阅读说明：本技术 一种紫外光辐射固化超哑肤感抗菌涂料 (Ultraviolet radiation curing ultra-matte skin-feel antibacterial coating ) 是由 彭健华 蒋卫华 吴勇 邓书春 于 2021-08-11 设计创作，主要内容包括：本发明涉及涂料技术领域,尤其涉及一种紫外光辐射固化超哑肤感抗菌涂料。直接在涂料体系中添加季铵盐、氨基类物质、季膦盐等抗菌单体,这些抗菌单体与涂料中的树脂基体相容性较差,会影响涂膜的光学特性。基于以上问题,本发明提供一种紫外光辐射固化超哑肤感抗菌涂料,本发明在涂料体系中添加两种自制的抗菌丙烯酸酯低聚物,两种抗菌丙烯酸酯低聚物协同作用,大幅度提高了涂料的抗菌性；另外,本发明自制的抗菌丙烯酸酯低聚物与丙烯酸树脂基体之间具有良好的相容性,有效保障了涂膜的力学和光学性能。(The invention relates to the technical field of coatings, in particular to an ultraviolet radiation curing ultra-matte skin-feel antibacterial coating. Antibacterial monomers such as quaternary ammonium salt, amino substances, quaternary phosphonium salt and the like are directly added into a coating system, and the compatibility of the antibacterial monomers and a resin matrix in the coating is poor, so that the optical characteristics of a coating film are influenced. Based on the problems, the invention provides the ultraviolet radiation curing ultra-matte skin-feel antibacterial coating, and the antibacterial property of the coating is greatly improved by adding two self-made antibacterial acrylate oligomers into a coating system and the synergistic effect of the two antibacterial acrylate oligomers; in addition, the self-made antibacterial acrylate oligomer has good compatibility with an acrylic resin matrix, and the mechanical and optical properties of the coating are effectively guaranteed.)

1. The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating is characterized by comprising the following components in parts by weight:

2. the ultraviolet radiation curable ultra-matte skin-feel antibacterial coating of claim 1, wherein the urethane acrylate is a 10-functional urethane acrylate.

3. The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating as claimed in claim 1, wherein the modified polyurethane acrylate is 3-functional fluorosilicone modified polyester acrylate.

4. The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating as claimed in claim 1, wherein the antibacterial acrylic oligomer is a compound of an antibacterial acrylic oligomer I and an antibacterial acrylic oligomer II in a mass ratio of 1: 1.

5. The ultraviolet radiation curable ultra-matte skin feel antibacterial coating according to claim 4, wherein the antibacterial acrylic oligomer I is prepared by the following steps:

(1) adding 3g of water into 50g of DC-5700, and completely hydrolyzing the DC-5700 in the water after stirring to obtain an antibacterial solution I;

(2) adding 18g of hydroxyethyl methacrylate, 0.1g of p-hydroxyanisole polymerization inhibitor, 0.1g of BHT antioxidant and 0.2g of catalyst tin dioctoate into 30g of organic solvent to prepare a mixed solution;

(3) adding the antibacterial solution I obtained in the step (1) into the mixed solution obtained in the step (2) and uniformly mixing to obtain a reaction solution, raising the temperature of the reaction solution to 100 ℃, continuously stirring, heating and refluxing for 8-10h to remove water, then carrying out reduced pressure distillation to remove the organic solvent, finally cooling the reaction solution to room temperature, filtering and discharging to obtain the antibacterial acrylic acid oligomer I.

6. The ultraviolet radiation curable ultra-matte skin feel antibacterial coating as claimed in claim 4, wherein the antibacterial acrylic oligomer II is prepared by the following steps:

(1) adding 5g of water into 50g of KP-J11, and stirring to fully hydrolyze KP-J11 to obtain an antibacterial solution II;

(2) adding 12g of hydroxyethyl methacrylate, 6g of 2, 3-epoxypropane methacrylate, 0.1g of polymerization inhibitor p-hydroxyanisole, 0.2g of catalyst tin dioctoate and 0.1g of BHT antioxidant into 30g of organic solvent to prepare a mixed solution;

(3) adding the antibacterial solution II into the mixed solution obtained in the step (2) and uniformly mixing to obtain a reaction solution, heating the reaction solution to 110 ℃, continuously stirring, heating and refluxing for 16-24h to remove water, then carrying out reduced pressure distillation to remove the organic solvent, finally cooling the reaction solution to room temperature, filtering and discharging to obtain the antibacterial acrylic acid oligomer II.

7. The UV-curable extra-matte skin-feel antibacterial paint as claimed in claim 1, wherein the acrylic monomer is one or a mixture of more than two of 1, 6-adipic acid diacrylate, diglycerol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and ethoxylated trimethylolpropane triacrylate.

8. The ultra-matte skin-feel antibacterial coating material cured by ultraviolet radiation as claimed in claim 1, wherein the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus and benzophenone.

9. The ultraviolet light radiation curing ultra-matte skin-feel antibacterial coating as claimed in claim 1, wherein the flatting agent is one or more of silica flatting powder, micronized wax powder and organic polyurea flatting agent.

10. The ultraviolet light radiation curing ultra-matte skin-feel antibacterial coating as claimed in claim 1, wherein the auxiliary agents comprise defoaming agents, dispersing agents, leveling agents and hand feeling agents.

11. The ultra-violet radiation curable extra-matte skin-feel antibacterial coating of any one of claims 1-9, wherein the coating can be applied on different substrates, including melamine boards, solid wood floors, particle boards, metal sheets or plastic sheets.

Technical Field

The invention relates to the technical field of coatings, in particular to an ultraviolet radiation curing ultra-matte skin-feel antibacterial coating.

Background

The super-matte skin-feeling decorative plate is generally accepted by the public in view of excellent skin-friendly touch feeling and soft super-matte visual effect, and is gradually applied to cabinet assembly, child room decoration and other furniture home decoration. Because high humidity and foreign matter residues exist in kitchens, bathrooms, rooms and other places, the places are the most serious places for breeding and spreading of bacteria and mold, every family needs to be cleaned and eliminated frequently and regularly, and the burden of family members is undoubtedly increased in the fast-paced society.

Because harmful bacteria and mould can be well killed and inhibited by some antibacterial disinfectants on the market, the antibacterial disinfectants are added into the super-matte skin-feel paint to obtain a certain effect, but a film-forming substance of a commercially available antibacterial agent, namely a non-UV paint, is free on the surface layer of the paint, and the antibacterial performance is reduced after multiple wiping, so that the antibacterial durability is poor.

A commercial antibacterial agent and some UV active monomers are subjected to catalytic reaction to synthesize a modified acrylic antibacterial monomer, and the modified acrylic antibacterial monomer is added into a UV super matte skin-feel paint to prepare a durable antibacterial UV paint so as to solve the problem of harmful bacteria in furniture home decoration.

Disclosure of Invention

Aiming at the problems in the prior art, the technical problems to be solved by the invention are as follows: antibacterial monomers such as quaternary ammonium salt, amino substances, quaternary phosphonium salt and the like are directly added into a coating system, and the compatibility of the antibacterial monomers and a resin matrix in the coating is poor, so that the optical characteristics of a coating film are influenced.

The technical scheme adopted by the invention for solving the technical problems is as follows: the invention provides an ultraviolet radiation curing ultra-matte skin-feel antibacterial coating which comprises the following components in parts by weight:

specifically, the urethane acrylate is a 10-functional urethane acrylate.

Specifically, the modified polyurethane acrylate is 3-functionality fluorosilicone modified polyester acrylate.

Specifically, the antibacterial acrylic oligomer is a compound consisting of an antibacterial acrylic oligomer I and an antibacterial acrylic oligomer II according to the mass ratio of 1: 1.

Specifically, the antibacterial acrylic oligomer I is prepared according to the following steps:

(1) adding 3g of water into 50g of DC-5700, and completely hydrolyzing the DC-5700 in the water after stirring to obtain an antibacterial solution I;

(2) adding 18g of hydroxyethyl methacrylate, 0.1g of p-hydroxyanisole polymerization inhibitor, 0.1g of BHT antioxidant and 0.2g of catalyst tin dioctoate into 30g of organic solvent to prepare a mixed solution;

(3) adding the antibacterial solution I obtained in the step (1) into the mixed solution obtained in the step (2) and uniformly mixing to obtain a reaction solution, raising the temperature of the reaction solution to 100 ℃, continuously stirring, heating and refluxing for 8-10h to remove water, then carrying out reduced pressure distillation to remove the organic solvent, finally cooling the reaction solution to room temperature, filtering and discharging to obtain the antibacterial acrylic acid oligomer I.

Specifically, the antibacterial acrylic acid oligomer II is prepared according to the following steps:

(1) adding 5g of water into 50g of KP-J11, and stirring to fully hydrolyze KP-J11 to obtain an antibacterial solution II;

(2) adding 12g of hydroxyethyl methacrylate, 6g of 2, 3-epoxypropane methacrylate, 0.1g of polymerization inhibitor p-hydroxyanisole, 0.2g of catalyst tin dioctoate and 0.1g of BHT antioxidant into 30g of organic solvent to prepare a mixed solution;

(3) adding the antibacterial solution II into the mixed solution obtained in the step (2) and uniformly mixing to obtain a reaction solution, heating the reaction solution to 110 ℃, continuously stirring, heating and refluxing for 16-24h to remove water, then carrying out reduced pressure distillation to remove the organic solvent, finally cooling the reaction solution to room temperature, filtering and discharging to obtain the antibacterial acrylic acid oligomer II.

Specifically, the acrylic monomer is one or a mixture of more than two of 1, 6-adipic acid diacrylate, diglycerol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and ethoxylated trimethylolpropane triacrylate.

Specifically, the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, diphenyl- (2,4, 6-trimethylbenzoyl) oxyphosphorus and benzophenone.

Specifically, the flatting agent is one or more of silicon dioxide flatting powder, micronized wax powder and organic polyurea flatting agent.

Specifically, the auxiliary agent comprises a defoaming agent, a dispersing agent, a leveling agent and a hand feeling agent.

Specifically, the ultraviolet radiation curing ultra-matte skin-feel antibacterial coating can be coated on different substrates for application, and the substrates comprise melamine boards, solid wood floors, shaving boards, metal sheets or plastic sheets.

The invention has the beneficial effects that:

(1) according to the invention, two self-made antibacterial acrylate oligomers are added into a coating system, and the two antibacterial acrylate oligomers have a synergistic effect, so that the antibacterial property of the coating is greatly improved;

(2) the self-made antibacterial acrylate oligomer has good compatibility with an acrylic resin matrix, and the mechanical and optical properties of a coating film are effectively guaranteed;

(3) the invention adopts the method of LED ultraviolet light precuring, excimer lamp ultraviolet irradiation and high-pressure mercury lamp ultraviolet irradiation to ensure that the cured coating film obtains the matte characteristic.

Detailed Description

The present invention will now be described in further detail with reference to examples.

The polyurethane acrylate adopted by the invention is 10-functional polyurethane acrylate which is described in Yongxing chemical 6195-100.

The modified polyurethane acrylate adopted by the invention is 3-functionality-degree fluorine-silicon modified polyester acrylate which is FSP 8818 in Guangzhou Ruoyo chemical industry.

The antibacterial acrylic acid oligomer adopted by the invention is a compound consisting of an antibacterial acrylic acid oligomer I and an antibacterial acrylic acid oligomer II according to the mass ratio of 1: 1.

The antibacterial acrylic acid oligomer I adopted by the invention is prepared according to the following steps:

(1) adding 3g of water into 50g of DC-5700, and completely hydrolyzing the DC-5700 in the water after stirring to obtain an antibacterial solution I;

(2) adding 18g of hydroxyethyl methacrylate, 0.1g of p-hydroxyanisole polymerization inhibitor, 0.1g of BHT antioxidant and 0.2g of catalyst tin dioctoate into 30g of organic solvent to prepare a mixed solution;

(3) adding the antibacterial solution I obtained in the step (1) into the mixed solution obtained in the step (2) and uniformly mixing to obtain a reaction solution, raising the temperature of the reaction solution to 100 ℃, continuously stirring, heating and refluxing for 8-10h to remove water, then carrying out reduced pressure distillation to remove the organic solvent, finally cooling the reaction solution to room temperature, filtering and discharging to obtain the antibacterial acrylic acid oligomer I.

The antibacterial acrylic acid oligomer II adopted by the invention is prepared according to the following steps:

(1) adding 5g of water into 50g of KP-J11, and stirring to fully hydrolyze KP-J11 to obtain an antibacterial solution II;

(2) adding 12g of hydroxyethyl methacrylate, 6g of 2, 3-epoxypropane methacrylate, 0.1g of polymerization inhibitor p-hydroxyanisole, 0.2g of catalyst tin dioctoate and 0.1g of BHT antioxidant into 30g of organic solvent to prepare a mixed solution;

(3) adding the antibacterial solution II into the mixed solution obtained in the step (2) and uniformly mixing to obtain a reaction solution, heating the reaction solution to 110 ℃, continuously stirring, heating and refluxing for 16-24h to remove water, then carrying out reduced pressure distillation to remove the organic solvent, finally cooling the reaction solution to room temperature, filtering and discharging to obtain the antibacterial acrylic acid oligomer II.

The acrylic monomer adopted by the invention is one or a mixture of more than two of 1, 6-adipic acid diacrylate, diglycerol diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate and ethoxylated trimethylolpropane triacrylate.

The photoinitiator adopted by the invention is one or more of 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-acetone, diphenyl- (2,4, 6-trimethyl benzoyl) oxyphosphorus and benzophenone.

The matting agent adopted by the invention is one or more of silicon dioxide matting powder, micronized wax powder and organic polyurea matting agent.

The auxiliary agents adopted by the invention comprise defoaming agents, dispersing agents, flatting agents and hand feeling agents.

The defoaming agent adopted by the invention is Tego 920; the dispersant is BYK 2009; the mark of the leveling agent is Tego 432; the handle was assigned the designation BKY 3500.

The base material adopted by the invention is melamine board, solid wood floor, shaving board, metal sheet or plastic sheet

Example 1

The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating comprises the following components in parts by weight:

example 2

The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating comprises the following components in parts by weight:

example 3

The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating comprises the following components in parts by weight:

example 4

The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating comprises the following components in parts by weight:

example 5

The ultraviolet radiation curing ultra-matte skin-feel antibacterial coating comprises the following components in parts by weight:

comparative example 1 the same as example 1 except that comparative example 1 used 10-functional polyurethane acrylate as new material SD 7510.

Comparative example 2 is the same as example 1 except that the 3-functionality fluorosilicone modified polyester acrylate adopted in comparative example 1 is a Guangzhou Songdao new material SD 7531.

Comparative example 3 is the same as example 1 except that the antibacterial acrylic oligomer used in comparative example 3 is a compound of antibacterial acrylic oligomer i and antibacterial acrylic oligomer ii in a mass ratio of 2: 1.

Comparative example 4 is the same as example 1 except that the antibacterial acrylic oligomer used in comparative example 4 is a compound of antibacterial acrylic oligomer i and antibacterial acrylic oligomer ii in a mass ratio of 1: 2.

Comparative example 5 is the same as example 1 except that the antibacterial acrylic oligomer used in comparative example 5 is only the antibacterial acrylic oligomer i.

The application comprises the following steps:

(1) surface treatment of substrates

Coating ZU42018 UV coating on the surface of the base material, curing, sanding and dedusting;

(2) the coatings obtained in examples 1 to 5 and comparative examples 1 to 5 were applied to a substrate at a coat weight of 40g/m²At 50 ℃ in the infraredLeveling to obtain finish paint;

(3) pre-curing and irradiating the finish paint in the step (2) by an LED ultraviolet lamp, wherein the irradiation energy is controlled to be 70-90%; then, performing ultraviolet irradiation on the finish paint by using an excimer lamp, wherein nitrogen needs to be continuously introduced when the excimer lamp works, so that the oxygen concentration is always kept to be less than 200ppm, and the irradiation energy is controlled to be 20-30%; and finally, carrying out ultraviolet irradiation of a high-pressure mercury lamp on the face paint, and controlling the irradiation energy to be 250-400mj to obtain the ultraviolet radiation curing ultra-matte skin-feel antibacterial panel.

And (3) performance testing:

the ultraviolet light radiation curing ultra-matte skin-feel antibacterial panels obtained in examples 1-5 and comparative examples 1-5 are subjected to glossiness, touch, hardness and antibacterial property tests, and the glossiness is tested according to GB 1743-79 (89); hardness was tested according to GB/T6739-; the antibacterial property is tested according to JC/T897-2014. The test results are shown in tables 1 and 2.

TABLE 1

Test item	Glossiness (60 degree)	Hardness (H)	Touch (touching)
				Example 1	2.5	3	Fine and smooth skin feeling
Example 2	3.6	3	Ice hard skinFeeling of
				Example 3	2.1	3	Silky skin feeling
Example 4	3.0	3	Smooth skin feel
				Example 5	3.3	3	Smooth skin feel
Comparative example 1	4.5	2	Ice hard skin feel
				Comparative example 2	4.6	2	Ice hard skin feel
Comparative example 3	2.8	3	Silky skin feeling
				Comparative example 4	3.0	3	Smooth skin feel
Comparative example 5	3.3	3	Smooth skin feel

TABLE 2

In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.