A light-cured high-durability metal and glass universal PVD primer and a preparation method thereof

Abstract

This invention relates to the field of coatings, particularly to the C09D163 / 00 field, and more specifically to a photocurable high-durability PVD primer for metals and glass, and its preparation method. The raw materials for preparing the primer, by weight, include: 8-12 parts aliphatic polyurethane acrylate, 10-18 parts modified polyester acrylate, 10-20 parts epoxy acrylate, 5-10 parts reactive monomer diluent, 5-10 parts adhesion promoter, 1-5 parts photoinitiator, 45-55 parts solvent, and 0.1-1 parts additives. The primer provided by this invention possesses both water-resistant and high-temperature resistant properties, achieving the technical effect of being suitable for both glass and metal substrates. The primer exhibits good storage stability, a simple preparation process, and has significant commercial value.

Description

Technical Field

[0001] This invention relates to the field of coatings, particularly to the field of C09D163 / 00, and more specifically to a photocurable high-durability PVD primer for metals and glass and its preparation method. Background Technology

[0002] Common coating processes include primer and topcoat. Primer is applied directly to the substrate surface, acting as a base material. During application, the primer forms a strong bond with the substrate, ensuring the coating adheres firmly and preventing peeling. It also fills in surface roughness and pores, resulting in a smoother finish and improved aesthetics and texture. Coatings are susceptible to wear, oxidation, and UV radiation, which can degrade their performance. Primer enhances stability and weather resistance, making the coating more durable and resistant to external damage. Topcoat is the second coat applied after primer, typically the final layer in a multi-coat system, and serves to protect the primer.

[0003] Primers typically need to possess high adhesion and weather resistance for better practical application. Existing technology CN116656216A discloses a high-temperature resistant UV primer for glass electroplating, comprising a UV polymer, epoxy acrylate, aliphatic polyurethane acrylic resin, monomers, initiators, additives, and solvents. It exhibits high adhesion and high-temperature resistance after bonding to the glass substrate surface. Existing technology CN103097473B discloses a primer composition for metal materials, which achieves high adhesion to various metal materials such as ordinary steel, stainless steel, aluminum alloy, copper, and galvanized steel, exhibiting excellent bond strength and durability. However, currently, there are relatively few PVD primers that can meet the requirements of being universally compatible with glass and metal substrates and are resistant to high temperatures and boiling water. Summary of the Invention

[0004] To address the aforementioned technical problems, the first aspect of this invention provides a photocurable, high-durability PVD primer suitable for both metals and glass. The raw materials used in its preparation, by weight, include: 8-12 parts aliphatic polyurethane acrylate, 10-18 parts modified polyester acrylate, 110-20 parts epoxy acrylate, 5-10 parts reactive monomer diluent, 5-10 parts adhesion promoter, 1-5 parts photoinitiator, 45-55 parts solvent, and 0.1-1 parts additives.

[0005] Preferably, the aliphatic polyurethane acrylate has a functionality of 2-6; when the functionality is 2, it includes ST808, ST852, ST2260H, ST8052, ST8052M, and ST8132; when the functionality is 6, it includes ST8736; all of which are purchased from Shanghai Santong.

[0006] More preferably, the aliphatic polyurethane acrylate has a viscosity of 50,000-70,000 cps at 60°C, which is ST808.

[0007] Preferably, the modified polyester acrylate includes ST6052, which is purchased from Santong Technology.

[0008] Preferably, the functionality of the epoxy acrylate is 2-6.

[0009] More preferably, the epoxy acrylate has a functionality of 2; as an implementable example, the 2-functionality epoxy acrylate includes one or more of ST500, ST502, ST5027, ST602, ST604M, ST605, ST615, and ST625, all of which are purchased from Shanghai Santong.

[0010] More preferably, the epoxy acrylate has a viscosity of 4000-6000 cps at 60°C, which is ST604M.

[0011] Preferably, the active monomer diluent is an acrylate monomer, including one or more of the following: dicyclopentenyl acrylate, isobornyl methacrylate, triethylene glycol diacrylate, pentaerythritol triacrylate, hydroxyethyl methacrylate, and tetrahydrofuran acrylate.

[0012] More preferably, the acrylate monomers include hydroxyethyl methacrylate and pentaerythritol triacrylate in a mass ratio of (3-6):(4-6).

[0013] Preferably, the adhesion promoter comprises a phosphate ester acrylate promoter and a silane coupling agent in a mass ratio of 1:(1-4).

[0014] More preferably, the phosphate ester acrylate accelerator has a viscosity of 100-600 cps at 60°C.

[0015] More preferably, the phosphate ester acrylate accelerator has a viscosity of 160-320 cps at 60°C, is model SZ1771, and is purchased from Shanghai Santong.

[0016] More preferably, the silane coupling agent includes one of Z-6040, Z-6020, Z-6030, Z-6011, and Z-6121, all of which are purchased from Dow Corning.

[0017] More preferably, the silane coupling agent is Z-6040.

[0018] This invention does not further limit the photoinitiator; any initiator that can promote the photocuring process of the system is acceptable, including but not limited to: STCure-184, STCure-1173, STCure-917, and STCure-1219 from Shanghai Santong; Jiu Ri photoinitiators 1103, 1055, and MBF; and one or more of IGM Omnirad 184 and IGM Omnirad 651. In this invention, IGM Omnirad 184 and IGM Omnirad 651 are preferred, with a mass ratio of 1:1.

[0019] Preferably, the solvent includes one or more of ethyl acetate, butyl acetate, methyl isobutyl ketone, propylene glycol methyl ether, xylene, ethanol, n-butanol, ethylene glycol butyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, butanone, and acetone.

[0020] More preferably, the solvent includes ethyl acetate, butyl acetate, methyl isobutyl ketone, and propylene glycol methyl ether in a mass ratio of (10-30):(10-20):(5-20):(1-10).

[0021] The additives in this invention may include antioxidants, defoamers, leveling agents, pigments, etc.; antioxidants include antioxidant 1010, antioxidant 168, etc.; defoamers include BYK-024, BYK-011, etc.; leveling agents include tego-1484, tego-410, BYK-306, etc.; pigments include iron oxide, chrome yellow, titanium dioxide, zinc oxide, etc.; they can be used as needed according to the actual production and processing conditions. The preferred additive in this invention is leveling agent BYK-306.

[0022] A second aspect of this invention provides a method for preparing a photocurable, high-durability PVD primer suitable for metals and glass, comprising the following steps:

[0023] S1. Feeding: Prepare epoxy acrylate, modified polyester acrylate, aliphatic polyurethane acrylate and reactive monomer diluent according to the formula ratio to obtain component A; prepare adhesion promoter, photoinitiator, additives and solvent according to the formula ratio to obtain component B.

[0024] S2. Dispersion: Disperse the prepared component A material at a high speed of 500-1000 rpm for 30-60 minutes. After mixing evenly, stop stirring to obtain solution A. Disperse the prepared component B material at a medium speed of 200-500 rpm for 5-20 minutes. After mixing evenly, stop stirring to obtain solution B.

[0025] S3. Mixing: Slowly pour solution B into solution A and stir at a low speed of 100-200 rpm until the mixture is homogeneous.

[0026] Beneficial effects

[0027] (i) In order to ensure that the primer has excellent adhesion performance, the present invention preferably uses aliphatic polyurethane acrylate ST808 and modified polyester acrylate ST6052 as raw materials; polyurethane acrylate has excellent low temperature resistance; high mechanical strength, excellent adhesion to glass substrates, and excellent resilience and good paintability, making it suitable for large-area bonding.

[0028] (ii) Polyurethane acrylate is prone to bubbling when exposed to moisture, and powdering after the primer has cured is relatively common. This limits the application of PVD primer in certain harsh environments. Therefore, this invention adds epoxy acrylate to the preparation system, which can reduce the foaming performance of the coating and improve the high temperature and water boiling resistance of the primer. However, the viscosity of epoxy acrylate should not be too high. In this invention, ST604M with a viscosity of 4000-6000 cps at 25°C is preferred. If the viscosity is too high, it will not be conducive to the uniformity of the raw material system and will lead to a certain decrease in the stability of the primer.

[0029] (III) In this invention, acrylate monomers are selected as active monomer diluents, especially the combination of hydroxyethyl methacrylate and pentaerythritol triacrylate. Hydroxyethyl methacrylate can improve the adhesion to glass substrates through hydrogen bonding, while pentaerythritol triacrylate can improve the curing speed and leveling performance of the primer, thereby improving the weather resistance of the primer.

[0030] (iv) In this invention, phosphate ester acrylates are selected, especially SZ1771 with a viscosity of 100-800cps at 60°C, which can significantly improve the adhesion performance of the primer on the surface of the metal substrate. This is mainly because the phosphate groups in the phosphate ester acrylate have a slight phosphating effect on the metal substrate, which is beneficial to improving the adhesion of the metal layer. At the same time, since the active monomer diluent in this invention includes hydroxyethyl methacrylate, it can achieve the technical effect of being applicable to both glass and hardware substrates.

[0031] (V) In order to improve the high temperature resistance of the primer, the inventors have found that the use of silane coupling agent Z-6040 can achieve the technical effect of high temperature resistance. At the same time, the combination of Z-6040 and phosphate ester acrylate accelerator makes the primer less prone to problems such as coating coloring and high temperature blistering after use, and the product stability is significantly improved.

[0032] (vi) The photocurable high-durability metal and glass universal PVD primer provided by the present invention has both water boiling resistance and high temperature resistance, and achieves the technical effect of being universal for both glass substrates and metal substrates. In addition, the primer of the present invention has good storage stability and simple preparation process, and has good commercial use value. Detailed Implementation

[0033] Example 1

[0034] The first aspect of this example provides a photocurable high-durability PVD primer for metals and glass, the raw materials of which are, by weight, 10 parts aliphatic polyurethane acrylate, 12.5 parts modified polyester acrylate, 14 parts epoxy acrylate, 9 parts reactive monomer diluent, 3 parts adhesion promoter, 50 parts solvent, 4 parts photoinitiator, and 0.1 parts additives.

[0035] The aliphatic polyurethane acrylate has a functionality of 2 and a viscosity of 50,000-70,000 cps at 60°C. It is designated ST808 and purchased from Shanghai Santong.

[0036] The modified polyester acrylate is ST6052, purchased from Shanghai Santong.

[0037] The epoxy acrylate mentioned is ST604M, with a functionality of 2 and a viscosity of 4000-6000 cps at 60°C, purchased from Shanghai Santong.

[0038] The active monomer diluent is hydroxyethyl methacrylate and pentaerythritol triacrylate in a mass ratio of 5:4; the hydroxyethyl methacrylate is Wanhua Chemical HEMA-98, and the pentaerythritol triacrylate is Changxing Chemical EM235.

[0039] The adhesion promoter is a phosphate ester acrylate promoter and a silane coupling agent Z-6040, with a mass ratio of 1:2; the phosphate ester acrylate promoter is ST1771, purchased from Shanghai Santong, and the silane coupling agent Z-6040 is purchased from Dow Corning.

[0040] The photoinitiators are IGM Omnirad 184 and IGM Omnirad 651 in a mass ratio of 1:1.

[0041] The additive is the leveling agent BYK-306.

[0042] The solvent is ethyl acetate, butyl acetate, methyl isobutyl ketone, and propylene glycol methyl ether in a mass ratio of 4:3:2:1.

[0043] The second aspect of this example provides a method for preparing a photocurable, high-durability PVD primer suitable for both metals and glass, specifically comprising the following steps:

[0044] S1. Feeding: Prepare epoxy acrylate, modified polyester acrylate, aliphatic polyurethane acrylate and reactive monomer diluent according to the formula ratio to obtain component A; prepare adhesion promoter, photoinitiator, additives and solvent according to the formula ratio to obtain component B.

[0045] S2. Dispersion: Disperse the prepared component A material at high speed of 800 rpm for 30 minutes. After mixing evenly, stop stirring to obtain solution A. Disperse the prepared component B material at medium speed of 400 rpm for 10 minutes. After mixing evenly, stop stirring to obtain solution B.

[0046] S3. Mixing: Slowly pour solution B into solution A and stir at a low speed of 100 rpm until the mixture is homogeneous.

[0047] Example 2

[0048] The specific implementation method of this example is the same as that of Example 1, except that the mass fractions of the raw materials are different. The raw materials are as follows by mass fraction: 12 parts aliphatic polyurethane acrylate, 10 parts modified polyester acrylate, 15 parts epoxy acrylate, 9 parts reactive monomer diluent, 2.5 parts adhesion promoter, 50 parts solvent, 4 parts photoinitiator, and 0.1 parts additives. The adhesion promoter is a phosphate acrylate promoter and a silane coupling agent Z-6040, with a mass ratio of 2:3.

[0049] Example 3

[0050] The specific implementation method of this example is the same as that of Example 1, except that the mass fractions of the raw materials are different. The raw materials are as follows by mass fraction: 8 parts aliphatic polyurethane acrylate, 10 parts modified polyester acrylate, 16.5 parts epoxy acrylate, 9 parts reactive monomer diluent, 4 parts adhesion promoter, 50 parts solvent, 4 parts photoinitiator, and 0.1 parts additives. The adhesion promoter is a phosphate acrylate promoter and a silane coupling agent Z-6040, with a mass ratio of 1:1.

[0051] Example 4

[0052] The specific implementation method in this example is the same as in Example 1, except that the aliphatic polyurethane acrylate is Shanghai Santong ST8142.

[0053] Comparative Example 1

[0054] The specific implementation method in this example is the same as in Example 1, except that the phosphate ester acrylate accelerator is Nippon Kayaku PM-2 (hydroxyethyl methacrylate phosphate), with a viscosity of 600-3000 mPa.s / 25℃.

[0055] Comparative Example 2

[0056] The specific implementation method in this example is the same as in Example 1, except that the silane coupling agent is Shin-Etsu KBE-903 from Japan.

[0057] Comparative Example 3

[0058] The specific implementation method in this example is the same as in Example 1, except that the adhesion promoter is 2 parts, which is the silane coupling agent Dow Corning Z-6040 (excluding ST1771).

[0059] Comparative Example 4

[0060] The specific implementation method in this example is the same as in Example 1, except that the adhesion promoter is 2 parts, which is ST1771 (excluding Dow Corning Z-6040).

[0061] Performance Evaluation

[0062] The primers obtained in Examples 1-4 and Comparative Examples 1-4 were electroplated onto glass substrates and their performance was tested. The test data are listed in Table 1. The specific electroplating methods were substrate treatment and vacuum electroplating, as detailed below:

[0063] Substrate preparation: Choose ordinary glass or tinplate as the substrate, and use a clean cloth dampened with isopropyl alcohol to remove contaminants from the substrate.

[0064] Vacuum electroplating:

[0065] 1. Primer electroplating: Air spraying is used, with an air pressure of 0.6 MPa; the spray gun nozzle diameter is 1.3 mm; the distance between the spray gun and the substrate is 25 cm; the paint mist atomization angle is 35°; the paint film thickness is 10 μm; preheating is done at 55℃ for 5 min; 900 mJ / cm² 2 UV curing followed by cooling at 25°C for 30 minutes after curing.

[0066] 2. Electroplated metal layer: Vacuum aluminum plating is performed on the surface of the photocurable coating. The thickness of the electroplating is 0.3 μm, and the areal density is 0.27 g / m³. 2 .

[0067] Test items:

[0068] 1. Adhesion test: Prepare samples of the products from the examples and comparative examples, and test them according to the standard GB / T9286-1998 using the cross-cut adhesion test.

[0069] 2. Water resistance test: Boil in water at 100℃ for 1 hour, observe whether blistering, peeling, or discoloration occurs on the surface, and measure the adhesion after boiling.

[0070] 3. High temperature resistance test: Bake at 180℃ for 2 hours, observe whether blistering, peeling, or discoloration occurs on the surface, and measure the adhesion after baking.

[0071] Table 1

[0072]

[0073] Note: "--" means: Since the first standard adhesion test is 0B, there is no need to conduct subsequent water and temperature resistance tests.

Claims

1. A photocurable, high-durability PVD primer for metals and glass, characterized in that, The raw materials for preparing the primer are as follows (by weight): 10 parts aliphatic polyurethane acrylate, 12.5 parts modified polyester acrylate, 14 parts epoxy acrylate, 9 parts reactive monomer diluent, 3 parts adhesion promoter, 50 parts solvent, 4 parts photoinitiator, and 0.1 parts additives. The aliphatic polyurethane acrylate has a functionality of 2 and a viscosity of 50,000-70,000 cps at 60°C. It is ST808 and was purchased from Shanghai Santong. The modified polyester acrylate mentioned is ST6052, purchased from Shanghai Santong; The epoxy acrylate mentioned is ST604M, with a functionality of 2 and a viscosity of 4000-6000 cps at 60°C, purchased from Shanghai Santong. The active monomer diluent is hydroxyethyl methacrylate and pentaerythritol triacrylate in a mass ratio of 5:4; the hydroxyethyl methacrylate is Wanhua Chemical HEMA-98, and the pentaerythritol triacrylate is Changxing Chemical EM235. The adhesion promoter is a phosphate ester acrylate promoter and a silane coupling agent Z-6040, with a mass ratio of 1:2; the phosphate ester acrylate promoter is ST1771, and the silane coupling agent Z-6040 is purchased from Dow Corning. The photoinitiators are IGM Omnirad 184 and IGM Omnirad 651 in a mass ratio of 1:1; The additive is the leveling agent BYK-306; The solvent is ethyl acetate, butyl acetate, methyl isobutyl ketone, and propylene glycol methyl ether in a mass ratio of 4:3:2:

1.

2. A photocurable, high-durability PVD primer for metals and glass, characterized in that, The raw materials for preparing the primer are as follows (by weight): 12 parts aliphatic polyurethane acrylate, 10 parts modified polyester acrylate, 15 parts epoxy acrylate, 9 parts reactive monomer diluent, 2.5 parts adhesion promoter, 50 parts solvent, 4 parts photoinitiator, and 0.1 parts additives. The aliphatic polyurethane acrylate has a functionality of 2 and a viscosity of 50,000-70,000 cps at 60°C. It is ST808 and was purchased from Shanghai Santong. The modified polyester acrylate mentioned is ST6052, purchased from Shanghai Santong; The epoxy acrylate mentioned is ST604M, with a functionality of 2 and a viscosity of 4000-6000 cps at 60°C, purchased from Shanghai Santong. The active monomer diluent is hydroxyethyl methacrylate and pentaerythritol triacrylate in a mass ratio of 5:4; the hydroxyethyl methacrylate is Wanhua Chemical HEMA-98, and the pentaerythritol triacrylate is Changxing Chemical EM235. The adhesion promoter is a phosphate ester acrylate promoter and a silane coupling agent Z-6040, with a mass ratio of 2:3; the phosphate ester acrylate promoter is ST1771, and the silane coupling agent Z-6040 is purchased from Dow Corning. The photoinitiators are IGM Omnirad 184 and IGM Omnirad 651 in a mass ratio of 1:1; The additive is the leveling agent BYK-306; The solvent is ethyl acetate, butyl acetate, methyl isobutyl ketone, and propylene glycol methyl ether in a mass ratio of 4:3:2:

1.

3. A photocurable, high-durability PVD primer for metals and glass, characterized in that, The raw materials for preparing the primer are as follows (by weight): 8 parts aliphatic polyurethane acrylate, 10 parts modified polyester acrylate, 16.5 parts epoxy acrylate, 9 parts reactive monomer diluent, 4 parts adhesion promoter, 50 parts solvent, 4 parts photoinitiator, and 0.1 parts additives. The aliphatic polyurethane acrylate has a functionality of 2 and a viscosity of 50,000-70,000 cps at 60°C. It is ST808 and was purchased from Shanghai Santong. The modified polyester acrylate mentioned is ST6052, purchased from Shanghai Santong; The epoxy acrylate mentioned is ST604M, with a functionality of 2 and a viscosity of 4000-6000 cps at 60°C, purchased from Shanghai Santong. The active monomer diluent is hydroxyethyl methacrylate and pentaerythritol triacrylate in a mass ratio of 5:4; the hydroxyethyl methacrylate is Wanhua Chemical HEMA-98, and the pentaerythritol triacrylate is Changxing Chemical EM235. The adhesion promoter is a phosphate ester acrylate promoter and a silane coupling agent Z-6040, with a mass ratio of 1:1; the phosphate ester acrylate promoter is ST1771, and the silane coupling agent Z-6040 is purchased from Dow Corning. The photoinitiators are IGM Omnirad 184 and IGM Omnirad 651 in a mass ratio of 1:1; The additive is the leveling agent BYK-306; The solvent is ethyl acetate, butyl acetate, methyl isobutyl ketone, and propylene glycol methyl ether in a mass ratio of 4:3:2:

1.

4. A photocurable, high-durability PVD primer for metals and glass, characterized in that, The raw materials for preparing the primer are as follows (by weight): 10 parts aliphatic polyurethane acrylate, 12.5 parts modified polyester acrylate, 14 parts epoxy acrylate, 9 parts reactive monomer diluent, 3 parts adhesion promoter, 50 parts solvent, 4 parts photoinitiator, and 0.1 parts additives. The aliphatic polyurethane acrylate is ST8142 resin, purchased from Shanghai Santong. The modified polyester acrylate mentioned is ST6052, purchased from Shanghai Santong; The epoxy acrylate mentioned is ST604M, with a functionality of 2 and a viscosity of 4000-6000 cps at 60°C, purchased from Shanghai Santong. The active monomer diluent is hydroxyethyl methacrylate and pentaerythritol triacrylate in a mass ratio of 5:4; the hydroxyethyl methacrylate is Wanhua Chemical HEMA-98, and the pentaerythritol triacrylate is Changxing Chemical EM235. The adhesion promoter is a phosphate ester acrylate promoter and a silane coupling agent Z-6040, with a mass ratio of 1:2; the phosphate ester acrylate promoter is ST1771, and the silane coupling agent Z-6040 is purchased from Dow Corning. The photoinitiators are IGM Omnirad 184 and IGM Omnirad 651 in a mass ratio of 1:1; The additive is the leveling agent BYK-306; The solvent is ethyl acetate, butyl acetate, methyl isobutyl ketone, and propylene glycol methyl ether in a mass ratio of 4:3:2:

1.

5. A method for preparing a photocurable high-durability PVD primer for metals and glass according to any one of claims 1-4, characterized in that, Includes the following steps: S1. Feeding: Prepare component A by mixing epoxy acrylate, modified polyester acrylate, aliphatic polyurethane acrylate, and reactive monomer diluent according to the formula ratio; prepare component B by mixing adhesion promoter, photoinitiator, additives, and solvent according to the formula ratio. S2. Dispersion: Disperse the prepared component A material at a high speed of 500-1000 rpm for 30-60 minutes. After mixing evenly, stop stirring to obtain solution A. Disperse the prepared component B material at a medium speed of 200-500 rpm for 5-20 minutes. After mixing evenly, stop stirring to obtain solution B. S3. Mixing: Slowly pour solution B into solution A and stir at a low speed of 100-200 rpm until homogeneous.

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