Antifouling paint suitable for glass fiber reinforced plastic substrate surface and preparation method thereof

Abstract

The invention relates to the related field of chemical materials, in particular to antifouling paint suitable for the surface of a glass fiber reinforced plastic base material and a preparation method, specifically, according to the characteristics of the glass fiber reinforced plastic base material, the formula of the antifouling paint is improved, and resin with high adhesive strength with the glass fiber reinforced plastic material is added; other anti-fouling resin is matched to prepare the anti-fouling paint; the antifouling paint can be directly coated on the surface of a glass fiber reinforced plastic base material without using connecting paint, and meanwhile, the antifouling paint forms an antifouling coating after being cured on the surface of the glass fiber reinforced plastic base material and has stable adhesive force.

Description

Technical Field

[0001] The invention relates to the field of chemical materials, and in particular to an antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate and a preparation method thereof. Background Art

[0002] Marine fouling organisms are a type of biological species that grow on man-made structures such as ships. They mainly include barnacles, oysters, mussels, seaweed and marine bacteria, which are extremely harmful to man-made structures. Taking large ocean-going ships as an example, once fouling organisms attach to them, the amount of attachment can reach 150kg / m2 within half a year, and the total amount of fouling attached to the surface of about 40,000 square meters underwater will reach 6,000 tons. The huge amount of fouling attachment not only increases the deadweight of the hull, but also changes the streamlined structure of the hull, increases the navigation resistance of the hull, and greatly increases fuel consumption. In addition, fouling organisms will cause the ship's maneuverability to deteriorate, the propeller propulsion efficiency to decrease, the noise to increase, and the sonar to be interfered with, forcing the ship to dock and clean up in advance, spending huge maintenance costs, and seriously affecting the service and combat effectiveness of the ship. At present, the main methods to prevent fouling organisms from attaching are mechanical removal, electrolysis of seawater and coating with antifouling coatings. Among them, coating with antifouling coatings is the most convenient and widely used method. Therefore, marine antifouling materials have become a research hotspot for domestic and foreign research institutions.

[0003] The antifouling paint widely used in the market is designed for ships with steel substrates. The coating below the waterline of the entire ship's outer plate requires surface treatment of the steel substrate first, then application of anti-corrosion paint, intermediate paint, and then application of antifouling paint.

[0004] Ships using FRP as hull material began to appear in the 1960s, which was a major change in the history of small ship development. Currently, there are about 2 million FRP ships in the world. FRP ships are suitable for small ships with a displacement of less than 500 tons. Compared with steel substrates, they can reduce the weight of the hull by 20%-30%, increase the ship's loading capacity, reduce resistance, and increase the speed.

[0005] FRP ships also have great advantages in anti-corrosion maintenance. The entire outer plate of the FRP ship does not need to be painted with anti-corrosion coating, only anti-fouling paint needs to be applied below the waterline of the outer plate.

[0006] At present, when antifouling paint is applied to FRP ships on the market, it is necessary to apply an intermediate paint once, and then apply antifouling paint on the intermediate paint coating to ensure the connection strength between the overall coating and the FRP substrate. Summary of the invention

[0007] The purpose of the present invention is to provide an antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate and a preparation method thereof, so as to solve the problems raised in the above-mentioned background technology.

[0008] To achieve the above-mentioned purpose, the present invention provides the following technical scheme: an antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate, the preparation ratio by weight is as follows: 20-30 parts of acrylate zinc resin, 5-10 parts of epoxy resin, 5-10 parts of acrylic resin, 20-40 parts of antifouling agent, 5-10 parts of pigment, 1-5 parts of auxiliary agent and 5-15 parts of solvent.

[0009] Preferably, the preparation ratio by weight is as follows: 20 parts of zinc acrylate resin, 5 parts of epoxy resin, 5 parts of acrylic resin, 20 parts of antifouling agent, 5 parts of pigment, 1 part of auxiliary agent and 5 parts of solvent.

[0010] Preferably, the weight ratio of the epoxy resin to the acrylic resin is 1:1, which determines the adhesion performance of the antifouling coating to the FRP substrate. Epoxy resin, as a plasticizer in the formula, can improve the flexibility of the antifouling coating. The weight ratio of epoxy resin to acrylic resin affects the adhesion matching of the entire coating to the FRP substrate; the epoxy resin is a bisphenol A type epoxy resin, the number average molecular weight of the epoxy resin is 8000-10000, the epoxy equivalent of the epoxy resin is 250-350g / eq, the number average molecular weight of the acrylic resin is 3000-5000, and the acid value of the acrylic resin is 10-20mg·KOH / g.

[0011] Preferably, the weight ratio of the total mass of epoxy resin and acrylic resin to the weight ratio of zinc acrylate resin is 1:5-8, which determines the antifouling performance of the antifouling coating. When the total mass weight ratio of epoxy resin to polyester resin exceeds the above ratio, the antifouling performance of the coating will be significantly reduced.

[0012] Preferably, the antifouling agent is one or two of cuprous oxide, cuprous thiocyanate, copper pyrithione, zinc pyrithione, mancozeb, pyrrolidine cyanide, and isothiazolinone.

[0013] Preferably, the pigment includes a body pigment and a coloring pigment, wherein the body pigment includes one or more of talc, precipitated barium sulfate, mica powder, wollastonite powder, light calcium carbonate, kaolin, zinc oxide, quartz powder, and feldspar powder; and the coloring pigment includes one or more of titanium dioxide, red iron oxide, black iron oxide, yellow iron oxide, ultramarine, carbon black, scarlet powder, toluidine red, chrome yellow, phthalocyanine blue, and phthalocyanine green.

[0014] Preferably, the auxiliary agent is an anti-settling agent.

[0015] Preferably, the anti-settling agent is one or two of hydrogenated castor oil, polyamide wax, organic bentonite, fumed silica, polyethylene wax, and aluminum stearate.

[0016] Preferably, the solvent is one or more of xylene, toluene, ethylbenzene, hexane, heptane, cyclohexane, butanol, isopropanol, ethylene glycol monomethyl ether, butyl acetate, and ethylene glycol methyl ether acetate.

[0017] Preferably, a method for preparing an antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate comprises the following steps:

[0018] Step 1: Add zinc acrylate resin, epoxy resin and acrylic resin with a preset ratio into a pull cylinder, disperse them evenly at high speed, and control the speed at 800-1000rpm;

[0019] Step 2, conveying the processed raw materials in step 1 into a disperser, adjusting the speed of the disperser to 300-500 rpm, then sequentially adding antifouling agents, excluding cuprous oxide, pigments, additives and solvents, adjusting the speed of the disperser to 800-1000 rpm, and dispersing for 15-30 minutes until the dispersion is uniform;

[0020] Step 3, move the dispersed raw materials in step 2 into a sand mill for sand grinding, the sand grinding time is controlled within 30min-1h, the grinding temperature is controlled below 50°C, until the test coating fineness is ≤80μm;

[0021] Step 4. After completing the sand grinding in step 3, move the raw materials into the high-speed disperser, adjust the speed to 300-500rpm, add cuprous oxide, and disperse at high speed at 800-1000rpm for 20-30min. Detect the fineness ≤80μm, adjust the viscosity to 80-90KU, and finally discharge and package.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: the present invention has a good adhesion effect on the surface of the FRP substrate, and does not require the use of an intermediate paint as a transition coating. The antifouling coating is compounded with acrylic zinc resin, epoxy resin and acrylic resin of a certain specification as the film-forming material of the coating, and an antifouling agent is added. Through the resin compounding system, the coating has good antifouling performance and good adhesion effect with the FRP substrate. The antifouling coating of the present invention is applied in the field of FRP ships, which can reduce the construction cost of the FRP ship outer plate coating, reduce manual labor time, reduce energy consumption, and reduce VOC emissions; specifically, the present invention improves the antifouling coating formula according to the characteristics of the FRP substrate material, adds a resin with strong adhesion strength to the FRP material, and prepares the antifouling coating with other antifouling resins; the antifouling coating can be directly applied on the surface of the FRP substrate without the use of a connecting paint, and the coating forms an antifouling coating after curing on the surface of the FRP substrate, which has stable adhesion. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 It is a schematic diagram of the method flow of the present invention. DETAILED DESCRIPTION

[0024] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0025] See also Figure 1 The present invention provides a technical solution: an antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate, wherein the preparation ratio by weight is as follows: 20-30 parts of acrylate zinc resin, 5-10 parts of epoxy resin, 5-10 parts of acrylate resin, 20-40 parts of antifouling agent, 5-10 parts of pigment, 1-5 parts of auxiliary agent and 5-15 parts of solvent. The acrylate zinc resin is a functional substance of the antifouling coating, which is a commercially available acrylate zinc resin, which has different hydrolysis rates according to different zinc monomer contents, can be slowly dissolved in seawater, and releases antifouling active substances. In the present invention, a acrylate zinc resin with a faster hydrolysis rate is used, and its zinc content accounts for 4%-8% of the resin weight.

[0026] Furthermore, the preparation ratio by weight is as follows: 20 parts of zinc acrylate resin, 5 parts of epoxy resin, 5 parts of acrylic resin, 20 parts of antifouling agent, 5 parts of pigment, 1 part of auxiliary agent and 5 parts of solvent.

[0027] Furthermore, the weight ratio of the epoxy resin to the acrylic resin is 1:1, the epoxy resin is a bisphenol A epoxy resin, the number average molecular weight of the epoxy resin is 8000-10000, the epoxy equivalent of the epoxy resin is 250-350g / eq, the number average molecular weight of the acrylic resin is 3000-5000, and the acid value of the acrylic resin is 10-20mg·KOH / g.

[0028] Furthermore, the weight ratio of the total mass of the epoxy resin and the acrylic resin to the zinc acrylate resin is 1:5-8.

[0029] Furthermore, the antifouling agent is one or two of cuprous oxide, cuprous thiocyanate, copper pyrithione, zinc pyrithione, mancozeb, pyrrolidone bromide, and isothiazolinone, and a mixture of cuprous oxide and copper pyrithione is preferred.

[0030] Furthermore, the pigment includes a body pigment and a coloring pigment, wherein the body pigment includes one or more of talc, precipitated barium sulfate, mica powder, wollastonite powder, light calcium carbonate, kaolin, zinc oxide, quartz powder, and feldspar powder; and the coloring pigment includes one or more of titanium dioxide, red iron oxide, black iron oxide, yellow iron oxide, ultramarine, carbon black, scarlet powder, toluidine red, chrome yellow, phthalocyanine blue, and phthalocyanine green.

[0031] Furthermore, the auxiliary agent is an anti-settling agent.

[0032] Furthermore, the anti-settling agent is one or two of hydrogenated castor oil, polyamide wax, organic bentonite, fumed silica, polyethylene wax, and aluminum stearate.

[0033] Furthermore, the solvent is one or more of xylene, toluene, ethylbenzene, hexane, heptane, cyclohexane, butanol, isopropanol, ethylene glycol monomethyl ether, butyl acetate, and ethylene glycol methyl ether acetate.

[0034] Furthermore, a method for preparing an antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate comprises the following steps:

[0035] Step 1: Add zinc acrylate resin, epoxy resin and acrylic resin with a preset ratio into a pull cylinder, disperse them evenly at high speed, and control the speed at 800-1000rpm;

[0036] Step 2, conveying the processed raw materials in step 1 into a disperser, adjusting the speed of the disperser to 300-500 rpm, then sequentially adding antifouling agents, excluding cuprous oxide, pigments, additives and solvents, adjusting the speed of the disperser to 800-1000 rpm, and dispersing for 15-30 minutes until the dispersion is uniform;

[0037] Step 3, move the dispersed raw materials in step 2 into a sand mill for sand grinding, the sand grinding time is controlled within 30min-1h, the grinding temperature is controlled below 50°C, until the test coating fineness is ≤80μm;

[0038] Step 4. After completing the sand grinding in step 3, move the raw materials into the high-speed disperser, adjust the speed to 300-500rpm, add cuprous oxide, and disperse at high speed at 800-1000rpm for 20-30min. Detect the fineness ≤80μm, adjust the viscosity to 80-90KU, and finally discharge and package.

[0039] Specifically, Example 1

[0040] Preparation of coating: 20 parts by weight of zinc acrylate resin, zinc content (8%); 4 parts by weight of epoxy resin, number average molecular weight 10000, epoxy equivalent 350g / eq; 4 parts by weight of acrylic resin, number average molecular weight 5000, acid value 20mg·KOH / g; 35 parts by weight of antifouling agent cuprous oxide, 5 parts by weight of copper pyrithione, 15 parts by weight of filler and pigment, 2 parts by weight of auxiliary agent, and 15 parts by weight of solvent;

[0041] After the coating is prepared, it is rolled on the FRP substrate. The thickness of the FRP substrate is 15 mm. Two rolls are applied. The dry film thickness of the antifouling coating is about 100 μm. The coating adhesion is tested using the pull-off method. The test results are shown in Table 1 below:

[0042] Table 1: Test structure

[0043] Sample number 1# 2# 3# Test results, mpa 2.26 2.12 2.42 Cross-section 100% connected surface 100% connected surface 100% connected surface

[0044] Example 2

[0045] Preparation of coating: 30 parts by weight of zinc acrylate resin, zinc content (4%); 6 parts by weight of epoxy resin, number average molecular weight 8000, epoxy equivalent 250g / eq; 6 parts by weight of acrylic resin, number average molecular weight 3000, acid value 10mg·KOH / g; 30 parts by weight of antifouling agent cuprous oxide, 5 parts by weight of copper pyrithione, 15 parts by weight of filler and pigment, 2 parts by weight of auxiliary agent, and 6 parts by weight of solvent;

[0046] After the coating was prepared, it was rolled on a FRP substrate with a thickness of 15 mm. Two coats of coating were applied and the dry film thickness of the antifouling coating was about 100 μm. The coating adhesion was tested using the pull-off method. The test results are shown in Table 1.

[0047] Example 3

[0048] Preparation of coating: 25 parts by weight of zinc acrylate resin, zinc content (6%); 5 parts by weight of epoxy resin, number average molecular weight 9000, epoxy equivalent 300g / eq; 5 parts by weight of acrylic resin, number average molecular weight 4000, acid value 15mg·KOH / g; 30 parts by weight of antifouling agent cuprous oxide, 5 parts by weight of copper pyrithione, 15 parts by weight of filler and pigment, 2 parts by weight of auxiliary agent, and 13 parts by weight of solvent;

[0049] After the coating was prepared, it was rolled on a FRP substrate with a thickness of 15 mm. Two coats of coating were applied and the dry film thickness of the antifouling coating was about 100 μm. The coating adhesion was tested using the pull-off method. The test results are shown in Table 1.

[0050] The above three embodiments use the established formula resin ratio of the patent to prepare antifouling paint, and conduct adhesion tests with FRP (glass fiber reinforced plastic) substrates. The results show that the adhesion is good.

[0051] The present invention has a good adhesion effect on the surface of the FRP substrate, and does not require the use of an intermediate paint as a transition coating. The antifouling coating is compounded with acrylic zinc resin, epoxy resin and acrylic resin of a certain specification as the film-forming material of the coating, and an antifouling agent is added. Through the resin compounding system, the coating has good antifouling performance and good adhesion effect with the FRP substrate. The antifouling coating of the present invention is applied in the field of FRP ships, which can reduce the construction cost of the FRP ship outer plate coating, reduce manual labor time, reduce energy consumption, and reduce VOC emissions; specifically, the present invention improves the antifouling coating formula according to the characteristics of the FRP substrate material, adds a resin with strong adhesion strength to the FRP material, and prepares the antifouling coating with other antifouling resins; the antifouling coating can be directly applied on the surface of the FRP substrate without the use of a connecting paint, and the coating forms an antifouling coating after curing on the surface of the FRP substrate, which has stable adhesion.

[0052] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate, characterized in that: The preparation proportions by weight are as follows: 20-30 parts of zinc acrylate resin, 5-10 parts of epoxy resin, 5-10 parts of acrylic resin, 20-40 parts of antifouling agent, 5-10 parts of pigment, 1-5 parts of auxiliary agent and 5-15 parts of solvent.

2. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The preparation proportions by weight are as follows: 20 parts of zinc acrylate resin, 5 parts of epoxy resin, 5 parts of acrylic resin, 20 parts of antifouling agent, 5 parts of pigment, 1 part of auxiliary agent and 5 parts of solvent.

3. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The weight ratio of the epoxy resin to the acrylic resin is 1:

1. The epoxy resin is a bisphenol A epoxy resin, the number average molecular weight of the epoxy resin is 8000-10000, the epoxy equivalent of the epoxy resin is 250-350g / eq, the number average molecular weight of the acrylic resin is 3000-5000, and the acid value of the acrylic resin is 10-20mg·KOH / g.

4. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The weight ratio of the total mass of the epoxy resin and the acrylic resin to the zinc acrylate resin is 1:5-8.

5. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The antifouling agent is one or two of cuprous oxide, cuprous thiocyanate, copper pyrithione, zinc pyrithione, mancozeb, bromopyrrolidone and isothiazolinone.

6. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The pigments include body pigments and coloring pigments, wherein the body pigments include one or more of talc, precipitated barium sulfate, mica powder, wollastonite powder, light calcium carbonate, kaolin, zinc oxide, quartz powder, and feldspar powder; and the coloring pigments include one or more of titanium dioxide, red iron oxide, black iron oxide, yellow iron oxide, ultramarine, carbon black, scarlet powder, toluidine red, chrome yellow, phthalocyanine blue, and phthalocyanine green.

7. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The auxiliary agent is an anti-settling agent.

8. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The anti-settling agent is one or two of hydrogenated castor oil, polyamide wax, organic bentonite, fumed silica, polyethylene wax and aluminum stearate.

9. The antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The solvent is one or more of xylene, toluene, ethylbenzene, hexane, heptane, cyclohexane, butanol, isopropanol, ethylene glycol monomethyl ether, butyl acetate, and ethylene glycol methyl ether acetate.

10. The method for preparing an antifouling coating suitable for the surface of a glass fiber reinforced plastic substrate according to claim 1, characterized in that: The following steps are involved: Step 1: Add the preset ratio of zinc acrylate resin, epoxy resin and acrylic resin into the pull cylinder, disperse them evenly at high speed, and control the speed at 800-1000rpm; Step 2, conveying the processed raw materials in step 1 into a disperser, adjusting the speed of the disperser to 300-500 rpm, then sequentially adding antifouling agents, excluding cuprous oxide, pigments, additives and solvents, adjusting the speed of the disperser to 800-1000 rpm, and dispersing for 15-30 minutes until the dispersion is uniform; Step 3, move the dispersed raw materials in step 2 into a sand mill for sand grinding, the sand grinding time is controlled within 30min-1h, the grinding temperature is controlled below 50°C, until the test coating fineness is ≤80μm; Step 4. After completing the sand grinding in step 3, move the raw materials into the high-speed disperser, adjust the speed to 300-500rpm, add cuprous oxide, and disperse at high speed at 800-1000rpm for 20-30min. Detect the fineness ≤80μm, adjust the viscosity to 80-90KU, and finally discharge and package.

Images