 parts of sulfuryl chloride, 5 - 8 parts of modified nano zinc oxide, 10-14 parts of mixed solution A, 2.8-3.3 parts of silane coupling agent KH-560, 14-20 parts of isopropanol. 2. A wear-resistant coated glass according to claim 1, characterized in that the particle size of the silica sol is 12-15 nm. 3. A kind of wear-resistant coated glass according to claim 1, is characterized in that, described modified nano-zinc oxide, comprises following preparation steps: Mix and stir 10-12mL stearic acid and 20-30mL isopropanol evenly, then add 1-1.5g nanometer zinc oxide, continue stirring at 18-20°C for 1-1.2h, let stand for 30-40min, remove the supernatant solution to obtain modified nano-zinc oxide. 4. A kind of wear-resistant coated glass according to claim 1, is characterized in that, described mixed solution A is made of 3-isocyanatopropyltriethoxysilane, orthosilicate methyl ester according to mass ratio 5-6.5 : Prepared by mixing 1-1.3. 5. A kind of wear-resistant coated glass according to claim 1, is characterized in that, described wear-resistant coating comprises following preparation steps: Weigh the raw materials according to the formula, add deionized water, silica sol, sulfuryl chloride, and modified nano-zinc oxide into the reaction vessel, add the mixed solution A dropwise, react at 80-85°C for 30-45min, and then cool down to 25±1.5°C , add silane coupling agent KH-560 and isopropanol, stir for 1-2h to obtain wear-resistant coating. 6. A kind of wear-resistant coated glass according to claim 1, is characterized in that, described erosion-resistant coating comprises following preparation steps: Step S1. Dissolve epoxy resin E-44 in acetone, add silicone resin TSR-144, silane coupling agent KH560, dibutyltin dilaurate, heat up to 80-90°C, reflux and stir for 1.5-2h, and mix well Uniform, cooled after the reaction, to obtain epoxy-modified silicone resin; Step S2. Mix and grind epoxy-modified silicone resin, polytetrafluoroethylene micropowder and defoamer BYK-141 to a fineness of 25-30 μm, then add curing agent T-31 and stir evenly to obtain an erosion-resistant coating. 7. A kind of wear-resistant coated glass according to claim 6, characterized in that, the epoxy resin E-44, acetone, organic silicon resin TSR-144, silane coupling agent KH560, dilauric acid dilaurate described in step S1 The mass ratio of butyltin is 40-50:40-50:20-30:2-3:1-1.2. 8. A kind of wear-resistant coated glass according to claim 6, characterized in that, the epoxy-modified silicone resin, polytetrafluoroethylene micropowder, defoamer BYK-141, curing agent T-31 described in step S2 The mass ratio is 20-30:20-30:20-30:1-5. 9. the preparation method of a kind of wear-resistant coated glass according to claim 1, is characterized in that, comprises following preparation steps: Step 1, using DC magnetron sputtering technology to prepare a silicon nitride primer layer on the surface of the glass body; Step 2, using DC magnetron sputtering technology to prepare a silver-coated layer on the surface of the glass body; Step 3. Filter the wear-resistant paint with a 3μm microporous membrane, add the wetting and leveling agent BYK-333 to mix, and apply it on the surface of the silver-plated layer by flow coating. After the surface is dry, dry it at a constant temperature of 40-50°C 1-2h, the preparation of the wear-resistant layer is completed; Step 4: Spray the corrosion-resistant paint on the outside of the wear-resistant layer, and dry it at 25±1.5°C for 24-30 hours to complete the preparation of the protective layer to obtain a wear-resistant coated glass. 10 . The method for preparing wear-resistant coated glass according to claim 9 , wherein the mass ratio of the wear-resistant coating to the wetting and leveling agent BYK-333 is 100:0.3-0.4.