An antibacterial, antiviral and antifouling coating and its preparation method

Abstract

The present invention relates to the technical field of anti-fouling coatings, and specifically relates to an antibacterial, antiviral and anti-fouling coating and a preparation method thereof. Conventional anti-fouling coatings do not have antibacterial and antiviral effects. Aiming at the above technical problems, the present invention provides an antibacterial, antiviral and anti-fouling coating. The composition and type of the resin matrix, reactive monomer and antibacterial agent in the coating formulation are all determined by repeated experiments and optimization. The antibacterial agent in the coating system is composed of a silver-zinc composite antibacterial agent and the silver ion antibacterial agent IONPURE IPI of Ishizuka Glass Co., Ltd. of Japan in a mass ratio of 4:1. This antibacterial agent has the best compatibility with the coating system of the present invention, making the antibacterial and antiviral effects of the anti-fouling coating film obtained by the present invention the most significant.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and particularly to an antibacterial, antiviral and antifouling coating and a preparation method thereof. Background Art

[0002] The surfaces of wooden furniture materials such as floors in daily life are easily contaminated by external stains, mainly because the wooden materials do not have an antifouling coating or the surface coating does not have antifouling properties. Moreover, wooden furniture materials are prone to mildew, blackening and breeding of various viruses in humid and dark environments, which not only affects the beauty of the furniture materials, but also seriously endangers human health.

[0003] Studies have shown that adding organosilicon-modified polyurethane acrylate to the coating system can endow the obtained cured coating with good stain resistance. The reason is that the organosilicon structure introduced into the molecular structure of polyurethane acrylate can significantly reduce the surface energy of the coating, making it difficult for pollutants to adhere to the coating surface.

[0004] The antifouling coatings formed by conventional antifouling coatings do not have antibacterial and antiviral effects. Generally, silver or copper nano-antibacterial agents are added to the coating system to make the antifouling coating obtain better antibacterial and antiviral effects. The antibacterial effect of pure nano-silver is excellent, but its price is expensive. And pure copper nano-antibacterial agents can achieve better antibacterial and antiviral effects only when the addition amount is particularly large (at least 5%). However, copper nanoparticles are harmful to the body, and the addition amount is not allowed to exceed 6000 ppm.

[0005] In order to solve the above problems, the present invention continuously optimizes and adjusts the scheme. After repeated research and experiments, it is finally determined to use a silver-zinc composite antibacterial agent and an antibacterial agent IONPURE as antibacterial agents in the coating system of the present invention, and select organosilicon-modified polyurethane acrylate, epoxy acrylate and polyurethane acrylate with the best compatibility with the coating system of the present invention as the resin matrix, which significantly improves the antibacterial and antiviral effects of the antifouling coating obtained by the present invention. Summary of the Invention

[0006] The problem existing in the prior art is that conventional antifouling coatings do not have antibacterial and antiviral effects. In view of the above technical problems, the present invention provides an antibacterial, antiviral and antifouling coating, and its formula includes the following components by weight ratio:

[0007]

[0008] The antibacterial agent includes a silver-zinc composite antibacterial agent and the silver ion antibacterial agent IONPURE IPI of Ishizuka Glass Co., Ltd., Japan;

[0009] The additive has a leveling and wetting effect.

[0010] Preferably, the silver-zinc composite antibacterial agent is antibacterial agent KF136.

[0011] Preferably, the optimal mass ratio between the antibacterial agent KF136 and the silver ion antibacterial agent IONPURE IPI of Nippon Sheet Glass Co., Ltd. is 4:1.

[0012] Preferably, the organosilicon-modified polyurethane acrylate includes one or more combinations of organosilicon-modified aliphatic polyurethane acrylates HM-5016 (hexa-functional), HM-5017 (hexa-functional), and HM-5019 (hexa-functional) produced by Jiangxi Kunlong New Materials Co., Ltd.

[0013] Preferably, the polyurethane acrylate is a hexa-functional polyurethane acrylate.

[0014] Preferably, the hexa-functional polyurethane acrylate is an aliphatic polyurethane acrylate oligomer 7600 produced by Guangdong Hengzhiguang Environmental Protection New Materials Co., Ltd.

[0015] Preferably, the epoxy acrylate is a di-functional epoxy acrylate.

[0016] Preferably, the di-functional epoxy acrylate is an epoxy acrylate oligomer 6200D produced by Guangdong Hengzhiguang Environmental Protection New Materials Co., Ltd.

[0017] Preferably, the reactive monomer includes one or more combinations of a difunctional acrylate monomer and a polyfunctional acrylate monomer.

[0018] Preferably, the difunctional acrylate monomer includes one or more combinations of HDDA, DPGDA, and TPGDA.

[0019] Preferably, the polyfunctional acrylate monomer includes one or more combinations of TMPTA, EB40, or EB140.

[0020] Preferably, the additives include an organosilicon leveling agent and a nonionic surface wetting agent, and the weight ratio of the organosilicon leveling agent to the nonionic surface wetting agent is 1.0 - 1.5:1.0 - 1.5.

[0021] Preferably, the organosilicon leveling agent is a polyether-based organosilicon leveling agent, and more preferably Degussa TEGO RAD2700.

[0022] Preferably, the nonionic surface wetting agent is Degussa WET500.

[0023] The present invention has the following beneficial effects:

[0024] (1) The coating obtained by the present invention not only has good stain resistance, wear resistance and scratch resistance, but also has good antibacterial and antiviral effects. It is a multifunctional coating with good market prospects.

[0025] (2) The present invention has found through research that for the anti-fouling coating obtained by the present invention, the composition and type of the resin matrix, reactive monomer and antibacterial agent in the coating formula will all affect the wear resistance, scratch resistance, antibacterial and antiviral properties of the obtained paint film. Through a large number of experimental studies, the present invention has finally determined the antibacterial agent composition with the best compatibility and the most significant effect on the coating system of the present invention (the antibacterial agent is composed of a silver-zinc composite antibacterial agent and the Nippon Ishizuka Glass silver ion antibacterial agent IONPURE IPI in a mass ratio of 4:1), which significantly improves the antibacterial and antiviral effects of the paint film of the anti-fouling coating obtained by the present invention. Detailed Embodiments

[0026] The present invention will be described in detail below with reference to the embodiments. However, it should be understood that the following embodiments are only illustrative examples of the implementation modes of the present invention, rather than limiting the scope of the present invention.

[0027] The auxiliary agent used in the following embodiments of the present invention is composed of an organosilicon leveling agent and a non-ionic surface wetting agent in a weight ratio of 1:1. The organosilicon leveling agent is Degussa TEGO RAD 2700, and the non-ionic surface wetting agent is Degussa WET500.

[0028] The photoinitiator in the following embodiments of the present invention is composed of photoinitiator 184, photoinitiator TPO, and photoinitiator MBF in a weight ratio of 4:1:1.

[0029] The silver-zinc composite antibacterial agent in the following embodiments of the present invention is antibacterial agent KF136, purchased from Huizhou Mingkai Antimicrobial Technology Co., Ltd.

[0030] Example 1

[0031] An antibacterial, antiviral and anti-fouling coating, the formula of which is as follows by weight:

[0032]

[0033] The antibacterial agent is a mixture composed of antibacterial agent KF136 and the Nippon Ishizuka Glass silver ion antibacterial agent IONPURE IPI in a mass ratio of 4:1.

[0034] Example 2

[0035] An antibacterial, antiviral and anti-fouling coating, the formula of which is as follows by weight:

[0036]

[0037]

[0038] The antibacterial agent is a mixture composed of antibacterial agent KF136 and Nippon Sheet Glass silver ion antibacterial agent IONPURE IPI in a mass ratio of 4:1.

[0039] Example 3

[0040] An antibacterial, antiviral and antifouling coating, the formula of which is as follows by weight ratio:

[0041]

[0042] The antibacterial agent is a mixture composed of antibacterial agent KF136 and Nippon Sheet Glass silver ion antibacterial agent IONPURE IPI in a mass ratio of 4:1.

[0043] Example 4 is the same as Example 1, except that 5% epoxy acrylate oligomer 6200D (difunctional) is further added in Example 4.

[0044] Example 5 is the same as Example 1, except that 10% epoxy acrylate oligomer 6200D is further added in Example 5.

[0045] In order to verify that organosilicon-modified polyurethane acrylates with different structures and different functionalities have an impact on the performance of the coating system of the present invention, the following experiments were carried out:

[0046] Comparative Example 1 is the same as Example 1, except that the organosilicon-modified polyurethane acrylate in Comparative Example 1 is organosilicon-modified aliphatic polyurethane acrylate HM-5017.

[0047] Comparative Example 2 is the same as Example 1, except that the organosilicon-modified polyurethane acrylate in Comparative Example 2 is organosilicon-modified aliphatic polyurethane acrylate HM-5019.

[0048] Comparative Example 3 is the same as Example 1, except that the organosilicon-modified polyurethane acrylate in Comparative Example 3 is difunctional organosilicon-modified aliphatic polyurethane acrylate HM-5101 (Jiangxi Kunlong).

[0049] Comparative Example 4 is the same as Example 1, except that the organosilicon-modified polyurethane acrylate in Comparative Example 4 is nonafunctional organosilicon-modified aliphatic polyurethane acrylate HM-2706 (Jiangxi Kunlong).

[0050] In order to verify that the structure and functionality of polyurethane acrylate have an impact on the performance of the coating system of the present invention, the following experiments were carried out:

[0051] Comparative Example 5 is the same as Example 1, except that the polyurethane acrylate in Comparative Example 5 is an aliphatic polyurethane acrylate oligomer 7636 (hexafunctional, Guangdong Hengzhiguang).

[0052] Comparative Example 6 is the same as Example 1, except that the polyurethane acrylate in Comparative Example 6 is an aliphatic polyurethane acrylate oligomer 7296-1 (difunctional, Guangdong Hengzhiguang).

[0053] Comparative Example 7 is the same as Example 1, except that the polyurethane acrylate in Comparative Example 7 is an aromatic polyurethane acrylate oligomer 71601 (hexafunctional, Guangdong Hengzhiguang).

[0054] Comparative Example 8 is the same as Example 1, except that the polyurethane acrylate in Comparative Example 8 is an aromatic polyurethane acrylate oligomer 7120-1 (difunctional, Guangdong Hengzhiguang).

[0055] Comparative Example 9 is the same as Example 1, except that the polyurethane acrylate in Comparative Example 9 is an aromatic polyurethane acrylate oligomer 7121-1 (difunctional, Guangdong Hengzhiguang).

[0056] Comparative Example 10 is the same as Example 1, except that the polyurethane acrylate in Comparative Example 10 is an aromatic polyurethane acrylate oligomer 7123 (difunctional, Guangdong Hengzhiguang).

[0057] Comparative Example 11 is the same as Example 1, except that the polyurethane acrylate in Comparative Example 11 is an aromatic polyurethane acrylate oligomer 7128 (difunctional, Guangdong Hengzhiguang).

[0058] In order to verify that the type of epoxy acrylate has an impact on the performance of the coating system of the present invention, the following experiments were carried out:

[0059] Comparative Example 12 is the same as Example 1, except that the epoxy acrylate in Comparative Example 12 is an epoxy acrylate oligomer 6102 (difunctional, Guangdong Hengzhiguang).

[0060] Comparative Example 13 is the same as Example 1, except that the epoxy acrylate in Comparative Example 13 is an epoxy acrylate oligomer 6103 (difunctional, Guangdong Hengzhiguang).

[0061] Comparative Example 14 is the same as Example 1, except that the epoxy acrylate in Comparative Example 14 is an epoxy acrylate oligomer 6106 (difunctional, Guangdong Hengzhiguang).

[0062] Comparative Example 15 is the same as Example 1, except that the epoxy acrylate in Comparative Example 15 is an epoxy acrylate oligomer 6116 (difunctional, Guangdong Hengzhiguang).

[0063] Comparative Example 16 is the same as Example 1, except that the epoxy acrylate in Comparative Example 16 is epoxy acrylate oligomer 6118 (bifunctional, Guangdong Hengzhiguang).

[0064] Comparative Example 17 is the same as Example 1, except that the epoxy acrylate in Comparative Example 17 is epoxy acrylate oligomer 6313 (bifunctional, Guangdong Hengzhiguang).

[0065] Comparative Example 18 is the same as Example 1, except that the epoxy acrylate in Comparative Example 18 is epoxy acrylate oligomer 6160M-3 (bifunctional, Guangdong Hengzhiguang).

[0066] In order to verify the influence of different antibacterial agents and the composition of antibacterial agents on the performance of the coating system of the present invention, the following experiments were carried out:

[0067] Comparative Example 19 is the same as Example 1, except that the antibacterial agent in Comparative Example 19 is only antibacterial agent KF136, and the addition amount is 1%.

[0068] Comparative Example 20 is the same as Example 1, except that the antibacterial agent in Comparative Example 20 is only silver ion antibacterial agent IONPURE IPI, and the addition amount is 1%.

[0069] Comparative Example 21 is the same as Example 1, except that the antibacterial agent in Comparative Example 21 is only nano copper-based antibacterial agent, and the addition amount is 1%. The nano copper antibacterial agent is purchased from Nanjing Tianshi Landun Biotechnology Co., Ltd., and the model is LD-701.

[0070] Comparative Example 22 is the same as Example 1, except that the antibacterial agent in Comparative Example 22 is a composite antibacterial agent composed of silver-based antibacterial agent 003-D1 produced by Guangdong Zanyu Antimildew Technology Co., Ltd. and zinc-based antibacterial agent 015-7W produced by Guangdong Zanyu Antimildew Technology Co., Ltd. in a mass ratio of 1:1.5, and the addition amount is 1%.

[0071] Comparative Example 23 is the same as Example 1, except that the antibacterial agent in Comparative Example 23 is a mixture composed of antibacterial agent KF136 and silver ion antibacterial agent IONPURE IPI of Nippon Sheet Glass in a mass ratio of 1:4.

[0072] Comparative Example 24 is the same as Example 1, except that the antibacterial agent in Comparative Example 24 is a mixture composed of antibacterial agent KF136 and silver ion antibacterial agent IONPURE IPI of Nippon Sheet Glass in a mass ratio of 1:1.

[0073] Comparative Example 25 was the same as Example 1, except that in Comparative Example 25, the antibacterial agent was a mixture composed of antibacterial agent KF136 and Nippon Sheet Glass silver ion antibacterial agent IONPURE IPI at a mass ratio of 2:1.

[0074] Performance Test

[0075] The anti-fouling coatings obtained in the examples and comparative examples of the present invention were respectively subjected to relevant performance tests, and the test results are shown in Table 1 and the continued Table 1.

[0076] Antibacterial property: Tested according to the film pasting method in Appendix B of the evaluation of antibacterial properties of furniture in the standard QB / T 4371-2012.

[0077] Antiviral property: Tested according to ISO 21702-2019 Determination of antiviral activity on plastics and other non-porous surfaces.

[0078] Anti-fouling property: Tested according to the fouling resistance test method described in the standard EN423.

[0079] Abrasion resistance: The test standard is GB / T21196.

[0080] Scratch resistance: The test standard is ISO1518-2:1992. The diameter of the steel ball at the tip of the steel needle used for testing is 1 mm. A unidirectional scratching experiment is carried out on the coating surface at a speed of 20 mm / s using an electric scratch tester. The scratching length is 50 mm, and the experiment is repeated 3-5 times. Take the average value. Continuously increase the load when the steel needle scratches, and record the load when the coating begins to be scratched by the tip of the steel needle, which is used as an index to evaluate the scratch resistance of the coating. The greater the load, the better the scratch resistance.

[0081] Table 1

[0082]

[0083] Continued Table 1

[0084]

[0085] In Table 1, the judgment criterion for excellent anti-fouling property is the anti-fouling property judgment criterion:

[0086] Deli Stationery - black marker pen: Doodle. After the doodle handwriting dries, wipe it with a dry cloth:

[0087] No trace: Excellent

[0088] There are very light traces: Good

[0089] There are slight traces but do not affect the pattern of the substrate: General

[0090] The doodle cannot be erased completely: Poor.

[0091] Wear resistance: A1 is superior to B1, B1 is superior to B2, and B2 is superior to B3.

[0092] Inspired by the ideal embodiments of the present invention described above, through the above description, relevant staff can completely make various changes and modifications without departing from the technical idea of this invention. The technical scope of this invention is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. An antibacterial, antiviral and antifouling coating, characterized in that: The composition includes the following ingredients by weight: Silicone modified polyurethane acrylate 25-35%; Hexafunctional polyurethane acrylate 10-20%; Difunctional epoxy acrylate 0-10%, and not 0; Antimicrobial agent 1-2%; Active monomer 40-50%; Photoinitiator 4-7%; Additives 2-5%; The antibacterial agent includes a silver-zinc composite antibacterial agent and Japanese Ishizuka nitrate silver ion antibacterial agent IONPURE IPI; The auxiliary agent has leveling and wetting effects; The silver-zinc composite antibacterial agent is antibacterial agent KF136; The mass ratio between the antimicrobial agent KF136 and the Japanese Ishizuka Nitrate silver ion antimicrobial agent IONPURE IPI is 4:1; The organosilicon-modified polyurethane acrylate includes HM-5016; The hexafunctional polyurethane acrylate is aliphatic polyurethane acrylate oligomer 7600; The difunctional epoxy acrylate is epoxy acrylate oligomer 6200D.

2. The antibacterial, antiviral and antifouling coating according to claim 1, characterized in that: The active monomer includes one or a combination of two or more of a difunctional acrylate monomer and a multifunctional acrylate monomer.

3. The antibacterial, antiviral and antifouling coating according to claim 2, characterized in that: The bifunctional acrylate monomer includes one or a combination of two or more of HDDA, DPGDA and TPGDA.

4. The antibacterial, antiviral and antifouling coating according to claim 2, characterized in that: The multifunctional acrylate monomer includes one or a combination of two or more of TMPTA, EB40 or EB140.

5. The antibacterial, antiviral and antifouling coating according to claim 1, characterized in that: The auxiliary agent comprises an organic silicon leveling agent and a non-ionic surface wetting agent, and the weight ratio of the organic silicon leveling agent to the non-ionic surface wetting agent is 1.0-1.5:1.0-1.5.

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