A kind of high temperature resistant glass electroplating UV primer and preparation method thereof

Abstract

The present invention relates to the technical field of photocurable coatings, in particular to the field of IPC C09D175, and more specifically to a high-temperature resistant glass electroplating UV primer and a preparation method thereof. The components include: 10-20 parts of UV polymer, 8-15 parts of epoxy acrylic resin, 4-10 parts of aliphatic polyurethane acrylic resin, 10-18 parts of monomer, 1-5 parts of initiator, 0.5-2 parts of auxiliary agent, and 30-70 parts of solvent. The initiator includes BP (benzophenone) and 2-EAQ (2-ethylanthraquinone), and the weight ratio of BP and 2-EAQ is 1: (1-2), which can improve the heat resistance of the primer and improve the adhesion of the primer; the UV polymer includes, acrylic modified alkyd resin, aliphatic acrylic resin, and the acrylic modified alkyd resin and aliphatic acrylic resin weight ratio are 1: (1.5-3), which can increase the adhesion of the coating to 5B, effectively improve the high temperature resistance of the coating, especially 180°C baking for 1h, and there is no bubbling, peeling, or coloring on the surface.

Description

Technical Field

[0001] The invention relates to the technical field of photocurable coatings, in particular to the field of IPC C09D175, and more specifically to a high-temperature resistant glass electroplating UV primer and a preparation method thereof. Background Art

[0002] Since high-temperature baking varnish or other thermosetting paints have too low production efficiency, UV vacuum electroplating coating technology has developed rapidly due to its high efficiency brought by not requiring high-temperature baking and instant curing. Its application areas have been continuously expanded to cosmetic packaging, automobile lampshades, and coating of various electronic product plastic shells. With the deepening of application and the continuous improvement of product requirements, UV curing coatings still have problems in terms of adhesion to various substrates and bonding with different coatings. The problems encountered in the industry are mainly concentrated on the phenomenon of blistering and paint peeling after adding UV topcoat.

[0003] CN113072870B discloses a UV roller-coated vacuum electroplating coating and a preparation method thereof. A UV vacuum electroplating coating that can be used for large-area roller coating has been developed. After roller coating on a metal substrate or a plastic substrate, a film product with excellent resistance to cold and heat and water boiling can be obtained. This type of film product has good toughness and can be pressed with various building materials to obtain a decorative building material product with a high metallic texture. The prepolymer is a mixture of difunctional aliphatic polyurethane acrylate, difunctional special modified epoxy acrylate, and special polyurethane acrylate. There are compatibility issues with conventional 184 photoinitiators, which to a certain extent affects the high temperature resistance of the coating and limits its application in high temperature scenes. Summary of the invention

[0004] In order to overcome the shortcomings of the background technology, the present invention provides a high-temperature resistant glass electroplating UV primer and a preparation method thereof. By optimizing the selection of raw materials and the ratio between components, the prepared primer can ensure good adhesion and plating properties on the glass while having excellent high-temperature resistance.

[0005] To achieve the purpose of the present invention, the first aspect of the present invention provides a high-temperature resistant glass electroplating UV primer, which comprises, by weight, 10-20 parts of UV polymer, 8-15 parts of epoxy acrylic resin, 4-10 parts of aliphatic polyurethane acrylic resin, 10-18 parts of monomer, 1-5 parts of initiator, 0.5-2 parts of auxiliary agent, and 30-70 parts of solvent.

[0006] Preferably, the UV oligomer has an average viscosity (25° C.) of 100-1000 cps and a solid content of 45-55 wt %.

[0007] Preferably, the UV oligomer comprises acrylic modified alkyd resin and aliphatic acrylic resin, and the weight ratio of the acrylic modified alkyd resin to the aliphatic acrylic resin is 1:(1.5-3).

[0008] Further preferably, the weight ratio of the acrylic modified alkyd resin to the aliphatic acrylic resin is 1:2.

[0009] More preferably, the viscosity (25°C) of the acrylic modified alkyd resin is 100-200 cps, purchased from Jiangsu Sanmu Chemical, model: 1350; the viscosity (25°C) of the aliphatic acrylic resin is 200-1000 cps, the solid content is 50wt%, model: RS-6371.

[0010] The epoxy acrylic resin has a functionality of 2-4 and an acid value of less than 5 mgKOH / g.

[0011] Preferably, the epoxy acrylic resin has a functionality of 2 and an acid value of less than 2 mgKOH / g, model: L-6132A, manufacturer: Guangdong Sanqi New Materials Co., Ltd.

[0012] The functionality of the aliphatic polyurethane acrylic resin is 2-3.

[0013] Preferably, the functionality of the aliphatic polyurethane acrylic resin is 2.

[0014] Preferably, the aliphatic polyurethane acrylic resin includes one of allnex EBECRYL 8213, Lancolu L-6205, allnex UCECOAT 7177, Changxing 6154B-80, Changxing 6121F-80, Meiyuan PU240, Liangzhi RJ426, and DSM U-25-20D.

[0015] Further preferably, the aliphatic polyurethane acrylic resin includes allnex EBECRYL 8213.

[0016] The monomers include one or a combination of two or more of HEMA (hydroxyethyl methacrylate), THFA (tetrahydrofuran acrylate), TPGDA (tripropylene glycol diacrylate), DPGDA (dipropylene glycol diacrylate), HDDA (hexanediol diacrylate), TMPTA (trimethylolpropane triacrylate), and PET3A (pentaerythritol triacrylate).

[0017] Preferably, the monomers include HEMA (hydroxyethyl methacrylate), DPGDA (dipropylene glycol diacrylate), and TMPTA (trimethylolpropane triacrylate), and the weight ratio of HEMA, DPGDA, and TMPTA is (6-10): (4-6): (3-6).

[0018] Further preferably, the weight ratio of HEMA, DPGDA and TMPTA is 8:5:5.

[0019] The photoinitiator includes a hydrogen abstraction type free radical photoinitiator.

[0020] Preferably, the hydrogen abstraction free radical photoinitiator includes at least one of benzophenone and its derivatives, thioxanthone and its derivatives, and anthraquinone and its derivatives.

[0021] The applicant has found that the hydrogen abstraction free radical photoinitiator includes benzophenone and its derivatives, anthraquinone and its derivatives, which can effectively improve the high temperature resistance of the primer. It may be that the two types of photoinitiators improve the compatibility between the resins in the system and the continuity between the chemical crosslinking points due to the π-π stacking effect between the molecules. Further research has found that the initiator includes BP (benzophenone) and 2-EAQ (2-ethylanthraquinone), and the weight ratio of BP and 2-EAQ is 1: (1-2), which can improve the heat resistance of the primer and improve the adhesion of the primer. When the amount of benzophenone is large, it is easy to cause light shielding of the bottom layer, and the addition of 2-ethylanthraquinone may reduce the photobleaching effect due to the conjugation effect of multiple benzene rings in the molecule, and improve the curing efficiency of the bottom layer. At the same time, there is a certain difference in the initiation rate between the two photoinitiators. In this system, the curing rate between the bottom layer and the surface layer may be balanced, avoiding the stress generated by the crosslinking of polymers between different layers, thereby improving the adhesion of the coating to 5B.

[0022] Further preferably, the hydrogen abstraction free radical photoinitiator includes benzophenone and its derivatives, anthraquinone and its derivatives.

[0023] More preferably, the initiator comprises BP (benzophenone) and 2-EAQ (2-ethylanthraquinone), and the weight ratio of BP to 2-EAQ is 1:(1-2).

[0024] More preferably, the weight ratio of BP to 2-EAQ is 1:2.

[0025] The auxiliary agents include leveling agents and wetting agents.

[0026] Preferably, the leveling agent includes one of silicone acrylate type, pure acrylate, polyester modified silicone oxane, and polyether modified silicone oxane.

[0027] Further preferably, the leveling agent includes silicone acrylate type, and the leveling agent includes Digo 2100.

[0028] The solvent includes at least one of ethyl acetate, butyl acetate, isopropanol, toluene and xylene.

[0029] Preferably, the solvent comprises ethyl acetate.

[0030] Preferably, the weight ratio of the UV polymer, epoxy acrylic resin and aliphatic polyurethane acrylic resin is 10:(10-14):(3-7).

[0031] Further preferably, the weight ratio of the UV polymer, epoxy acrylic resin and aliphatic polyurethane acrylic resin is 10:(12-14):(4-6).

[0032] More preferably, the weight ratio of the UV polymer, epoxy acrylic resin and aliphatic polyurethane acrylic resin is 10:13:5.

[0033] Preferably, the weight ratio of the UV oligomer to the monomer is 2:(3-4).

[0034] Further preferably, the weight ratio of the UV oligomer to the monomer is 5:9.

[0035] A second aspect of the present invention provides a method for preparing a high temperature resistant glass electroplating UV primer, comprising the following steps:

[0036] S1, choose an environment that is shielded from ultraviolet light and illuminated by yellow light;

[0037] S2, mixing the monomer, the photoinitiator and the solvent, and stirring until they are completely dissolved;

[0038] S3, add UV polymer, epoxy acrylic resin, aliphatic polyurethane acrylic resin and additives in sequence, stir until completely dissolved, and obtain.

[0039] Beneficial Effects

[0040] 1. The hydrogen abstraction free radical photoinitiator includes benzophenone and its derivatives, anthraquinone and its derivatives, which can effectively improve the high temperature resistance of the primer.

[0041] 2. The initiator includes BP (benzophenone) and 2-EAQ (2-ethylanthraquinone), and the weight ratio of BP to 2-EAQ is 1:(1-2), which can improve the heat resistance of the primer and enhance the adhesion of the primer.

[0042] 3. The UV polymer includes acrylic modified alkyd resin and aliphatic acrylic resin, wherein the weight ratio of acrylic modified alkyd resin to aliphatic acrylic resin is 1:(1.5-3), which can improve the adhesion of the coating to 5B and effectively improve the high temperature resistance of the coating, especially after baking at 180°C for 1h, there is no bubbling, peeling or coloring on the surface.

[0043] 4. The weight ratio of the UV oligomer to the monomer is 2:(3-4), which can stabilize the coating performance and improve the compatibility between systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 The coating surface is obtained by baking the coating at 180° C. for 1 hour as in Example 1.

[0045] Figure 2 The coating surface prepared in Comparative Example 1 was baked at 180° C. for 1 hour.

[0046] Figure 3 The coating surface prepared in Comparative Example 2 was baked at 180° C. for 1 hour.

[0047] Figure 4 The coating surface prepared in comparative example 3 was obtained after the coating was baked at 180° C. for 1 hour.

[0048] Figure 5 The coating of the primer on the glass beer bottle was prepared in Example 4.

[0049] Figure 6 The coating surface prepared in Comparative Example 4 was obtained after the coating was baked at 180° C. for 1 hour. DETAILED DESCRIPTION

[0050] Example 1

[0051] A high-temperature resistant glass electroplating UV primer comprises the following components by weight: 10 parts of UV oligomer, 15 parts of epoxy acrylic resin, 8 parts of aliphatic polyurethane acrylic resin, 18 parts of monomer, 3 parts of initiator, 1.1 parts of auxiliary agent and 50 parts of solvent.

[0052] The UV polymer is acrylic acid modified alkyd resin and acrylic resin, and the weight ratio of the acrylic acid modified alkyd resin and acrylic resin is 1:2.

[0053] The viscosity (25°C) of the acrylic modified alkyd resin is 100-200 cps, purchased from Jiangsu Sanmu Chemical, model: 1350; the viscosity (25°C) of the aliphatic acrylic resin is 200-1000 cps, the solid content is 50wt%, model: RS-6371.

[0054] The epoxy acrylic resin has a functionality of 2 and an acid value of less than 2 mgKOH / g. Model: L-6132A. Manufacturer: Guangdong Sanqi New Materials Co., Ltd.

[0055] The aliphatic polyurethane acrylic resin is EBECRYL 8213 produced by Allnex.

[0056] The monomers are HEMA (hydroxyethyl methacrylate), DPGDA (dipropylene glycol diacrylate), and TMPTA (trimethylolpropane triacrylate), and the weight ratio of HEMA, DPGDA, and TMPTA is 8:5:5.

[0057] The initiators are BP (benzophenone) and 2-EAQ (2-ethylanthraquinone), and the weight ratio of BP to 2-EAQ is 1:2.

[0058] The auxiliary agent is a leveling agent, and the leveling agent is Digo 2100.

[0059] The solvent is ethyl acetate.

[0060] A method for preparing a high temperature resistant glass electroplating UV primer comprises the following steps:

[0061] S1, choose an environment that is shielded from ultraviolet light and illuminated by yellow light;

[0062] S2, mixing the monomer, photoinitiator and solvent, and stirring at 300 rpm until completely dissolved;

[0063] S3, add UV polymer, epoxy acrylic resin, aliphatic polyurethane acrylic resin and additives in sequence, and stir at 600 rpm until completely dissolved.

[0064] Example 2

[0065] The specific implementation is the same as in Example 1; the difference is that in Example 2, 12 parts of UV oligomer, 12 parts of epoxy acrylic resin, and 4 parts of aliphatic polyurethane acrylic resin are used.

[0066] Example 3

[0067] The specific implementation is the same as Example 1; the difference is that in Example 3, 11 parts of UV oligomer, 11 parts of epoxy acrylic resin, and 6 parts of aliphatic polyurethane acrylic resin are used.

[0068] Comparative Example 1

[0069] The specific implementation is the same as Example 1; the difference is that the UV polymer in Comparative Example 1 is an unsaturated polyester resin, model: 2126, purchased from Changxing Chemical Industry Co., Ltd., Taiwan, China.

[0070] Comparative Example 2

[0071] The specific implementation method is the same as Example 1; the difference is that in Comparative Example 2, the UV polymer is 15 parts, the epoxy acrylic resin is 13 parts, and the monomer is 10 parts. The UV polymer is an unsaturated polyester resin, model: 2126, purchased from Changxing Chemical Industry Co., Ltd., Taiwan, China.

[0072] Comparative Example 3

[0073] The specific implementation method is the same as Example 1; the difference is that in Comparative Example 3, 15 parts of UV oligomer, 10 parts of epoxy acrylic resin, 8 parts of aliphatic polyurethane acrylic resin, and 13 parts of monomer are used.

[0074] Comparative Example 4

[0075] The specific implementation method is the same as that of Example 1; the difference is that the initiator in Comparative Example 4 is 1173 (2-hydroxy-2-methyl-1-phenyl-1-propanone).

[0076] Performance Testing Methods

[0077] The primers obtained in the examples and comparative examples were electroplated onto glass substrates and then performance tests were performed. The test data are listed in Table 1. The specific electroplating methods include substrate treatment and vacuum electroplating, as follows:

[0078] Substrate treatment: Ordinary glass is selected as the substrate, and contaminants on the substrate are removed with a clean cloth dipped in isopropyl alcohol.

[0079] Vacuum plating:

[0080] ①, Primer electroplating: air spraying, air pressure 0.3Mpa; spray gun caliber 1.3mm; spray gun and substrate surface distance 25cm, paint mist atomization angle 35°, paint film thickness 10μm; 55℃ preheating 5min; 900mj / cm 2 UV curing, cooling at room temperature for 30 minutes after curing;

[0081] ② Electroplated metal layer: vacuum aluminum is plated on the surface of the photocurable coating. The thickness of the electroplating is 0.3 μm and the surface density is 0.27 g / m 2 .

[0082] 1) Adhesion test reference standard GB / T 9286-1998, using the hundred grid method.

[0083] 2) High temperature resistance test: bake at 180℃ for 1h, and observe whether the surface has blistering, peeling, or coloring. The test results are as follows: Figure 1-4 shown.

[0084] Comparative Example 1-3 had no adhesion due to bubbling and peeling from the substrate, so no adhesion test was performed and the sample was indicated by "-".

[0085] like Figure 5 As shown, the primer prepared in the example is electroplated onto the outer surface of a glass beer bottle.

[0086] Performance test data

[0087] Table 1

[0088]

[0089]

Claims

1. A high temperature resistant glass electroplating UV primer, characterized in that: The components include, by weight: 10-20 parts of UV oligomer, 8-15 parts of epoxy acrylic resin, 4-10 parts of aliphatic polyurethane acrylic resin, 10-18 parts of monomer, 1-5 parts of initiator, 0.5-2 parts of auxiliary agent, and 30-70 parts of solvent; The initiator is benzophenone and 2-ethylanthraquinone, and the weight ratio of benzophenone to 2-ethylanthraquinone is 1:(1-2); The UV oligomer is an acrylic acid modified alkyd resin and an aliphatic acrylic resin, and the weight ratio of the acrylic acid modified alkyd resin to the aliphatic acrylic resin is 1:(1.5-3); The monomer includes one or a combination of two or more of HEMA, THFA, TPGDA, DPGDA, HDDA, TMPTA, and PET3A; The weight ratio of the UV polymer, epoxy acrylic resin and aliphatic polyurethane acrylic resin is 10: (10-14): (3-7); The acrylic acid modified alkyd resin was purchased from Jiangsu Sanmu Chemical Industry, model: 1350; the aliphatic acrylic resin model: RS-6371; The weight ratio of the UV oligomer to the monomer is 2:(3-4).

2. The high temperature resistant glass electroplating UV primer according to claim 1, characterized in that: The UV oligomer has an average viscosity of 100-1000 cps and a solid content of 45-55 wt %.

3. The high temperature resistant glass electroplating UV primer according to claim 2, characterized in that: The epoxy acrylic resin has a functionality of 2-4 and an acid value of less than 5 mgKOH / g.

4. The high temperature resistant glass electroplating UV primer according to claim 3, characterized in that: The functionality of the aliphatic polyurethane acrylic resin is 2-3.

5. A method for preparing a high temperature resistant glass electroplating UV primer according to claim 1, characterized in that: The following steps are involved: S1, choose an environment that is shielded from ultraviolet light and illuminated by yellow light; S2, mixing the monomer, the photoinitiator and the solvent, and stirring until they are completely dissolved; S3, add UV polymer, epoxy acrylic resin, aliphatic polyurethane acrylic resin and additives in sequence, stir until completely dissolved, and obtain.

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