Impact-resistant electroplating primer for elastomer plastic balls as well as preparation method and application of impact-resistant electroplating primer

Abstract

The invention discloses an impact-resistant electroplating primer for elastomer plastic balls. The impact-resistant electroplating primer is prepared from the following raw materials in parts by weight: 30-50 parts of modified alkyd resin, 15-25 parts of C9 petroleum resin, 1-5 parts of a drier, 45-55 parts of a solvent and 0.1-1 part of an auxiliary agent. By adopting the combination of the soybean oil modified alkyd resin and the TDI modified alkyd resin, the adhesive force of the primer can be improved, the toughness of the primer is improved, and the durability of the adhesive force of a paint film is improved to a certain extent. The composition of the cobalt iso-octoate drier, the zirconium iso-octoate drier and the manganese iso-octoate drier is adopted, the weight ratio of the cobalt iso-octoate drier to the zirconium iso-octoate drier to the manganese iso-octoate drier is 1: 1: 1, brittleness of a paint film can be improved, and a transparent and bright paint film layer is formed. The coating is applied to balls made of ABS and PS blanks, has good adhesive force and can bear natural aging for one year, and a paint film is not prone to falling off after being impacted.

Description

Technical Field

[0001] The invention relates to the field of coating compositions, and in particular to an impact-resistant electroplating primer for elastomeric plastic balls, a preparation method and an application thereof. Background Art

[0002] Existing plastic colored balls are mostly low-brightness. Electroplating a primer on the surface of the balls, followed by vacuum sputtering of an aluminum film, can enhance their brightness. Spraying a colored topcoat further enhances the decorative aesthetic. Existing colored balls have long storage cycles, become brittle after long-term natural aging, and are prone to paint loss after impact. Furthermore, the production process involves numerous steps, and insufficient primer curing can cause mold and reduce product yields. Therefore, developing an electroplated primer that resists aging and impact is crucial.

[0003] Chinese invention patent application CN119684881A discloses a high-flash-point alkyd protective coating and its preparation method. The coating's film-forming system, composed of a high-molecular-weight alkyd resin and a high-solubility aromatic solvent oil, enhances the coating's hydrolysis resistance while also providing improved substrate adhesion and chemical resistance. However, the coating exhibits long surface and through-drying times. Chinese invention patent application CN1840594A discloses a petroleum resin-modified high-solids alkyd anti-rust primer. This anti-rust primer, prepared by combining a medium-oil drying alkyd resin with a petroleum resin, exhibits low pollution, fast drying, and superior anti-rust performance. However, the primer suffers from poor impact resistance and is prone to paint chipping. Summary of the Invention

[0004] In order to develop an anti-aging and impact-resistant electroplating primer, the first aspect of the present invention provides an impact-resistant electroplating primer for elastomeric plastic balls. The raw materials prepared by weight include: 30-50 parts of modified alkyd resin, 15-25 parts of C9 petroleum resin, 1-5 parts of drying agent, 45-55 parts of solvent, and 0.1-1 part of auxiliary agent.

[0005] As an embodiment, the modified alkyd resin includes at least two of soybean oil modified alkyd resin, epoxy modified alkyd resin, acrylic acid modified alkyd resin, isocyanate modified alkyd resin, and polyurethane modified alkyd resin.

[0006] As an embodiment, the acid value of the soybean oil-modified alkyd resin is ≤12 mgKOH / g, and the outflow viscosity at 25° C. is 25-55 s.

[0007] As an embodiment, the iron-cobalt colorimetric ratio of the soybean oil-modified alkyd resin is 15-17#.

[0008] As an embodiment, the acid value of the isocyanate-modified alkyd resin is less than 8 mgKOH / g, and the outflow viscosity at 25° C. is 5-9 s.

[0009] As an embodiment, the color of the isocyanate-modified alkyd resin is less than 7# color and the density is 0.9-1.

[0010] As an embodiment, the density of the isocyanate-modified alkyd resin is 0.96.

[0011] As an embodiment, the isocyanate-modified alkyd resin includes at least one of a TDI-modified alkyd resin, an MDI-modified alkyd resin, or a TDI-MDI mixed modified alkyd resin.

[0012] As an embodiment, the modified alkyd resin includes a combination of soybean oil modified alkyd resin and TDI modified alkyd resin.

[0013] As an embodiment, the weight ratio of the soybean oil modified alkyd resin to the TDI modified alkyd resin is (10-15): (20-30).

[0014] As an embodiment, the weight ratio of the soybean oil modified alkyd resin to the TDI modified alkyd resin is 12:28.

[0015] As an embodiment, the C9 petroleum resin is thermally polymerized 11#C9 petroleum resin.

[0016] The present invention adopts a combination of soybean oil-modified alkyd resin and TDI-modified alkyd resin, which can improve the adhesion problem of the primer, enhance the toughness of the primer, avoid the aging and brittle effect of the primer during long-term storage, thereby extending the adhesion time of the primer and enhancing the long-term adhesion of the primer.

[0017] As an embodiment, the drier is a metal isooctanoate drier, including at least one of a cobalt isooctanoate drier, a zirconium isooctanoate drier, and a manganese isooctanoate drier.

[0018] As an embodiment, the drier is a combination of a cobalt isooctanoate drier, a zirconium isooctanoate drier and a manganese isooctanoate drier.

[0019] As an embodiment, the weight ratio of the cobalt isooctanoate drier, the zirconium isooctanoate drier and the manganese isooctanoate drier is (1-3): (1-3): (1-3).

[0020] As an embodiment, the weight ratio of the cobalt isooctanoate drier, the zirconium isooctanoate drier and the manganese isooctanoate drier is 1:1:1.

[0021] The present invention adopts a combination of a cobalt isooctanoate drier, a zirconium isooctanoate drier, and a manganese isooctanoate drier in a weight ratio of 1:1:1, which can improve the brittleness of the paint film and form a translucent paint film layer. The reason may be that the combination of the cobalt isooctanoate drier, the zirconium isooctanoate drier, and the manganese isooctanoate drier can accelerate the surface drying speed of the paint film, prevent the paint film surface from fogging, and affect the appearance. At the same time, it delays the actual drying speed, avoids the paint film from being too brittle, improves the toughness of the paint film, and prevents the paint film from easily falling off after being impacted.

[0022] As an embodiment, the solvent is a combination of solvent oil and white spirit.

[0023] As an embodiment, the solvent oil is 200# solvent oil, and the white spirit is 120# white spirit.

[0024] As an embodiment, the weight ratio of the solvent oil to the white spirit is (20-25): (25-30).

[0025] As an embodiment, the weight ratio of the solvent oil to the white spirit is 24:25.

[0026] As an embodiment, the auxiliary agent includes at least a leveling agent and an adhesion promoter, and the adhesion promoter is a silicone adhesion promoter.

[0027] As an embodiment, the silicone adhesion promoter is KH-792.

[0028] This application introduces the silane coupling agent KH-792 as an adhesion promoter, which can improve the adhesion durability between the paint film and the substrate, improve the aging resistance of the paint film, prevent the paint film from falling off during transportation bumps and collisions, and improve the product yield.

[0029] A second aspect of the present invention provides a method for preparing an impact-resistant electroplating primer for an elastomeric plastic ball, comprising the following steps:

[0030] The prepared raw materials are mixed in sequence, stirred at 500-1000 rpm for 20-40 minutes at room temperature (15-35° C.), and filtered to obtain a primer.

[0031] As an embodiment, the filtration is performed using a filter bag, and the pore size of the filter bag is 1-3 μm.

[0032] The third aspect of the present invention provides an application of an impact-resistant electroplating primer for elastomeric plastic balls, which is applied to ABS and PS blanks.

[0033] As an embodiment, the primer is electroplated onto ABS (acrylonitrile-butadiene-styrene copolymer) or PS (polystyrene) blanks and then baked at 50-70° C. for 2-4 hours.

[0034] As an embodiment, the electroplating thickness of the primer is 15-30 μm.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) The impact-resistant electroplating primer for elastomeric plastic balls of the present invention adopts a combination of soybean oil-modified alkyd resin and TDI-modified alkyd resin, which can improve the adhesion problem of the primer, increase the toughness of the primer, and improve the adhesion durability of the paint film to a certain extent.

[0037] (2) The impact-resistant electroplating primer for the elastomeric plastic ball of the present invention adopts a combination of a cobalt isooctanoate drier, a zirconium isooctanoate drier and a manganese isooctanoate drier in a weight ratio of 1:1:1, which can improve the brittleness of the paint film and form a transparent paint film layer.

[0038] (3) The impact-resistant electroplating primer for the elastomeric plastic ball of the present invention introduces the silane coupling agent KH-792 as an adhesion promoter, which can improve the adhesion durability between the paint film and the substrate, and will not cause the paint film to fall off during the bumpy and collision process of transportation, thereby improving the product yield rate.

[0039] (4) The impact-resistant electroplating primer for elastomeric plastic balls of the present invention is applied to balls made of ABS and PS blanks, has good adhesion, can withstand one year of natural aging, and the paint film is not easy to fall off after being impacted.

[0040] (5) The elastomeric plastic ball of the present invention is coated with an impact-resistant electroplating primer. After electroplating and curing, aluminum is sputtered onto the paint film by vacuum electroplating to form a covering aluminum film. The paint film and the aluminum film have good bonding properties, which can achieve smooth processing of the Christmas ball. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a photo of the electroplating effect of the electroplating primer prepared in Example 1 applied to a Christmas ball;

[0042] Figure 2 This is a photo of the electroplating effect of the electroplating primer prepared in Example 2 applied to a Christmas ball;

[0043] Figure 3 This is a photo of the electroplating effect of the electroplating primer prepared in Example 3 applied to a Christmas ball;

[0044] Figure 4 This is a photo of the electroplating effect of the electroplating primer prepared in Example 4 applied to a Christmas ball. DETAILED DESCRIPTION

[0045] Example 1

[0046] The invention discloses an impact-resistant electroplating primer for elastomeric plastic balls. The raw materials for its preparation comprise, by weight, 40 parts of modified alkyd resin, 18 parts of C9 petroleum resin, 3 parts of drying agent, 49 parts of solvent and 0.5 parts of auxiliary agent.

[0047] The modified alkyd resin is a soybean oil modified alkyd resin with an acid value of ≤12 mgKOH / g, an outflow viscosity of 25-55s at 25°C, and an iron-cobalt colorimetric color of 15-17#. It is purchased from Henan Aohui Industrial Coatings Co., Ltd. and is model 389-9 alkyd resin.

[0048] The C9 petroleum resin is thermally polymerized 11#C9 petroleum resin purchased from Puyang Hengtai Petrochemical.

[0049] The drier is a combination of a cobalt isooctanoate drier and a zirconium isooctanoate drier, with a weight ratio of 1:2.

[0050] The cobalt 2-ethylhexanoate drier and the zirconium 2-ethylhexanoate drier were both purchased from Shanghai Taoyuan Cobalt Industry Co., Ltd.

[0051] The solvent is a combination of solvent oil and white spirit, with a weight ratio of 24:25.

[0052] The solvent oil is 200# solvent oil, and the white oil is 120# white oil.

[0053] The auxiliary agent is a leveling agent, and the leveling agent is an organic silicone acrylate leveling agent purchased from Digo, model TEGO2100.

[0054] A method for preparing an impact-resistant electroplating primer for an elastomeric plastic ball comprises the following steps:

[0055] The prepared raw materials were mixed in sequence, stirred at 800 rpm for 30 min at room temperature of 25° C., and filtered to obtain a primer.

[0056] The filtration is carried out using a filter bag, and the pore size of the filter bag is 1 μm.

[0057] Example 2

[0058] An impact-resistant electroplating primer for elastomeric plastic balls and a preparation method thereof, the specific implementation method is the same as that of Example 1, except that the modified alkyd resin is a TDI-modified alkyd resin with an acid value of less than 8 mgKOH / g, an outflow viscosity of 5-9s at 25°C, a color of less than 7#, and a density of 0.96 g / cm 3 , purchased from Shandong Keyao Chemical Co., Ltd., model WST-1190.

[0059] Example 3

[0060] An impact-resistant electroplating primer for elastomeric plastic balls and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the modified alkyd resin is a combination of soybean oil-modified alkyd resin and TDI-modified alkyd resin, with a weight ratio of 12:28.

[0061] The soybean oil modified alkyd resin has an acid value of ≤12 mgKOH / g, an outflow viscosity of 25-55s at 25° C., and an iron-cobalt colorimetric color of 15-17#. It was purchased from Henan Aohui Industrial Coatings Co., Ltd. and is model 389-9 alkyd resin.

[0062] The TDI modified alkyd resin has an acid value of less than 8 mgKOH / g, an outflow viscosity of 5-9s at 25°C, a color less than 7#, and a density of 0.96 g / cm 3 , purchased from Shandong Keyao Chemical Co., Ltd., model WST-1190.

[0063] The drier is a combination of a cobalt isooctanoate drier, a zirconium isooctanoate drier and a manganese isooctanoate drier, with a weight ratio of 1:1:1.

[0064] The cobalt 2-octanoate drier, zirconium 2-octanoate drier and manganese 2-octanoate drier were all purchased from Shanghai Taoyuan Cobalt Industry Co., Ltd.

[0065] Example 4

[0066] An impact-resistant electroplating primer for elastomeric plastic balls and a preparation method thereof. The specific implementation method is the same as that of Example 3, except that the raw materials for preparation include, by weight, 40 parts of modified alkyd resin, 18 parts of C9 petroleum resin, 3 parts of drying agent, 49 parts of solvent, and 1 part of auxiliary agent.

[0067] The auxiliary agents are a leveling agent and an adhesion promoter, with a weight ratio of 0.5:0.5.

[0068] The leveling agent is an organic silicone acrylate leveling agent purchased from Digo, model TEGO2100.

[0069] The adhesion promoter was purchased from Nanjing Chuangshi Chemical Additives Co., Ltd., model number KH-792.

[0070] Performance Testing

[0071] The electroplating primer prepared in the embodiment was electroplated onto an ABS ball with a film thickness of 20 μm and baked at 60°C for 3 hours. Then, a Christmas ball was prepared according to the conventional process. After being placed for half a year, it was free-fallen 20 times from a height of 3 meters. The test results are shown in FIG. Figure 1-4 .

[0072] Figure 1After 20 free falls, it was observed that the paint film was partially peeled off and the aging resistance was average; the coating surface was partially fogged and the drying performance was poor.

[0073] Figure 2 After 20 free falls, obvious paint film peeling was observed, and the aging resistance was poor; the coating remained bright and dried well.

[0074] Figure 3 After 20 free falls, slight paint peeling was observed and the aging resistance was average; the coating remained bright and dried well.

[0075] Figure 4 After 20 free falls, it was observed that the paint did not fall off and the aging resistance was excellent; the coating remained bright and dried well.

[0076] The electroplating primer prepared in the example was electroplated onto an ABS ball, and the surface dry time and through dry time of the paint film were tested. The test results are shown in Table 1.

[0077] Table 1

[0078] Tack-free time Working time Example 1 60℃，3h 70℃，10h Example 2 50℃，3h 70℃，5h Example 3 50℃，3h 70℃，10h Example 4 50℃，3h 70℃，15h

Claims

1. An impact-resistant electroplating primer for elastomeric plastic balls, characterized in that: The raw materials prepared include, by weight: 30-50 parts of modified alkyd resin, 15-25 parts of C9 petroleum resin, 1-5 parts of drying agent, 45-55 parts of solvent and 0.1-1 part of auxiliary agent.

2. The impact-resistant electroplating primer for elastomeric plastic balls according to claim 1, characterized in that: The modified alkyd resin includes at least two of soybean oil modified alkyd resin, epoxy modified alkyd resin, acrylic acid modified alkyd resin, isocyanate modified alkyd resin and polyurethane modified alkyd resin.

3. The impact-resistant electroplating primer for elastomeric plastic balls according to claim 2, characterized in that: The acid value of the soybean oil-modified alkyd resin is ≤12 mgKOH / g, and the outflow viscosity at 25° C. is 25-55 s.

4. The impact-resistant electroplating primer for elastomeric plastic balls according to claim 2, characterized in that: The acid value of the isocyanate-modified alkyd resin is less than 8 mgKOH / g, and the outflow viscosity at 25° C. is 5-9 s.

5. The impact-resistant electroplating primer for elastomeric plastic balls according to claim 4, characterized in that: The isocyanate-modified alkyd resin includes at least one of TDI-modified alkyd resin, MDI-modified alkyd resin or TDI-MDI mixed modified alkyd resin.

6. The impact-resistant electroplating primer for elastomeric plastic balls according to claim 5, characterized in that: The weight ratio of the soybean oil modified alkyd resin to the TDI modified alkyd resin is (10-15):(20-30).

7. The impact-resistant electroplating primer for elastomeric plastic balls according to claim 1, characterized in that: The drier is a metal isooctanoate drier, including at least one of a cobalt isooctanoate drier, a zirconium isooctanoate drier, and a manganese isooctanoate drier.

8. The impact-resistant electroplating primer for elastomeric plastic balls according to claim 1, characterized in that: The auxiliary agent at least includes a leveling agent and an adhesion promoter, and the adhesion promoter is an organic silicon adhesion promoter.

9. A method for preparing the impact-resistant electroplating primer for elastomeric plastic balls according to any one of claims 1 to 8, characterized in that: The following steps are involved: The prepared raw materials are mixed in sequence, stirred at 500-1000 rpm for 20-40 minutes at room temperature, and filtered to obtain a primer.

10. An application of the impact-resistant electroplating primer for elastomeric plastic balls according to any one of claims 1 to 8, characterized in that: Applied to ABS and PS blanks.

Images