阅读说明：本技术 一种长效抗菌涂层、制备方法及其应用 (Long-acting antibacterial coating, preparation method and application thereof ) 是由 李鹏伟 宋亚穷 王尧尧 于 2021-08-18 设计创作，主要内容包括：本发明提供了一种长效抗菌涂层、制备方法及其应用,属于长效抗菌涂层制备技术领域。其技术方案为：该长效抗菌涂层由A组分和B组分按1:10的重量份的原料组成；制备方法为：将天然抗菌剂成分引入到异氰酸酯有机分子中,利用异氰酸酯与醇羟基的反应活性,在涂层固化时,将抗菌剂接枝到大分子支链、硅油末端或无机物表面。本发明的有益效果为：本发明将天然抗菌剂成分引入到异氰酸酯有机分子中,利用异氰酸酯与醇羟基的反应活性,在涂层固化时,将抗菌剂接枝到大分子支链、硅油末端或无机物表面,抗菌耐久性更好；在涂层固化过程中,有效抗菌成分随硅油或大分子链运动游离至表面,抗菌有效性更好。(The invention provides a long-acting antibacterial coating, a preparation method and application thereof, and belongs to the technical field of long-acting antibacterial coating preparation. The technical scheme is as follows: the long-acting antibacterial coating consists of a component A and a component B according to the weight part of 1: 10; the preparation method comprises the following steps: the natural antibacterial agent is introduced into organic isocyanate molecules, and the antibacterial agent is grafted to a macromolecular branched chain, the tail end of silicone oil or the surface of an inorganic substance by utilizing the reactivity of isocyanate and alcoholic hydroxyl when a coating is cured. The invention has the beneficial effects that: according to the invention, the natural antibacterial agent is introduced into organic molecules of isocyanate, and the antibacterial agent is grafted to a macromolecular branched chain, the tail end of silicone oil or the surface of an inorganic substance by utilizing the reactivity of isocyanate and alcoholic hydroxyl when a coating is cured, so that the antibacterial durability is better; in the coating curing process, the effective antibacterial component moves along with the silicone oil or the macromolecular chain and is dissociated to the surface, so that the antibacterial effectiveness is better.)

1. A long-acting antibacterial coating is characterized by consisting of a component A and a component B according to the weight part of 1:10, and the components are mixed and stirred uniformly and then sprayed for construction;

the component A is prepared from the following raw materials in parts by weight: 80-95 parts of isocyanate curing agent, 5-10 parts of active antibacterial agent and 0.01-0.2 part of catalyst;

the component B is prepared from the following raw materials in parts by weight: 10-30 parts of nano hydroxyl acrylic acid dispersoid, 30-40 parts of nano polycarbon polyurethane dispersoid, 2-10 parts of film-forming additive, 2-5 parts of dispersant, 2-5 parts of thickening agent, 0.2-0.5 part of wetting agent, 0.2-0.5 part of defoaming agent, 15-35 parts of inorganic filler, 0.2-0.5 part of hydroxyl silicone oil and 10-20 parts of deionized water.

2. The long-acting antimicrobial coating according to claim 1, wherein the isocyanate curing agent is a hydrophilic aliphatic polyisocyanate of hexamethylene diisocyanate having a viscosity of 500-1000 mpa.s.

3. The long-lasting antimicrobial coating of claim 1, wherein the catalyst is dibutyltin dilaurate.

4. The long-acting antibacterial coating according to claim 1, wherein the content of the nano hydroxyl acrylic dispersion is 40% -65%, the particle size range is 30nm-200nm, and the hydroxyl content is 2% -4%;

the solid content of the nano polycarbonate polyurethane dispersion is 45-70%, the particle size range is 30-200nm, and the hydroxyl content is 2-4%.

5. The long-acting antimicrobial coating of claim 1, wherein the coalescent is one or more of propylene glycol, DPNB, DPM, TPNB;

the thickening agent is one or more of association type thickening agent and alkali swelling type thickening agent;

the active antibacterial agent is one or more of citronellol, geraniol, eugenol and carvacrol.

6. The long-acting antimicrobial coating according to claim 1, wherein the inorganic filler spatial configuration comprises one or more of zero-dimensional inorganic substance, one-dimensional inorganic substance, and two-dimensional inorganic substance;

the zero-dimensional inorganic substance comprises one or more of calcium carbonate powder, silicon dioxide powder and titanium dioxide, the filler is modified in advance, hydroxyl is carried on the surface of the filler, and the particle size is 0.3-4 microns;

the one-dimensional inorganic substance comprises one or more of barium sulfate whisker, asbestos powder and attapulgite, the surface of the filler is provided with hydroxyl, the length is 1-5 microns, and the length-diameter ratio is (10-30);

the two-dimensional inorganic substance comprises one or more of kaolin, montmorillonite and mica powder, the diameter is 3-5 microns, and the thickness is 0.5-2 microns.

7. The long-acting antimicrobial coating of claim 1, wherein the hydroxy silicone oil is a hydroxy-terminated polydimethylsiloxane.

8. A method of preparing a long-acting antimicrobial coating according to any one of claims 1 to 10, comprising the steps of:

the preparation process of the step 1 and the component A is as follows:

sequentially adding the isocyanate and the organic tin catalyst in parts by weight into a dispersion machine, regulating the rotation speed of the dispersion machine to 100rmp/min, and heating the temperature to 60 ℃; slowly adding a natural antibacterial agent into the dispersion machine, and reacting for 120min to obtain a component A and isocyanate with an active antibacterial agent;

the preparation process of the component B in the step 2 is as follows:

adding the film-forming aid, the defoaming agent, the dispersing agent, the wetting agent, the thickening agent and a proper amount of water into the nano hydroxyl acrylic acid dispersoid in parts by weight, dispersing at a dispersion speed of 500rpm/min for 20 min; adding the inorganic filler and the hydroxyl silicone oil in parts by weight, and dispersing at a dispersion rate of 1000rpm/min for 40min until the fineness is less than 30um and no oil pit exists; slowly adding the polycarbonate polyurethane dispersoid and deionized water in parts by weight, and dispersing for 20 min; finally, adding the thickening agent in parts by weight to adjust the viscosity to obtain coating slurry of the component B;

and 3, uniformly mixing and stirring the component A and the component B according to the proportion of 1:10, and spraying the mixture on the surface of a test plate by using an airless spray gun to obtain the long-acting antibacterial coating.

9. A long-acting antibacterial coating prepared based on the preparation method of the long-acting antibacterial coating according to claim 8.

10. The long-acting antibacterial coating according to claim 9 is applied to the surface of a base material such as an internal and external wall of a building, furniture, a ceramic plate, a steel plate and the like as a surface coating.

Technical Field

The invention relates to the technical field of preparation of long-acting antibacterial coatings, in particular to a long-acting antibacterial coating, a preparation method and application thereof.

Background

With the pursuit of people for quality of life, the antibacterial performance of materials gradually becomes one of the important indexes of a plurality of life products. The antibacterial agent is mainly divided into organic antibacterial agent and metal antibacterial agent, and the organic antibacterial agent comprises various plant essential oils, organic metal compounds, quaternary ammonium salt, etc.; the metal antibacterial agent mainly comprises silver, copper, zinc and the like. For metal antibacterial agents, copper and the like have colors, and zinc has low antibacterial ability, so the most widely used metal antibacterial agent is silver, but silver belongs to heavy metals and still causes harm to human bodies after long-term contact. The natural antibacterial agent is extracted from plants, and has high safety, but the antibacterial agent belongs to a small molecular compound, is easy to migrate in polymer resin, is difficult to realize long-acting antibacterial, and has the antibacterial effect which is not the same as that of a metal antibacterial agent when the antibacterial agent is added in the same dosage.

The invention aims to solve the problems of long-term maintenance of the antibacterial effect of a natural antibacterial agent in a coating and improvement of the antibacterial effect of an antibacterial agent added in the same dosage.

Disclosure of Invention

The invention aims to provide a long-acting antibacterial coating, a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme: a long-acting antibacterial coating is composed of a component A and a component B according to the weight part of 1: 10;

the component A is prepared from the following raw materials in parts by weight: 80-95 parts of isocyanate curing agent, 5-20 parts of active antibacterial agent and catalyst: 0.01-0.2 weight parts;

the component B is prepared from the following raw materials in parts by weight: 10-30 parts of nano hydroxyl acrylic acid dispersoid, 30-40 parts of nano polycarbon polyurethane dispersoid, 2-10 parts of film-forming additive, 2-5 parts of dispersant, 2-5 parts of thickening agent, 0.2-0.5 part of wetting agent, 0.2-0.5 part of defoaming agent, 15-35 parts of inorganic filler, 0.2-0.5 part of hydroxyl silicone oil and 10-20 parts of deionized water.

As a further optimization scheme of the long-acting antibacterial coating provided by the invention, the isocyanate curing agent is hydrophilic aliphatic polyisocyanate of Hexamethylene Diisocyanate (HDI) with the viscosity of 500-1000 mpa.s.

As a further optimization scheme of the long-acting antibacterial coating provided by the invention, the catalyst is dibutyltin dilaurate.

As a further optimization scheme of the long-acting antibacterial coating provided by the invention, the solid content of the nano-hydroxyl acrylic acid dispersoid is 40-65%, the particle size range is 30-200nm, and the hydroxyl content is 2-4%.

The solid content of the nano polycarbonate polyurethane dispersion is 45-70%, the particle size range is 30-200nm, and the hydroxyl content is 2-4%.

As a further optimization scheme of the long-acting antibacterial coating provided by the invention, the film-forming auxiliary agent is one or more of propylene glycol, DPNB, DPM and TPNB.

The thickening agent is one or more of association type thickening agent and alkali swelling type thickening agent.

The active antibacterial agent is one or more of citronellol, geraniol, eugenol and carvacrol.

As a further optimization scheme of the long-acting antibacterial coating provided by the invention, the space configuration of the inorganic filler comprises one or more of zero-dimensional inorganic matters, one-dimensional inorganic matters and two-dimensional inorganic matters.

The zero-dimensional inorganic substance comprises one or more of calcium carbonate powder, silicon dioxide powder and titanium dioxide, the filler is modified in advance, the surface of the filler is provided with hydroxyl, and the particle size is 0.3-4 microns.

The one-dimensional inorganic substance comprises one or more of barium sulfate whisker, asbestos powder and attapulgite, the surface of the filler is provided with hydroxyl, the length is 1-5 microns, and the length-diameter ratio is (10-30).

The two-dimensional inorganic substance comprises one or more of kaolin, montmorillonite and mica powder, the diameter is 3-5 microns, and the thickness is 0.5-2 microns.

As a further optimization scheme of the long-acting antibacterial coating provided by the invention, the hydroxyl silicone oil is hydroxyl-terminated polydimethylsiloxane.

In order to better achieve the above object, the present invention also provides a method for preparing a long-acting antibacterial coating, comprising the steps of:

the preparation process of the step 1 and the component A is as follows:

sequentially adding the isocyanate and the organic tin catalyst in parts by weight into a dispersion machine, regulating the rotation speed of the dispersion machine to 100rmp/min, and heating the temperature to 60 ℃; slowly adding a natural antibacterial agent into the dispersion machine, reacting for 120min to obtain a component A and isocyanate with an activated antibacterial agent;

the preparation process of the component B in the step 2 is as follows:

adding the film-forming aid, the defoaming agent, the dispersing agent, the wetting agent, the thickening agent and a proper amount of water into the nano hydroxyl acrylic acid dispersoid in parts by weight, dispersing at a dispersion speed of 500rpm/min for 20 min; adding the inorganic filler and the hydroxyl silicone oil in parts by weight, and dispersing at a dispersion rate of 1000rpm/min for 40min until the fineness is less than 30um and no oil pit exists; slowly adding the polycarbonate polyurethane dispersoid and deionized water in parts by weight, and dispersing for 20 min; finally, adding the thickening agent in parts by weight to adjust the viscosity to obtain coating slurry of the component B;

and 3, uniformly mixing and stirring the component A and the component B according to the proportion of 1:10, and spraying the mixture on the surface of a test plate by using an airless spray gun to obtain the long-acting antibacterial coating.

The long-acting antibacterial coating is prepared by the preparation method of the long-acting antibacterial coating.

The long-acting antibacterial coating is applied to the surfaces of base materials such as internal and external walls of buildings, furniture, ceramic plates, steel plates and the like as a surface coating.

The application of the long-acting antibacterial coating in preparation provided by the invention is to adopt a two-component system, wherein the component B takes a hydroxyl acrylic acid dispersoid and a polyurethane dispersoid as resin base materials, and the component A is an isocyanate curing agent; introducing a natural antibacterial agent into isocyanate organic molecules of the A component through pretreatment; after the two component materials are mixed, the antibacterial agent is grafted to the macromolecule branch chain, the end of the silicone oil or the surface of an inorganic substance by utilizing the reactivity of isocyanate and alcoholic hydroxyl when the coating is cured.

Compared with the prior art, the invention has the beneficial effects that: firstly, introducing an antibacterial substance into organic molecules of isocyanate; by utilizing the reactivity of isocyanate and alcoholic hydroxyl, the antibacterial agent is grafted to a macromolecule branched chain, the tail end of silicon oil or the surface of an inorganic substance when the coating is cured, and effective antibacterial components move along with the silicon oil or the macromolecule chain to be dissociated to the surface in the curing process of the coating, so that the better antibacterial effect of the coating is realized, and meanwhile, the antibacterial agent is chemically bonded with the substrate, so that the antibacterial lasting effect of the coating is prolonged.

Detailed Description

The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications or substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and scope of the invention. The experimental methods and reagents of the formulations not specified in the examples are in accordance with the conventional conditions in the art.

Example 1

Step one, preparing component A

Sequentially adding 94.9 parts by weight of isocyanate and 0.1 part by weight of organotin catalyst into a dispersion machine, regulating the rotation speed of the dispersion machine to 100rmp/min, and heating to 60 ℃; slowly adding 5 parts of natural antibacterial agent into the dispersion machine, and reacting for 120min to obtain a component A and isocyanate with an activated antibacterial agent;

step two, preparing the component B

Adding 7 parts by weight of film-forming additive, 0.3 part by weight of defoaming agent, 3 parts by weight of dispersant, 0.25 part by weight of wetting agent, 2 parts by weight of thickener and 3 parts by weight of deionized water into 20 parts by weight of nano hydroxyl acrylic acid dispersoid, and dispersing at the dispersion rate of 500rpm/min for 20 min; sequentially adding 5 parts by weight of light calcium carbonate, 8 parts by weight of heavy calcium carbonate, 12 parts by weight of titanium dioxide, 2 parts by weight of kaolin and 0.2 part by weight of hydroxyl silicone oil, and dispersing at a dispersion speed of 1000rpm/min for 40min until the fineness is less than 30um and no oil pits exist; finally, slowly adding 30 parts by weight of the polycarbon polyurethane dispersoid and 5 parts by weight of deionized water, dispersing for 20min, and then adding 2.25 parts by weight of the thickening agent to adjust the viscosity to obtain coating slurry;

step three, preparing a coating sample plate, and mixing the component A and the component B according to the ratio of about 1: mixing and stirring uniformly according to the proportion of 10, wherein the content of the mixed antibacterial agent accounts for 0.45 percent of the total mass, then spraying by using an airless spray gun to prepare 30 coating sample plates with the specification of 6cm by 6cm, and carrying out antibacterial performance detection.

Example 2

Step one, preparing component A

Adding 87.9 parts by weight of isocyanate and 0.1 part by weight of organotin catalyst into a dispersion machine in sequence, regulating the rotation speed of the dispersion machine to 100rmp/min, and heating the temperature to 60 ℃; slowly adding 8 parts of natural antibacterial agent into the dispersion machine, and reacting for 120min to obtain a component A and isocyanate with an activated antibacterial agent;

step two: the preparation method is the same as that of example 1

Step three: a coating panel was prepared by mixing a component a and a component B in a ratio of about 1: mixing and stirring uniformly according to the proportion of 10, wherein the content of the mixed antibacterial agent accounts for 0.73 percent of the total mass, then spraying by using an airless spray gun to prepare 30 coating sample plates with the specification of 6cm by 6cm, and carrying out antibacterial performance detection.

Example 3

The method comprises the following steps: preparation of component A

Sequentially adding 88.9 parts by weight of isocyanate and 0.1 part by weight of organotin catalyst into a dispersion machine, regulating the rotation speed of the dispersion machine to 100rmp/min, and heating to 60 ℃; slowly adding 11 parts of natural antibacterial agent into the dispersion machine, and reacting for 120min to obtain a component A and isocyanate with an activated antibacterial agent;

step two: preparation of component B

Adding 5 parts by weight of film-forming additive, 0.3 part by weight of defoaming agent, 2 parts by weight of dispersant, 0.5 part by weight of wetting agent, 2 parts by weight of thickener and 8 parts by weight of deionized water into 25 parts by weight of nano hydroxyl acrylic acid dispersoid, and dispersing at the dispersion rate of 500rpm/min for 20 min; sequentially adding 5 parts by weight of light calcium carbonate, 3 parts by weight of heavy calcium carbonate, 12 parts by weight of titanium dioxide, 2 parts by weight of kaolin and 0.2 part by weight of hydroxyl silicone oil, and dispersing at a dispersion speed of 1000rpm/min for 40min until the fineness is less than 30um and no oil pits exist; finally, slowly adding 25 parts by weight of the polycarbon polyurethane dispersoid and 8 parts by weight of deionized water, dispersing for 20min, and then adding 2 parts by weight of the thickening agent to adjust the viscosity to obtain coating slurry;

step three: a coating panel was prepared by mixing a component a and a component B in a ratio of about 1: mixing and stirring uniformly according to the proportion of 10, wherein the content of the mixed antibacterial agent accounts for 1.00 percent of the total mass, then spraying by using an airless spray gun to prepare 30 coating sample plates with the specification of 6cm by 6cm, and carrying out antibacterial performance detection.

Comparative example 1

The method comprises the following steps: the component A is isocyanate curing agent without adding antibacterial agent

Step two: preparing a component B, namely adding 3 parts by weight of film-forming additive, 0.5 part by weight of defoaming agent, 2 parts by weight of dispersing agent, 0.5 part by weight of wetting agent, 2.5 parts by weight of thickening agent and 5 parts by weight of deionized water into 15 parts by weight of nano hydroxyl acrylic acid dispersoid, and dispersing at a dispersion speed of 500rpm/min for 20 min; sequentially adding 5 parts by weight of light calcium carbonate, 2 parts by weight of heavy calcium carbonate, 5 parts by weight of talcum powder, 12 parts by weight of titanium dioxide and 0.5 part by weight of nano-silver antibacterial agent, and dispersing at a dispersion speed of 1000rpm/min for 40min until the fineness is less than 30um and no oil pits exist; and finally, slowly adding 35 parts of the polycarbonate polyurethane dispersion and a proper amount of water, dispersing for 30min, and adding a thickening agent to adjust the viscosity to obtain coating slurry.

Step three: preparing a coating sample plate, and mixing the component A and the component B in a ratio of 1: mixing and stirring uniformly according to the proportion of 10, preparing 30 coating sample plates with the specification of 6cm by 6cm, and detecting the antibacterial performance.

Comparative example 2

Adding 3 parts by weight of film-forming additive, 0.5 part by weight of defoaming agent, 2 parts by weight of dispersant, 0.5 part by weight of wetting agent, 2.5 parts by weight of thickening agent and 5 parts by weight of deionized water into 50 parts by weight of acrylic acid dispersoid, and dispersing at a dispersion speed of 500rpm/min for 10 min; sequentially adding 5 parts by weight of light calcium carbonate, 2 parts by weight of heavy calcium carbonate, 5 parts by weight of talcum powder, 12 parts by weight of titanium dioxide and 0.5 part by weight of nano-silver antibacterial agent, dispersing at a dispersion rate of 1000rpm/min for 30min, and adding a thickening agent to adjust viscosity to obtain antibacterial coating slurry; and finally, spraying 30 coating sample plates with the specification of 6cm by using an airless spray gun, and detecting the antibacterial performance.

Comparative example 3

The method comprises the following steps: the component A is isocyanate curing agent without adding antibacterial agent

Step two: preparing a component B, namely adding 3 parts by weight of film-forming additive, 0.5 part by weight of defoaming agent, 2 parts by weight of dispersing agent, 0.5 part by weight of wetting agent, 2.5 parts by weight of thickening agent and 12 parts by weight of deionized water into 15 parts by weight of nano hydroxyl acrylic acid dispersoid, and dispersing at a dispersion speed of 500rpm/min for 20 min; sequentially adding 5 parts by weight of light calcium carbonate, 2 parts by weight of heavy calcium carbonate, 5 parts by weight of talcum powder, 12 parts by weight of titanium dioxide and 0.5 part by weight of natural antibacterial agent, and dispersing at a dispersion speed of 1000rpm/min for 40min until the fineness is less than 30um and no oil pits exist; and finally, slowly adding 35 parts of the polycarbon polyurethane dispersoid and 5 parts of water by weight, dispersing for 30min, and then adding a thickening agent to adjust the viscosity to obtain coating slurry.

Step three: preparing a coating sample plate, and mixing the component A and the component B in a ratio of 1: mixing and stirring uniformly according to the proportion of 10, preparing 30 coating sample plates with the specification of 6cm by 6cm, and detecting the antibacterial performance.

Test method

1. Experimental strains: escherichia coli AS1.90 with inoculated bacterial liquid concentration of 6.5 × 10⁵cfu/mL; staphylococcus aureus AS1.89, inoculated bacterial liquid concentration 9.2X 10⁵cfu/mL。

2. And (3) testing by using 30 coating sample plates with the specifications of 6cm by 6cm, setting a blank group and a control group, carrying out an antibacterial test according to HG/T3950-2007, and culturing for 24 hours to obtain the antibacterial rate before aging treatment.

3. And (3) adopting a 30W ultraviolet lamp with the wavelength of 253.7nm, wherein the ultraviolet lamp conforms to GB19258, the distance between the test sample and the ultraviolet lamp is 0.8-1.0 m, irradiating for 100h, and carrying out an antibacterial test on the statically treated test sample according to HG/T3950-2007 to obtain the antibacterial rate after the ageing treatment.

4. The antibacterial performance retention rate (after aging treatment)/antibacterial rate (after aging treatment) is obtained, so that the antibacterial durability of different formula schemes can be obtained by comparing data.

The results of the performance tests obtained for the different examples and comparative examples are given in table 1 below.

As can be seen from Table 1, the amounts of the antibacterial agents added (after the A/B ratio) in examples 1, 2 and 3 are higher than those in comparative examples 1, 2 and 3 by 0%, 0.28% and 0.55%, respectively, as compared with comparative examples 1, 2 and 3; wherein, the comparative example 1 and the comparative example 2 adopt nano-silver antibacterial agents, the comparative example 3 adopts natural antibacterial agents, and the three adopt the prior technical scheme provided by the technical method; wherein, the comparative example 2 adopts a single-component system, acrylic resin is taken as a base material, and the comparative examples 1 and 3 adopt a two-component system.

Antibacterial properties (before aging treatment): the antibacterial rate of the example 1 is lower than that of the comparative example 2, and the antibacterial effect of the nano-silver antibacterial agent is better than that of a natural antibacterial agent with the same dosage of addition; the antibacterial rate of the example 1 is higher than that of the comparative example 1, which shows that the antibacterial effect of the double-component system is better than that of the single-component system taking the acrylic resin as the base material; the antibacterial rate of the example 1 is higher than that of the comparative example 3, which shows that the antibacterial effect of the coating can be improved by adopting the technical scheme with the same addition amount.

Antibacterial properties (after aging treatment): the antibacterial retention rate of comparative example 3 is lower than that of comparative example 1, which shows that the antibacterial durability of the natural antibacterial rate is not as good as that of the nano-silver antibacterial agent; from the aspect of antibacterial retention rate, the antibacterial agent of the embodiment 1, the embodiment 2 and the embodiment 3 are obviously improved compared with the antibacterial agent of the comparative example 1, the comparative example 2 and the comparative example 3.

The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention, and any local variations in the formulation and process thereof should be considered within the scope of the present invention.