A strong acid and strong alkali resistant protective ink applied to glass AG process and a preparation method thereof

Abstract

The application relates to a strong-acid and strong-alkali resistant protective ink applied to a glass AG process and a preparation method thereof, and belongs to the technical field of coating. The glass protective ink provided by the application comprises a protective agent and a diluent; the protective agent comprises the following components in parts by weight: etherified phenolic resin 30-35 parts, epoxy resin 25-30 parts, additive 0.5-1 part, filler 20-30 parts, solvent 5-10 parts and silane coupling agent 3-6 parts; the mass ratio of the protective agent to the diluent is 1:(0.8-1.2). The glass protective ink provided by the application adopts a spraying process, is simple to use and operate, and is high in production efficiency; after high-temperature curing and film forming, the strong-acid and strong-alkali resistant performance of the ink protective layer is excellent, the ink protective layer keeps high adhesion on the glass, after etching, the ink is removed by using a strong-alkali deinking solution, the glass surface is not damaged, and the yield of a glass AG process production line is greatly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to a kind of strong acid and strong alkali resistant protective ink applied to glass AG process and preparation method thereof. BACKGROUND

[0002] The most common treatment process of glass surface is AG process, which changes the glass from a reflective surface to a matte non-reflective surface (uneven surface), reduces the reflectivity of light from 8% to below 1%, and thus creates a clear and transparent visual effect. For the front cover glass screen, AG process can reduce the interference of ambient light, reduce screen reflection, make the image clearer, color more saturated, and brighter. On the back cover, the glass surface is often treated by AG process to etch brand logos or other pattern designs, thereby improving the appearance and touch of the product.

[0003] AG process is mainly divided into spray AG, coating AG and chemical etching AG. Chemical etching AG is a chemical etching process, which is processed by a special chemical process. The etched surface is uniform, corrosion and scratch resistant, the roughness range can be between 0.08-2.0, the glossiness can be up to 150, the transmittance is above 20-90%, which is comparable to the transmittance of smooth glass. It is the most widely used AG process technology. Since chemical etching AG uses hydrogen fluoride, nitric acid or frosting liquid to soak one side of the glass to form different texture patterns, patterns or frosted visual effects, and then uses strong alkali cleaning agent to clean the glass surface to remove residual acid and dirt to obtain the desired AG glass. In order to form the desired pattern and avoid accidental etching and damage to the appearance, a protective film is needed to protect the non-etched surface or the part that does not need to be etched from being corroded. The most common protection method on the market is to print protective ink.

[0004] However, the existing protective ink cannot effectively meet the requirements of glass AG process processing, has poor strong acid and strong alkali resistance, and is difficult to balance between protection and deinking, resulting in low production yield of glass AG process, slow deinking speed and residue, and low processing efficiency. Therefore, it is particularly important to develop a kind of strong acid and strong alkali resistant glass protective ink applied to glass panel AG process. SUMMARY

[0005] The present application aims to overcome the shortcomings of the prior art and provide a kind of strong acid and strong alkali resistant protective ink applied to glass AG process and preparation method thereof. The protective ink used in the present application has excellent strong acid and strong alkali cleaning agent resistance, can be used by spraying, is simple to operate, can be deinked with strong alkali deinking solution after etching of the glass surface, is clean and residue-free, and does not damage the glass surface.

[0006] To achieve the above object, the technical scheme adopted by the present application is:

[0007] In the first aspect, the present application provides a kind of strong acid and strong alkali resistant ink applied to glass AG process protection, including protective agent and diluent;Protective agent includes the following weight parts of components: etherified phenolic resin 30-35 parts, epoxy resin 25-30 parts, auxiliary 0.5-1 part, filler 20-30 parts, solvent 5-10 parts, silane coupling agent 3-6 parts;The mass ratio of protective agent and with diluent is 1 :(0.8-1.2).

[0008] Etherified phenolic resin has excellent acid resistance, and good compatibility, compact structure, high stability, and can crosslink with silane coupling agent;And epoxy resin has good matrix adhesion and corrosion resistance.Etherified phenolic resin, epoxy resin and silane coupling agent are used in combination, the protective ink has excellent adhesion on glass, and has certain strong acid and strong alkali resistance.

[0009] Diluent is generally selected to have good volatility and low toxicity ethyl acetate, using the above specific protective agent and diluent ratio, the ink can be easily sprayed to the state, convenient to use.The formed coating can protect the glass from being etched by strong acid etching solution or strong alkali cleaning agent in AG process, and can be removed by strong alkali deinking liquid in a short time, the glass surface is clean without residue, and plays a role in protecting the specific area of glass panel in chemical etching.

[0010] Under the above specific etherified phenolic resin, epoxy resin, silane coupling agent and other component ratio, the protective ink sprayed on the glass panel can maintain good adhesion on the glass after acid etching solution or strong alkali cleaning agent treatment, and the deinking time can be controlled within 3-5min;If the amount of etherified phenolic resin is too much, and the amount of epoxy resin is insufficient, the deinking time will be shortened, but the alkali resistance will be significantly reduced;If the amount of etherified phenolic resin is insufficient, and the amount of epoxy resin is too much, the deinking time will be increased, and the acid resistance will be significantly reduced.

[0011] The amount of silane coupling agent also affects the acid and alkali resistance of the ink.If the amount of silane coupling agent is too large, the reaction activity is high, which causes the ink coating to be too brittle, the adhesion on the glass to be reduced, and the deinking time to be long, the glass to still have residual points after deinking, and the protection effect to be poor;If the amount of silane coupling agent is too small, the adhesion of the ink to the glass will be poor, the acid and alkali resistance will be significantly reduced, and the glass panel protection function in AG process will be unable to play.

[0012] The present application provides a glass protection ink with excellent acid etching resistance and alkali cleaning agent resistance by using a combination of etherified phenolic resin, epoxy resin and silane coupling agent in a specific ratio, the coating formed can protect specific glass panels from corrosion by strong acid and strong alkali in the AG process, and can be removed by short-time ink removal liquid treatment without residue.

[0013] Preferably, the viscosity of the etherified phenolic resin is 1500-2500 cP; further preferably, the viscosity of the etherified phenolic resin is 1500-1800 cP. The viscosity is measured at 25°C using a rotary viscometer. The etherified phenolic resin with a viscosity in the range of 1500-2500 cP is prepared to obtain a protective ink with good spraying effect, ensuring that the ink can be successfully cured and play a good protection role; when the viscosity is 1500-1800 cP, the coating formed has stronger acid resistance. Too high or too low viscosity is not conducive to the spraying use of the ink, thereby affecting the protection effect.

[0014] Preferably, the epoxy equivalent weight of the epoxy resin is 450-500 g / eq. At this epoxy equivalent weight, the ink can maintain good acid and alkali resistance. If the epoxy equivalent weight is too high, the number of reactive groups in the resin is small, and the crosslinking density during curing will decrease the alkali resistance; if the epoxy equivalent weight is too low, the reactive groups are prone to incomplete reaction during curing, the ink is easily penetrated by alkali solution, and the ink removal speed is slow.

[0015] Preferably, the silane coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. The above silane coupling agent can connect inorganic groups and organic groups, and after crosslinking and curing, the ink material is tightly combined with the glass panel, thereby improving the adhesion of the ink on the glass and enhancing the acid and alkali resistance.

[0016] Further preferably, the silane coupling agent is 3-mercaptopropyltrimethoxysilane. The use of 3-mercaptopropyltrimethoxysilane as the silane coupling agent has good adhesion of the ink to the glass panel, and the adhesion of the coating after treatment with acid etching solution or strong alkali cleaning agent can reach 5B, thereby achieving the best protection effect.

[0017] Further preferably, the auxiliary agent is a leveling agent, the filler is talc, and the solvent is a mixture of propylene glycol methyl ether acetate and ethylene glycol monobutyl ether. The use of a mixture of propylene glycol methyl ether acetate and ethylene glycol monobutyl ether as the solvent can fully mix the components, adjust the viscosity of the ink and enhance the operability; and the ink has a moderate evaporation speed during curing, which can ensure the smooth curing of the coating.

[0018] Further preferably, the mass ratio of propylene glycol methyl ether acetate to ethylene glycol monobutyl ether in the solvent is 1:1. With this ratio, the boiling point of the solvent is moderate, and the ink coating is not prone to bubbling or volatilizing too quickly to cause defects during the curing process, and the protective effect of the ink coating is optimal.

[0019] Further preferably, the strong-acid-and-strong-base-resistant protective ink for glass AG process comprises the following components by weight: etherified phenolic resin 35 parts, epoxy resin 25 parts, leveling agent 0.5 parts, talc 25 parts, propylene glycol methyl ether acetate 5 parts, ethylene glycol monobutyl ether 5 parts, 3-mercaptopropyltrimethoxysilane 5 parts, and diluent 100 parts. With this ratio, the ink has moderate viscosity and strong operability, and the sprayed thickness is uniform; the cured coating formed by the ink has an adhesion of 5B after being treated with a strong-acid or strong-base cleaning agent, and can well protect the glass panel from corrosion by acid / alkali liquid in the process; after being treated with a deinking liquid, the glass surface is quickly deinked within 4 minutes and has no residue, and the overall effect is optimal.

[0020] In a second aspect, the present application provides a preparation method of the above-mentioned strong-acid-and-strong-base-resistant protective ink for glass AG process, comprising the following steps: mixing the components of the protective agent and then uniformly dispersing and mixing at 200-400 r / min, continuously dispersing at 600-1000 r / min for 20-40 min, and then adding and uniformly mixing the diluent to obtain the strong-acid-and-strong-base-resistant protective ink for glass AG process.

[0021] In a third aspect, the present application provides the use of the above-mentioned strong-acid-and-strong-base-resistant protective ink for glass AG process in glass chemical etching.

[0022] Preferably, the use comprises the following steps: spraying the above-mentioned strong-acid-and-strong-base-resistant protective ink for glass AG process on the surface of glass, baking at 150-200℃ for 30-40 min, cooling to obtain a glass ink protective layer, and then performing chemical etching to achieve the use of the strong-acid-and-strong-base-resistant protective ink for glass AG process in glass chemical etching; the thickness of the glass ink protective layer is 20-30 μm.

[0023] The chemical etching process is as follows: the glass forming the glass ink protective layer is immersed in a 10% hydrofluoric acid solution or other etching liquid for 10-20 min to form the desired texture pattern or frosting effect; it is then taken out and cleaned with a strong alkali cleaning agent with pH=13-14 for 3-5 min; it is then immersed in a strong alkali deinking liquid at 80℃ for 3-5 min for deinking, washed with clean water and dried to obtain the required finished AG glass.

[0024] In the spraying process, the thickness of the glass ink protective layer is controlled to be 20-30 mu m, the coating has excellent acid and alkali resistance, and the ink removal time is moderate. The application mode of the glass protective ink provided by the application is simple and easy to operate. The glass ink protective layer formed has good resistance to acid / alkali solution in the AG process, and can still be well attached to the glass panel after process treatment, thereby playing a protective effect; and can be removed after 3-5 min of ink removal, without residue, and has high application value in glass chemical etching.

[0025] Compared with the prior art, the beneficial effects of the application are:

[0026] The glass protective ink provided by the application can be applied by a spraying process and is simple to operate; has high production efficiency; after high-temperature curing to form a film, has excellent resistance to strong acid and strong alkali cleaning agents and can still maintain high glass adhesion; after surface etching, the ink can be removed with a strong alkali ink removal solution, without residue, without damaging the glass surface, thereby protecting the glass and achieving ink removal without residue, and greatly improving the yield of the glass AG process. DETAILED DESCRIPTION

[0027] To better illustrate the purpose, technical solution and advantages of the application, the application will be further described below in combination with specific examples. In the following examples, the test methods used are conventional methods unless otherwise specified; and the materials, reagents, etc. used are commercially available reagents and materials unless otherwise specified.

[0028] In the following examples and comparative examples, the preparation method of the glass ink protective layer is as follows:

[0029] (1) The components in the protective agent are added while being dispersed at a dispersion speed of 200-400 r / min; after the materials are completely added, they are dispersed at 600-1000 r / min for 20-40 min until the components are fully mixed; the protective agent and the diluent are mixed and stirred uniformly at a weight ratio of 1:1 to obtain a strong acid and alkali resistant protective ink for glass AG process.

[0030] (2) The glass protective ink obtained is sprayed on one side of the glass, baked at a temperature of 180 DEG C for 40 min, and cooled to form a glass ink protective layer, with the coating thickness controlled to be 25 mu m.

[0031] In the following examples and comparative examples, the test method for acid resistance is as follows:

[0032] The prepared glass with a glass ink protective layer is immersed in a 10% HF solution for 20 min, and then the adhesion of the ink on the glass is tested by the crosshatch method, and the results are recorded in accordance with the national standard GB / T9286. The higher the adhesion, the better the acid resistance.

[0033] In the following examples and comparative examples, the test method for alkali resistance is as follows:

[0034] The prepared glass with a glass ink protective layer was immersed in a strong alkali cleaning agent (pH = 13-14) at 80℃ for 5min, and after taking out, the adhesion of the ink on the glass was tested by the grid method, and the results were recorded according to the national standard GB / T 9286, the higher the adhesion, the better the alkali resistance.

[0035] In the following examples and comparative examples, the test method for stripping performance is as follows:

[0036] The prepared glass with a glass ink protective layer was placed in a strong alkali stripping liquid at 80℃, the ink stripping time was recorded, and whether the ink was left on the glass was observed, the shorter the stripping time and the cleaner the glass without residue, the better the ink stripping performance.

[0037] The sources of raw materials used in the examples and comparative examples of the present application are as follows:

[0038] Etherified phenolic resin: CR-101 of Shengquan Company, viscosity 1500-1800cP / 25℃;

[0039] Etherified phenolic resin: CR-109 of Shengquan Company, viscosity 1800-2500cP / 25℃;

[0040] Etherified phenolic resin: CR-102 of Shengquan Company, viscosity 300-800cP / 25℃;

[0041] Epoxy resin: NPEL-128 of Nanya Company, epoxy equivalent weight 160g / eq-210g / eq;

[0042] Epoxy resin: NPES-901 of Nanya Company, epoxy equivalent weight 450-500g / eq;

[0043] Epoxy resin: NPES-902 of Nanya Company, epoxy equivalent weight 600g / eq-660g / eq;

[0044] Silane coupling agent: Z-6300 of Dow Corning Company, vinyl trimethoxysilane;

[0045] Silane coupling agent: Z-6040 of Dow Corning Company, 3-(2,3-epoxypropoxy) propyl trimethoxysilane;

[0046] Silane coupling agent: Z-6062 of Dow Corning Company, 3-mercaptopropyl trimethoxysilane;

[0047] Leveling agent: BYK-307 of BYK Company, polyether modified dimethyl siloxane.

[0048] Other materials, reagents, etc. used in the examples were obtained from commercial sources unless otherwise stated.

[0049] Example 1

[0050] An example of the application of the strong acid and alkali resistant protective ink for glass AG process, the application of the strong acid and alkali resistant protective ink for glass AG process of the example includes the following components by weight: etherified phenolic resin (CR-101) 35 parts, epoxy resin (NPES-901) 30 parts, leveling agent (BYK-307) 1 part, talc 20 parts, propylene glycol methyl ether acetate 5 parts, ethylene glycol monobutyl ether 5 parts, silane coupling agent (Z-6062) 5 parts, ethyl acetate 81 parts.

[0051] Example 2

[0052] An example of the application of the strong acid and alkali resistant protective ink for glass AG process, the application of the strong acid and alkali resistant protective ink for glass AG process of the example includes the following components by weight: etherified phenolic resin (CR-101) 30 parts, epoxy resin (NPES-901) 25 parts, leveling agent (BYK-307) 0.5 parts, talc 30 parts, propylene glycol methyl ether acetate 2.5 parts, ethylene glycol monobutyl ether 2.5 parts, silane coupling agent (Z-6062) 4.5 parts, ethyl acetate 114 parts.

[0053] Example 3

[0054] An example of the application of the strong acid and alkali resistant protective ink for glass AG process, the application of the strong acid and alkali resistant protective ink for glass AG process of the example includes the following components by weight: etherified phenolic resin (CR-101) 33 parts, epoxy resin (NPES-901) 29 parts, leveling agent (BYK-307) 0.7 parts, talc 25 parts, propylene glycol methyl ether acetate 3 parts, ethylene glycol monobutyl ether 3 parts, silane coupling agent (Z-6062) 6 parts, ethyl acetate 100 parts.

[0055] Example 4

[0056] The difference between example 4 and example 1 is only that etherified phenolic resin CR-109 is used.

[0057] Example 5

[0058] An embodiment of the application applied to the strong acid and alkali resistant protective ink for glass AG process, the strong acid and alkali resistant protective ink applied to the glass AG process of the embodiment comprises the following components by weight: etherified phenolic resin (CR-101) 35 parts, epoxy resin (NPES-901) 25 parts, leveling agent (BYK-307) 0.5 parts, talc 25 parts, propylene glycol methyl ether acetate 5 parts, ethylene glycol monobutyl ether 5 parts, silane coupling agent (Z-6062) 5 parts, ethyl acetate 100 parts.

[0059] Example 6

[0060] Example 6 differs from Example 5 only in that the silane coupling agent (Z-6062) is 3 parts.

[0061] Example 7

[0062] Example 7 differs from Example 5 only in that the silane coupling agent (Z-6062) is 6 parts.

[0063] Example 8

[0064] Example 8 differs from Example 5 only in that the silane coupling agent Z-6300 is used.

[0065] Example 9

[0066] Example 9 differs from Example 5 only in that the silane coupling agent Z-6040 is used.

[0067] Comparative Example 1

[0068] Comparative Example 1 differs from Example 5 only in that the etherified phenolic resin (CR-101) is 40 parts and the epoxy resin (NPES-901) is 20 parts.

[0069] Comparative Example 2

[0070] Comparative Example 2 differs from Example 5 only in that the etherified phenolic resin (CR-101) is 20 parts and the epoxy resin (NPES-901) is 40 parts.

[0071] Comparative Example 3

[0072] Comparative Example 3 differs from Example 5 only in that the epoxy resin NPEL-128 is used.

[0073] Comparative Example 4

[0074] Comparative Example 4 differs from Example 5 only in that the epoxy resin NPES-902 is used.

[0075] Comparative Example 5

[0076] Comparative Example 5 differs from Example 5 only in that the silane coupling agent (Z-6062) is 7 parts.

[0077] Comparative Example 6

[0078] Comparative Example 6 differs from Example 5 only in that the silane coupling agent (Z-6062) is 2 parts.

[0079] Comparative Example 7

[0080] Comparative Example 7 differs from Example 5 only in that the solvent is 10 parts of n-butanol.

[0081] Comparative Example 8

[0082] Comparative Example 8 differs from Example 5 only in that the propylene glycol methyl ether acetate is 9 parts and the ethylene glycol monobutyl ether is 1 part.

[0083] Comparative Example 9

[0084] Comparative Example 9 differs from Example 1 only in that the etherified phenolic resin CR-102 is used.

[0085] The glass protective inks in the above examples and comparative examples were prepared into a spray coating of a glass ink protective layer, and then the acid resistance, alkali resistance and deinking time were measured, with the results shown in Table 1.

[0086] Table 1 Performance test results of examples and comparative examples

[0087]

[0088]

[0089] From the performance comparison of the glass protective inks of the examples and comparative examples in Table 1, it can be seen that:

[0090] (1) Comparative Examples and Comparative Examples 1-2: The ratio of the etherified phenolic resin and the epoxy resin defined in the present application can ensure that the glass protective ink has excellent acid and alkali resistance, plays a protective effect, and can be deinked smoothly in a short time. If the amount of etherified phenolic resin is too much and the amount of epoxy resin is insufficient, the deinking time is shortened, but the alkali resistance is significantly deteriorated. If the amount of etherified phenolic resin is insufficient and the amount of epoxy resin is too much, the deinking time is increased, and the acid resistance is significantly deteriorated.

[0091] (2) Comparative Examples 1, 4 and Comparative Example 9: The viscosity of the etherified phenolic resin affects the ink spraying performance and acid resistance. Within the limited viscosity range, the ink has good spraying effect and plays a good protective role. When the viscosity is 1500-1800 cP, the formed coating has stronger acid resistance.

[0092] (3) Comparative Example 5 and Comparative Examples 3 and 4: the ink protection effect and comprehensive performance are better at a limited epoxy resin epoxy equivalent; when the epoxy equivalent of the epoxy resin is too small, the ink curing is incomplete, the acid and alkali resistance is poor, when the epoxy equivalent is too large, the crosslinking density is low, the acid and alkali resistance of the ink is reduced, and the ink removal speed is slow.

[0093] (4) Comparative Example 5 and Comparative Examples 5-6: the specific silane coupling agent dosage has a great influence on the ink performance; when the silane coupling agent dosage is too large, the reaction activity is high, the ink after curing is brittle, the glass adhesion is poor, and the ink removal is slow, and there are residual points after the glass is removed; when the silane coupling agent dosage is too small, the ink adhesion with the glass is poor, and the acid and alkali resistance is reduced.

[0094] (5) Comparative Example 5 and Comparative Examples 7 and 8: specific solvents and ratios are used to better control the smooth curing of the coating, the surface has no defects, and the protection effect of the ink coating is ensured. Using other solvents or changing the ratio may cause defects in the cured ink coating, thereby reducing the acid and alkali resistance.

[0095] Finally, it should be explained that the above examples are only used to illustrate the technical solutions of the present application, but not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present application.

Claims

1. A glass protective ink, characterized in that, It includes a protective agent and a diluent; the protective agent is composed of the following components in parts by weight: 30-35 parts etherified phenolic resin, 25-30 parts epoxy resin, 0.5-1 part additives, 20-30 parts filler, 5-10 parts solvent, and 3-6 parts silane coupling agent; the mass ratio of the protective agent to the diluent is 1:(0.8-1.2). The epoxy equivalent of the epoxy resin is 450-500 g / eq; The viscosity of the etherified phenolic resin is 1500-2500 cp; The solvent is a mixture of propylene glycol methyl ether acetate and ethylene glycol monobutyl ether; In the solvent, the mass ratio of propylene glycol methyl ether acetate to ethylene glycol monobutyl ether is 1:

1.

2. The glass protective ink according to claim 1, characterized in that, The silane coupling agent is at least one of vinyltrimethoxysilane, vinyltriethoxysilane, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and 3-mercaptotrimethoxysilane.

3. The glass protective ink according to claim 2, characterized in that, The additive is a leveling agent, and the filler is talc.

4. The glass protective ink according to claim 1, characterized in that, The product comprises the following components in parts by weight: 35 parts etherified phenolic resin, 25 parts epoxy resin, 0.5 parts leveling agent, 25 parts talc, 5 parts propylene glycol methyl ether acetate, 5 parts ethylene glycol monobutyl ether, 5 parts 3-mercaptotrimethoxysilane, and 100 parts diluent.

5. The method for preparing the glass protective ink according to any one of claims 1-4, characterized in that, Includes the following steps: After mixing the components of the protective agent, disperse and mix them at 200-400 r / min, continue to disperse at 600-1000 r / min for 20-40 min, and then add the diluent and mix well to obtain the glass protective ink.

6. The application of the glass protective ink according to any one of claims 1-4 in glass chemical etching.

7. The application of the glass protective ink according to claim 6 in glass chemical etching, characterized in that, The application includes the following steps: spraying the glass protective ink according to any one of claims 1-5 onto the glass surface, baking it at 150-200℃ for 30-40 minutes, cooling it to obtain a glass ink protective layer, and then performing chemical etching to realize the application of the glass protective ink in glass chemical etching; the thickness of the glass ink protective layer is 20-30μm.

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