CN112175480B

CN112175480B - Composite bactericidal antiviral anti-aging coating for helmet surface layer and preparation method thereof

Info

Publication number: CN112175480B
Application number: CN202011047946.5A
Authority: CN
Inventors: 吕晓正
Original assignee: Changzhou Qinyuan New Material Co ltd
Current assignee: Changzhou Qinyuan New Material Co ltd
Priority date: 2020-09-28
Filing date: 2020-09-28
Publication date: 2021-10-15
Anticipated expiration: 2040-09-28
Also published as: CN112175480A

Abstract

The application relates to the field of coatings, and particularly discloses a composite bactericidal antiviral anti-aging coating for a helmet surface layer and a preparation method thereof. The composite bactericidal antiviral anti-aging coating for the surface layer of the helmet is prepared from the following raw materials in parts by weight: 30-60 parts of alicyclic epoxy resin, 5-15 parts of solvent, 0.5-2.0 parts of auxiliary agent, 2-5 parts of superfine alumina powder, 2-5 parts of scratch-resistant powder, 5-13 parts of bactericidal and antiviral modifier, 1-3 parts of wax slurry, 0.5-1.5 parts of ultraviolet absorbent and 30-60 parts of curing agent, wherein the bactericidal and antiviral modifier is prepared by compounding nano zinc oxide and nano cuprous oxide; the preparation method comprises the following steps: mixing part of the materials preliminarily, grinding and sieving, mixing the rest materials secondarily, and compounding with a curing agent to prepare the inorganic bactericidal antiviral anti-aging coating; the coating prolongs the sterilization performance of the helmet surface coating after long-term use. In addition, the preparation method has the advantages of simplicity, easiness in operation and wide application range.

Description

Composite bactericidal antiviral anti-aging coating for helmet surface layer and preparation method thereof

Technical Field

The application relates to the field of coatings, in particular to a composite bactericidal antiviral anti-aging coating for a helmet surface layer and a preparation method thereof.

Background

In modern transportation, the helmet is used more and more frequently and is contacted with a human body abnormally and closely, in the actual use process, the surface of the helmet is easily attached by germs brought by hands, rainwater or pollutants in the air, and meanwhile, in the long-term use process of the helmet, due to the fact that the helmet is exposed to wind and sunlight for a long time, the coating is required to have good ageing resistance so as to improve the antibacterial durability of the coating.

The existing bactericidal and antiviral coatings generally utilize organic and inorganic bactericides and mildewcides, wherein the organic bactericides and mildewcides can release harmful substances such as substituted aromatic hydrocarbon, organic bromine or dithiocarbamate to kill bacteria, but the substances have strong irritation to skin, and organic components of the substances are slowly decomposed and lose efficacy in the using process, so that the long-acting bactericidal effect cannot be achieved, and the use rate of the substances in the antibacterial coating is not high; in the antibacterial and antiviral coating modified by the inorganic antibacterial agent, inorganic nano antibacterial materials such as nano silver or a complex thereof, nano titanium dioxide, nano copper oxide, nano zinc oxide and the like are commonly used, and the inorganic nano antibacterial materials can generate the effects of membrane damage, respiratory depression, protein inactivation, DNA degradation and the like on bacteria, so that the antibacterial and antiviral effects are achieved. Among these inorganic antibacterial materials, the nano silver antibacterial materials have the problems of high price and easy oxidation failure, and although nano titanium dioxide adopts ultraviolet light catalysis to achieve the antibacterial effect, the ultraviolet light has great harm to human bodies, and the expected effect is difficult to achieve in indoor or dark occasions, so that all the inorganic antibacterial materials have the defects. However, the nano copper oxide is used as one of inorganic nano antibacterial materials, has a unique 'contact killing' mechanism, can quickly and efficiently kill germs on the surface, and is widely used in antibacterial coatings.

In view of the above-mentioned related technologies, the applicant believes that the existing inorganic antibacterial material is added into the helmet coating only by using a single antibacterial agent, namely nano copper oxide, in the actual use process, and the antibacterial performance is poor, and after long-term use, the surface of the coating is easy to corrode and age, so that the long-term antibacterial and virus-killing performance of the helmet surface coating is reduced.

Disclosure of Invention

In order to prolong the sterilizing and antiviral performances of the surface coating of the helmet after long-term use, the application provides a composite sterilizing, antiviral and anti-aging coating for the surface layer of the helmet, which is prepared from the following raw materials in parts by weight: 30-60 parts of alicyclic epoxy resin, 5-15 parts of solvent, 0.5-2.0 parts of auxiliary agent, 2-5 parts of superfine alumina powder, 2-5 parts of scratch-resistant powder, 5-13 parts of bactericidal and antiviral modifier, 1-3 parts of wax slurry, 0.5-1.5 parts of ultraviolet absorbent and 30-60 parts of curing agent, wherein the bactericidal and antiviral modifier is prepared by compounding nano zinc oxide and nano cuprous oxide.

By adopting the technical scheme, the compound material of nano zinc oxide and nano cuprous oxide is selected as the inorganic antibacterial material to be added into the coating, and the compound material has the surface and space dual antibacterial disinfection effect, compared with the common inorganic antibacterial material, the material has the characteristics of large specific surface area and high antibacterial activity, not only can damage electrolyte and protein shells of germs attached to the surface, but also can generate ionized charges to efficiently kill germs in the adjacent space, thereby effectively prolonging the sterilization performance of the surface coating of the helmet, and thus, the corrosion performance of surface bacteria to the coating is greatly reduced, and the sterilization performance of the surface coating of the helmet after long-term use is effectively prolonged.

Further, the nano zinc oxide in the bactericidal and antiviral modifier is needle-shaped nano zinc oxide with the diameter of 20-30 nm and the length-diameter ratio of more than 100, and the nano cuprous oxide in the bactericidal and antiviral modifier is any one of flaky nano cuprous oxide or porous nano cuprous oxide.

By adopting the technical scheme, as the nano zinc oxide and the nano cuprous oxide materials with special shapes are adopted, the effective combination form is formed by compounding the zinc oxide and the cuprous oxide materials, the needle-shaped zinc oxide particles are inserted into the flaky nano cuprous oxide structure or inserted into the porous nano cuprous oxide, the structural performance of the sterilizing and antiviral modifier is improved by the composite structure formed between the needle-shaped zinc oxide particles and the flaky nano cuprous oxide structure, the nano cuprous oxide and the nano zinc oxide structure are organically combined to form the compound structure due to the construction of the composite structure, the defect of poor durability caused by poor combination performance of the two traditional materials is overcome, the nano cuprous oxide firstly has a unique contact killing mechanism, the germs on the surface are killed quickly and efficiently, and the electrolyte and the cuprous oxide which damage germs attached to the surface are damaged, And the rest bacteria or viruses are efficiently killed by the ionized charges generated by the zinc oxide particles, so that a multi-stage sterilization mechanism is formed, the sterilization and virus killing effects are effectively improved, and the sterilization performance of the helmet surface coating after long-term use is fundamentally and effectively prolonged.

Further, the bactericidal and antiviral modifier is prepared by compounding needle-shaped nano zinc oxide and porous nano cuprous oxide, and comprises the following steps: adding peach gum into deionized water, grinding, dispersing, sieving, dialyzing, and collecting dialysate; mixing copper acetate solution, dialysate, span-80 and liquid paraffin, homogenizing, and adjusting pH to 8.5 to obtain mixed solution; taking needle-shaped nano zinc oxide particles, mixing the needle-shaped nano zinc oxide particles, the mixed solution and the glucose solution according to the mass ratio of 1: 3-5: 10-15, stirring, mixing, centrifuging, collecting lower-layer precipitates, washing, drying, grinding, dispersing, calcining, standing and cooling to obtain the collected bactericidal and antiviral modifier.

Through adopting above-mentioned technical scheme, because what this application adopted is that the peach gum is the binder template, decompose the processing after high temperature calcination, can form a plurality of holes on cuprous oxide surface, structure through the compound needle-like zinc oxide material of porous cuprous oxide of this appearance, can make cuprous oxide load more zinc oxide particles, make deep sterilization antiviral performance improve, thereby make cuprous oxide and zinc oxide material prepare through the scheme of integral structure, the stable structural performance of material has been improved, the performance of disinfecting after long-term use of helmet surface coating has also effectively been prolonged.

Further, the calcination treatment comprises the following steps: and (3) carrying out heat preservation and calcination for 10-12 hours at 350-400 ℃ in an air atmosphere under a shaking environment at 500 r/min.

Through adopting above-mentioned technical scheme, because this application has adopted the vibration environment to calcine the processing, inside some needle-like zinc oxide materials that do not combine with porous cuprous oxide can progressively gomphosis to the material under the vibration environment to form the load, improved the structural relation between the two, thereby prolonged the performance that the helmet surface coating disinfected after long-term the use.

Further, the scratch-resistant powder is polyurethane elastomer particles with the particle size of 7-9 microns.

Through adopting above-mentioned technical scheme, because this application has adopted polyurethane elastomer granule to be modified material, elastomer material can effectively gomphosis to the inside of coating, when it receives external force to scrape, because form effectual load and combine between it and the resin, reduced the destruction intensity of scraping to the coating structure to coating material's scraping resistance performance has been improved.

Further, the auxiliary agent is prepared from a dispersing agent and a defoaming agent according to a mass ratio of 6: 4.

By adopting the technical scheme, the dispersing agent and the auxiliary agent prepared by the defoaming agent are adopted, so that the dispersibility of the bactericidal and antiviral modifier in the coating is improved, the phenomenon of agglomeration of the bactericidal and antiviral modifier is prevented, and the generation of bubbles in the coating is reduced under the action of the defoaming agent, so that the structure and the mechanical strength of the whole paint film are improved, and the service life of the coating is prolonged.

Further, the curing agent is a silicone resin having an amino functional group.

By adopting the technical scheme, because the organic silicon resin material modified by the amino functional group is adopted, the durability of the organic silicon resin material is effectively improved by the amino modification scheme, the durability of the coating material prepared in the way is effectively improved, and meanwhile, the coating with ultrahigh durability, scratch resistance and wear resistance is obtained by combining the resin material and the scratch-resistant material, so that the durability of the coating material is improved.

In a second aspect, the application provides a preparation method of a composite bactericidal antiviral anti-aging coating for a helmet surface layer, which comprises the following steps: s1, sequentially adding a solvent, an auxiliary agent and a half mass of alicyclic epoxy resin at a low-speed stirring speed, continuously stirring, increasing the rotation speed to a medium-speed stirring speed, sequentially adding superfine aluminum oxide powder, scratch-resistant powder and a sterilizing and antiviral modifier again, increasing the rotation speed to a high speed, and collecting the obtained product after stirring; s2, grinding the stirred slurry and collecting screened slurry; s3, placing the sieved slurry at a low-speed stirring speed, mixing and stirring the remaining half mass of alicyclic epoxy resin, wax slurry and ultraviolet absorbent to obtain a composite nano inorganic bactericidal antiviral anti-aging coating A component; s4, mixing the component A and the curing agent according to the formula, and stirring uniformly to obtain the inorganic bactericidal antiviral anti-aging coating.

By adopting the technical scheme, due to the scheme of adding, stirring and mixing the raw materials for multiple times, the components can be well combined, meanwhile, the agglomeration phenomenon of the sterilizing and antiviral modifier material in the material is reduced, the prepared coating material is uniform and stable in structure, and the durability and the mechanical strength of the coating are improved.

Further, the low-speed stirring speed, the medium-speed stirring speed and the high-speed stirring speed in the step S1 are respectively 200-400 rpm, 500-800 rpm and 1000-1200 rpm.

By adopting the technical scheme, according to the properties of different materials, the materials are stirred at different rates after being added, the materials are uniformly and thoroughly mixed under low-speed stirring, the dispersibility of the particles is improved by medium-speed stirring, the particles are not easy to agglomerate, and the overall performance of the coating is stable and uniform by high-speed stirring, so that the structural stability of the coating is improved, and the mechanical property and the durability of the coating are improved.

Further, the grinding process in step S3 includes the following specific steps: s11, collecting the stirred slurry, placing the stirred slurry in a nano sand mill, controlling the particle size of a grinding medium to be 0.2mm, grinding for 8-10 h to obtain grinding slurry, and sieving by a 10-micron sieve to obtain sieving slurry.

By adopting the technical scheme, because the sand mill is adopted for grinding treatment, the whole coating is controlled to be uniform and fine, the sterilizing and antiviral modifier and the scraping-resistant powder are prevented from reducing the smoothness of the coating, and the mechanical property and the durability of the coating are effectively improved.

In summary, the present application includes at least one of the following beneficial technical effects:

firstly, the application adopts nano zinc oxide and nano cuprous oxide materials with special shapes, and aims to form an effective combination form by compounding the zinc oxide and the cuprous oxide materials, improve the structural performance of the bactericidal and antiviral modifier and overcome the defect of poor durability caused by poor combination performance of the two traditional materials.

Secondly, polyurethane elastomer particles are adopted as a modified material, the elastomer material can be effectively embedded into the coating, and when the coating is scraped by external force, the damage strength of the scraping to the coating structure is reduced due to the effective load and combination formed between the elastomer material and resin, so that the scraping resistance of the coating material is improved.

Thirdly, the scheme of adding, stirring and mixing the raw materials for multiple times is adopted, good combination of all the components can be guaranteed, meanwhile, the agglomeration phenomenon of the sterilizing and antiviral modifier material in the material is reduced, the prepared coating material is uniform and stable in structure, the durability and the mechanical strength of the coating are improved, the prepared coating can be used as varnish, pigment can also be added to prepare solid-color paint, and the application scene is rich.

Drawings

FIG. 1 is a flow chart of a preparation method of the composite bactericidal antiviral anti-aging coating for the surface layer of the helmet provided by the application;

FIG. 2 is a scanning electron microscope image of acicular nano-zinc oxide particles used in the preparation method of the composite bactericidal antiviral anti-aging coating for helmet surface layer according to an embodiment of the present application;

FIG. 3 is a scanning electron microscope image of acicular nano-zinc oxide particles used in the preparation method of the composite bactericidal antiviral anti-aging coating for helmet surface layer according to an embodiment of the present application;

FIG. 4 is a scanning electron microscope image of acicular nano-zinc oxide particles used in the preparation method of the composite bactericidal antiviral anti-aging coating for helmet surface layer according to an embodiment of the present application;

FIG. 5 is a scanning electron microscope image of nano cuprous oxide flakes used in the method for preparing the composite bactericidal antiviral anti-aging coating for helmet skins according to the present application;

FIG. 6 is a scanning electron microscope image of the porous nano-cuprous oxide used in the preparation method of the composite bactericidal antiviral anti-aging coating for helmet surface layer according to the embodiment of the present application;

fig. 7 is a scanning electron microscope image of the composite bactericidal antiviral anti-aging coating for the helmet surface layer in example 4 of the present application, which is prepared by compositing the nano cuprous oxide flakes with the needle-like zinc oxide.

Detailed Description

The present application will be described in further detail with reference to the following drawings and examples.

In the embodiment of the present application, the used apparatuses and raw materials and auxiliary materials are as follows, but not limited thereto: a machine: the dispersion machine is an SDF-110 high-speed dispersion machine, the sand mill is a WSS-0.4L disk sand mill, and the air spraying equipment is a set.

Medicine preparation: alicyclic epoxy resin YYR-8207, alicyclic epoxy resin ER-662, ultraviolet absorbent UV-234, ultraviolet absorbent UV-531, dispersant 5040 produced by Maill chemical industry and synthetic fertilizer novel universal ring environmental protection technology defoamer XWC-T118.

Examples

Example 1

Firstly, adding peach gum into deionized water according to the mass ratio of 1:100, stirring, mixing, grinding, dispersing, sieving with a 1000-mesh sieve, collecting sieved gel, placing the sieved gel in a dialysis bag with the molecular weight of 8000 for dialysis treatment, and collecting dialysate;

respectively weighing 45g of copper acetate solution, 10g of dialysate, 2g of span-80 and 10g of liquid paraffin, placing the copper acetate solution, the dialysate, the span-80 and the liquid paraffin into a homogenizer, homogenizing, collecting homogenized liquid, and adjusting the pH to 8.5 by using sodium hydroxide solution with the mass fraction of 5% to obtain mixed liquid;

taking needle-shaped nano zinc oxide particles with the diameter of 20nm and the length-diameter ratio of 100, stirring and mixing the needle-shaped zinc oxide particles, the mixed solution and a glucose solution with the mass fraction of 5.6% according to the mass ratio of 1:5:10, placing the mixture at 1500r/min for centrifugal separation, collecting lower-layer precipitates, alternately washing the lower-layer precipitates with ethanol and deionized water, collecting the washed particles, placing the washed particles at 55 ℃ for drying for 10 hours, grinding, dispersing and collecting dispersed microspheres, placing the dispersed microspheres at 350 ℃ in an air atmosphere, carrying out heat preservation and calcination for 10 hours under a shaking environment at 500r/min, standing, cooling to room temperature, and collecting the bactericidal and antiviral modifier;

respectively weighing 30g of alicyclic epoxy resin YYR-8207, 5g of solvent, 0.5g of auxiliary agent, 2g of 0.1 mu m alumina powder, 2g of 7 mu m polyurethane elastomer particles as scratch-resistant powder, 5g of bactericidal and antiviral modifier, 1g of wax slurry, 0.5g of ultraviolet absorbent and 30g of curing agent, wherein the solvent is prepared from n-butyl acetate, propylene glycol methyl ether acetate and xylene according to a mass ratio of 4: 3: 3, the auxiliary agent is prepared from a dispersing agent 5040 and a defoaming agent XWC-T118 according to a mass ratio of 6: 4, preparing a composition;

under the low-speed stirring rate of 200rpm, sequentially adding a solvent, an auxiliary agent and half of alicyclic epoxy resin in the formula, continuously stirring for 5min, increasing the rotating speed to 500rpm, sequentially adding superfine aluminum oxide powder, scratch-resistant powder and a sterilizing and antiviral modifier again, finally increasing the rotating speed to 1000rpm, continuously stirring for 10min, collecting the stirred slurry, placing the slurry into a nano sand mill, controlling the particle size of a grinding medium to be 0.2mm, grinding for 8h to obtain grinding slurry, passing the grinding slurry through a 10-micron screen, placing the screened slurry under 500rpm, mixing and stirring the remaining half of alicyclic epoxy resin, 6900-20X wax slurry and an ultraviolet absorbent UV-234 to obtain a composite nano inorganic sterilizing and antiviral aging-resistant coating A component; and mixing the component A and a curing agent according to a formula, wherein the curing agent is silicon resin with amino functional groups, and uniformly stirring to obtain the inorganic bactericidal antiviral anti-aging coating.

Example 2

respectively weighing 47g of copper acetate solution, 12g of dialysate, 2g of span-80 and 12g of liquid paraffin, placing the copper acetate solution, the dialysate, the span-80 and the liquid paraffin into a homogenizer, homogenizing, collecting homogenized liquid, and adjusting the pH to 8.5 by using sodium hydroxide solution with the mass fraction of 5% to obtain mixed liquid;

taking needle-shaped nano zinc oxide particles with the diameter of 20nm and the length-diameter ratio of 100, stirring and mixing the needle-shaped zinc oxide particles, the mixed solution and a glucose solution with the mass fraction of 5.6% according to the mass ratio of 1:5:10, placing the mixture at 1750r/min for centrifugal separation, collecting lower-layer precipitates, alternately washing the lower-layer precipitates with ethanol and deionized water, collecting the washed particles, placing the washed particles at 57 ℃ for drying for 11 hours, grinding, dispersing and collecting dispersed microspheres, placing the dispersed microspheres at 375 ℃ in an air atmosphere, performing heat preservation and calcination in a shaking environment at 500r/min for 11 hours, standing and cooling to room temperature, and collecting the bactericidal and antiviral modifier;

respectively weighing 40g of alicyclic epoxy resin YYR-8207, 10g of solvent, 0.7g of auxiliary agent, 3g of 0.1 mu m alumina powder, 3g of 7 mu m polyurethane elastomer particles as scratch-resistant powder, 8g of bactericidal and antiviral modifier, 2g of wax slurry, 1.0g of ultraviolet absorbent and 45g of curing agent, wherein the solvent is prepared from n-butyl acetate, propylene glycol methyl ether acetate and xylene according to a mass ratio of 4: 3: 3, the auxiliary agent is prepared from a dispersing agent 5040 and a defoaming agent XWC-T118 according to a mass ratio of 6: 4, preparing a composition;

under the low-speed stirring rate of 300rpm, sequentially adding a solvent, an auxiliary agent and half of alicyclic epoxy resin in the formula, continuously stirring for 5min, increasing the rotating speed to 700rpm, sequentially adding superfine aluminum oxide powder, scratch-resistant powder and a sterilizing and antiviral modifier again, finally increasing the rotating speed to 1100rpm, continuously stirring for 10min, collecting the stirred slurry, placing the slurry into a nano sand mill, controlling the particle size of a grinding medium to be 0.2mm, grinding for 9h to obtain grinding slurry, passing the grinding slurry through a 10-micron screen, placing the screened slurry under 750rpm, mixing and stirring the remaining half of alicyclic epoxy resin, 6900-20X wax slurry and an ultraviolet absorbent UV-234 to obtain a composite nano inorganic sterilizing and antiviral aging-resistant coating A component; and mixing the component A and a curing agent according to a formula, wherein the curing agent is silicon resin with amino functional groups, and uniformly stirring to obtain the inorganic bactericidal antiviral anti-aging coating.

Example 3

respectively weighing 50g of copper acetate solution, 15g of dialysate, 3g of span-80 and 15g of liquid paraffin, placing the copper acetate solution, the dialysate, the span-80 and the liquid paraffin into a homogenizer, homogenizing, collecting homogenized liquid, and adjusting the pH to 8.5 by using sodium hydroxide solution with the mass fraction of 5% to obtain mixed liquid;

taking needle-shaped nano zinc oxide particles with the diameter of 20nm and the length-diameter ratio of 100, stirring and mixing the needle-shaped zinc oxide particles, the mixed solution and a glucose solution with the mass fraction of 5.6% according to the mass ratio of 1:5:10, placing the mixture at 2000r/min for centrifugal separation, collecting lower-layer precipitates, alternately washing the lower-layer precipitates with ethanol and deionized water, collecting the washed particles, placing the washed particles at 60 ℃ for drying for 12 hours, grinding, dispersing and collecting dispersed microspheres, placing the dispersed microspheres in an air atmosphere at 400 ℃, carrying out heat preservation and calcination for 12 hours under a shaking environment at 500r/min, standing and cooling to room temperature, and collecting the bactericidal and antiviral modifier;

60g of alicyclic epoxy resin ER-662, 15g of solvent, 2.0g of auxiliary agent, 5g of 0.1 mu m alumina powder, 5g of 7 mu m polyurethane elastomer particles serving as scratch-resistant powder, 13g of bactericidal and antiviral modifier, 3g of 6900-20X wax slurry, 1.5g of ultraviolet absorbent and 60g of curing agent are respectively weighed, wherein the solvent is prepared from n-butyl acetate, propylene glycol methyl ether acetate and xylene according to a mass ratio of 4: 3: 3, the auxiliary agent is prepared from a dispersing agent 5040 and a defoaming agent XWC-T118 according to a mass ratio of 6: 4, preparing a composition;

under the low-speed stirring rate of 400rpm, sequentially adding a solvent, an auxiliary agent and a half mass of alicyclic epoxy resin in the formula, continuously stirring for 5min, increasing the rotating speed to 800rpm, sequentially adding superfine aluminum oxide powder, scratch-resistant powder and a sterilizing and antiviral modifier again, finally increasing the rotating speed to 1200rpm, continuously stirring for 10min, collecting the stirred slurry, placing the slurry into a nano sand mill, controlling the particle size of a grinding medium to be 0.2mm, grinding for 10h to obtain grinding slurry, passing the grinding slurry through a 10-micron screen, placing the screened slurry into 800rpm, mixing and stirring the remaining half mass of alicyclic epoxy resin, wax slurry and an ultraviolet absorbent UV-531 to obtain a composite nano inorganic sterilizing and antiviral aging-resistant coating component A; and mixing the component A and a curing agent according to a formula, wherein the curing agent is silicon resin with amino functional groups, and uniformly stirring to obtain the inorganic bactericidal antiviral anti-aging coating.

Example 4

The modified antibacterial antiviral modifier is prepared by mixing the flaky nano-porous cuprous oxide with the acicular nano-zinc oxide and grinding for 6 hours in example 4 instead of the antibacterial antiviral modifier in example 1, and the rest conditions and component proportions are the same as those in example 1.

Performance test

Respectively carrying out performance tests on the inorganic antibacterial antiviral anti-aging coating prepared in the embodiment 1-4, coating and curing the coating prepared in the embodiment 1-4 into a coating, and specifically testing the antibacterial property, antibacterial durability, antifungal property and adhesiveness (scratch resistance) of the inorganic antibacterial antiviral anti-aging coating prepared by scanning through a scanning electron microscope with nano cuprous oxide and nano zinc oxide.

Detection method/test method

(1) And (3) antibacterial property: the test strains used Escherichia coli ATCC8739, Staphylococcus aureus ATCC 6538. The antibacterial performance of the fiber is evaluated by adopting a bacteriostatic circle method, and the relevant detection standard is derived from AATCC90-1982 'antibacterial fiber determination method-plate culture medium method'. The bacteriostatic ring method is a qualitative test method and is mostly used for identifying dissoluble bacteriostatic materials and products containing the dissoluble bacteriostatic materials. The antibacterial material is continuously dissolved and is diffused by agar to form different concentration gradients so as to show the antibacterial effect. And comparing the diameters of the inhibition zones of the antibacterial material and the reference material to evaluate the performance of the antibacterial material. The larger the inhibition zone is, the better the inhibition effect is. When the diameter of the inhibition zone is larger than 14mm, the patient is judged to have the inhibition effect; if the diameter of the inhibition zone is less than or equal to 14mm, judging that the inhibition zone has no inhibition effect; if the results are about bacteriostatic in all the 3 repeated tests, judging the product to be qualified; the reference material does not correspondingly generate a bacteriostatic zone, otherwise, the test is invalid;

(2) scratch resistance: a rotating friction rubber wheel method is adopted, and the rubber wheel is controlled to rotate at a speed of 500g/500 for processing;

(3) resistance to mold: the molds include Aspergillus brasilense ATCC9642, Chaetomium globosum ATCC6205, Trichoderma viride ATCC9645, Aureobasidium pullulans ATCC15233, and the mildew resistance test was carried out by the Petri dish method (suitable for testing the mold resistance of the paint using a small sample) according to the national standard GB/T1741-1979 (1989). The prepared sample is coated on a sterilized filter paper sheet (the front and the back of the filter paper sheet are coated), and the filter paper sheet is horizontally placed on the surface of a culture medium after being irradiated by 3d ultraviolet light. The strain suspension is uniformly and finely sprayed on the sample plate by a sprayer, and the sample plate is covered with a dish after being slightly dried. The cover opening is marked with the sample, the number and the date, and the mixture is put into an incubator to be cultured at 29 to 30 ℃; checking whether the mildew on the surface of the template is normal after 28 d;

(4) antibacterial durability: after 5000h xenon lamp accelerated aging, testing the inhibition and killing effect change of the coating on viruses, bacteria and mould;

(5) and (3) virus killing: the coating was placed at 1m³In the closed space, the area of the coating is controlled to be 1m²Spraying the virus on the coatingIn the upper space, the virus killing rate in the space is detected after 1 h.

The specific detection results are shown in the following table 1:

TABLE 1 Performance test Table

Referring to the comparison of the performance tests of table 1, it can be found that:

comparing the performances of examples 1-3, it is demonstrated that the antibacterial and scratch resistance properties of example 3 are the best, since the ratio of the added materials is the highest in example 3, demonstrating that the solution of the present application is practicable.

Comparing the performances of the embodiment 1 and the embodiment 4, the bactericidal antiviral modifier is prepared by mixing the flaky nano porous copper oxide with the acicular nano zinc oxide and grinding the mixture for 6-8 h in the embodiment 4, so that the bactericidal antiviral modifier in the embodiment 1 is replaced, the antibacterial performance and the durability are reduced, and compared with the structure of a sheet layer, the porous structure can improve the load performance, so that the antibacterial durability and the scratch resistance of the coating are improved.

Comparative example

Comparative examples 1 to 5

In comparative examples 1 to 5, commercially available nano-porous cuprous oxide mixed with nano-zinc oxide compounded particles were used in place of the bactericidal antiviral modifier in example 1, and the other conditions and component ratios were the same as in example 1, as shown in table 2.

TABLE 2 raw material composition of composite bactericidal antiviral anti-aging coating for helmet surface layer in comparative examples 1-5

Comparative examples 6 to 9

In comparative examples 6 to 9, titanium dioxide was used instead of the anti-scratch powder in the composite bactericidal antiviral anti-aging coating for helmet skins, as shown in Table 3.

TABLE 3 COMPARATIVE EXAMPLES 6-9 COMPOSITE STERILIZING, ANTI-VIRUS AND ANTI-AGEING COATING COMPOSITION FOR HELMET SURFACE

Weight/kg	Comparative example 6	Comparative example 7	Comparative example 8	Comparative example 9
					Cycloaliphatic epoxy resins	30	30	30	30
Solvent(s)	5	5	5	5
					Auxiliary agent	0.5	0.5	0.5	0.5
Ultrafine alumina powder	2	2	2	2
					Titanium white powder	2	3	4	5
Bactericidal antiviral modifier	5	5	5	5
					Wax slurry	1	1	1	1
Ultraviolet absorber	0.5	0.5	0.5	0.5
					Curing agent	30	30	30	30

Comparative examples 10 to 15

Comparative examples 10 to 15 epoxy resin E51 was used in place of the alicyclic epoxy resin in the composite antibacterial antiviral anti-aging paint for helmet skins, and the remaining components were the same as in example 1, as shown in table 4.

TABLE 4 raw material composition of composite bactericidal antiviral anti-aging coating for helmet skin in comparative examples 10-15

The performance test tests are respectively carried out on the comparative examples 1-15, the coatings prepared in the comparative examples 1-15 are coated and cured to form coatings, and specifically, the scanning electron microscope scanning of the nano cuprous oxide and the nano zinc oxide is tested to test the antibacterial property, antibacterial durability, antifungal property and adhesiveness (scratch resistance) of the prepared inorganic bactericidal antiviral aging-resistant coatings.

Detection method/test method

(3) resistance to mold: the molds include Aspergillus brasilense ATCC9642, Chaetomium globosum ATCC6205, Trichoderma viride ATCC9645, Aureobasidium pullulans ATCC15233, and the mildew resistance test was carried out by the Petri dish method (suitable for testing the mold resistance of the paint using a small sample) according to the national standard GB/T1741-1979 (1989). The prepared sample is coated on a sterilized filter paper sheet (the front and the back of the filter paper sheet are coated), and the filter paper sheet is horizontally placed on the surface of a culture medium after being irradiated by 3d ultraviolet light. The strain suspension is uniformly and finely sprayed on the sample plate by a sprayer, and the sample plate is covered with a dish after being slightly dried. The cover opening is marked with the sample, the number and the date, and the mixture is put into an incubator to be cultured at 29 to 30 ℃; after 28d, the surface of the template is checked to see whether the mildew is normal.

(5) and (3) virus killing: the coating is placed in a closed space with the thickness of 1m3, the area of the coating is controlled to be 1m2, the virus is sprayed into the space above the coating, and the virus killing rate in the space is detected after 1 h.

The specific test results are shown in table 5 below:

TABLE 5 Performance test Table

Referring to the comparison of the performance tests of table 5, it can be found that:

comparing the performances of comparative examples 1-5 with example 1, the antibacterial performance and antibacterial durability of comparative examples 1-5 are significantly reduced because the particles compounded by mixing nano-porous copper oxide and nano-zinc oxide are adopted to replace the bactericidal and antiviral modifier in example 1, the structure is an effective compound, and the effective combination system in example 1 cannot be achieved in actual use.

Comparing the performances of the comparative examples 6-9 with the performances of the example 1, because the titanium dioxide is adopted in the comparative examples 6-9 to replace the scratch-resistant powder in the composite bactericidal antiviral anti-aging coating for the helmet surface layer, the bonding performance between the titanium dioxide structure and the matrix resin is poor, and because the titanium dioxide only has the reinforcing effect and does not have the scratch-resistant effect, the antibacterial performance of the comparative examples 6-9 is not reduced, but the durability and the scratch-resistant performance are greatly reduced.

Finally, comparing comparative examples 10-15 with example 1, comparative examples 10-15 using epoxy resin E51 instead of the resin of example 1 of the present application resulted in a substantial decrease in overall durability and scratch resistance, which demonstrates that the amino functional group-modified silicone resin material employed in the present application is effective in improving the durability of the silicone resin material.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims

1. The composite bactericidal antiviral anti-aging coating for the helmet surface layer is characterized by being prepared from the following raw materials in parts by weight:

30-60 parts of alicyclic epoxy resin;

5-15 parts of a solvent;

0.5-2.0 parts of an auxiliary agent;

2-5 parts of superfine alumina powder;

2-5 parts of scratch-resistant powder;

5-13 parts of a bactericidal antiviral modifier;

1-3 parts of wax slurry;

0.5-1.5 parts of ultraviolet absorbent;

30-60 parts of a curing agent; the sterilizing and antiviral modifier is prepared by compounding nano zinc oxide and nano cuprous oxide; the nano zinc oxide in the bactericidal and antiviral modifier is needle-shaped nano zinc oxide with the diameter of 20-30 nm and the length-diameter ratio of more than 100, and the nano cuprous oxide in the bactericidal and antiviral modifier is any one of flaky nano cuprous oxide or porous nano cuprous oxide; the scratch-resistant powder is polyurethane elastomer particles with the particle size of 7-9 mu m; the curing agent is a silicone resin with amino functional groups.

2. The composite bactericidal antiviral anti-aging coating for the helmet surface layer according to claim 1, wherein the bactericidal antiviral modifier is prepared by compounding needle-shaped nano zinc oxide and porous nano cuprous oxide, and comprises the following steps:

adding peach gum into deionized water, grinding, dispersing, sieving, dialyzing, and collecting dialysate; mixing copper acetate solution, dialysate, span-80 and liquid paraffin, homogenizing, and adjusting pH to 8.5 to obtain mixed solution;

taking needle-shaped nano zinc oxide particles, mixing the needle-shaped nano zinc oxide particles, the mixed solution and the glucose solution according to the mass ratio of 1: 3-5: 10-15, stirring, mixing, centrifuging, collecting lower-layer precipitates, washing, drying, grinding, dispersing, calcining, standing and cooling to obtain the bactericidal and antiviral modifier.

3. The composite bactericidal antiviral anti-aging coating for the surface layer of the helmet as claimed in claim 2, wherein the calcination treatment is: and (3) carrying out heat preservation and calcination for 10-12 hours at 350-400 ℃ in an air atmosphere under a shaking environment at 500 r/min.

4. The composite bactericidal antiviral anti-aging coating for the helmet surface layer as claimed in claim 1, wherein the auxiliary agent is a mixture of a dispersing agent and a defoaming agent in a mass ratio of 6: 4.

5. The preparation method of the composite bactericidal antiviral anti-aging coating for the surface layer of the helmet as claimed in claim 1, characterized by comprising the following steps:

s1, sequentially adding a solvent, an auxiliary agent and a half mass of alicyclic epoxy resin at a stirring speed of 200-400 rpm, continuously stirring, increasing the rotating speed to 500-800 rpm, sequentially adding superfine aluminum oxide powder, scratch-resistant powder and a sterilizing and antiviral modifier again, finally increasing the rotating speed to 1000-1200 rpm, and collecting stirring slurry after stirring;

s2, grinding the stirred slurry and collecting screened slurry;

s3, placing the sieved slurry at a low-speed stirring speed, and mixing and stirring the remaining half mass of alicyclic epoxy resin, wax slurry and ultraviolet absorbent to obtain a composite bactericidal antiviral anti-aging coating A component for the surface layer of the helmet, wherein the low-speed stirring speed is any one of 500rpm, 750rpm and 800 rpm;

s4, mixing the component A and the curing agent according to the formula, and stirring uniformly to obtain the composite bactericidal antiviral anti-aging coating for the surface layer of the helmet.

6. The method for preparing the composite bactericidal antiviral anti-aging coating for the surface layer of the helmet as claimed in claim 5, wherein the grinding treatment in step S2 comprises the following specific steps:

s21, collecting the stirred slurry, placing the stirred slurry in a nano sand mill, controlling the particle size of a grinding medium to be 0.2mm, grinding for 8-10 h to obtain grinding slurry, and sieving by a 10-micron sieve to obtain sieving slurry.