Graphene-containing antibacterial heat-generating building decoration wall cloth and preparation method thereof

Abstract

The invention relates to the technical field of wall cloth, in particular to graphene-containing antibacterial and heat-generating building decoration wall cloth and a preparation method thereof, the graphene-containing antibacterial and heat-generating building decoration wall cloth comprises a base cloth layer, an antibacterial and heat-generating functional layer and a surface protection layer; the antibacterial heat-generating functional layer is prepared from the following raw materials in parts by weight: 5 to 12 parts of modified graphene, 30 to 50 parts of waterborne polyurethane emulsion, 3 to 8 parts of an antibacterial additive, 1 to 3 parts of a dispersing agent, 2 to 5 parts of a film-forming agent, 1 to 4 parts of a toughening agent and 20 to 40 parts of deionized water; the modified graphene is prepared by modifying with a modifying solution and ball-milling with a ball-milling material. Through the synergistic effect of the modified liquid and the ball milling material, not only is the dispersity of the graphene improved, but also the antibacterial and heat generation performance of the graphene is synergistically enhanced, so that the wall cloth has efficient antibacterial and rapid heat generation functions.

Description

Technical Field

[0001] This invention relates to the field of wall covering technology, specifically to an antibacterial and heat-generating architectural decorative wall covering containing graphene and its preparation method. Background Technology

[0002] As an important material for interior decoration, architectural wall coverings not only beautify spaces but are also increasingly developing in terms of functionality, such as antibacterial, heat insulation, and heat generation. With people's increasing demands for healthy and comfortable living environments, wall coverings with both antibacterial and heat-generating functions have received widespread attention.

[0003] Graphene, as a novel two-dimensional carbon material, possesses excellent thermal and electrical conductivity, mechanical properties, and antibacterial properties, and is widely used in the modification of functional materials. However, pristine graphene suffers from the problem of easy agglomeration of its sheets, resulting in poor dispersion in composite materials and hindering the full realization of its superior properties, thus limiting its application in architectural decorative wall coverings. Furthermore, the antibacterial and thermal properties of single graphene still have room for improvement, failing to meet the demands of high-end interior decoration for multifunctional and high-performance materials.

[0004] While existing research has explored the application of graphene in wallcoverings, it primarily utilizes unmodified graphene or simple coupling agents, resulting in limited modification effects and persistent issues such as poor dispersibility and insufficient antibacterial and thermal properties. Furthermore, the lack of targeted modification system design hinders the achievement of good compatibility between graphene and the wallcovering substrate, leading to easy detachment of the functional layer and a short lifespan. Therefore, developing a technical solution that optimizes graphene performance through specific modification processes to enhance the antibacterial and thermal properties and lifespan of wallcoverings has significant practical implications and application value. Summary of the Invention

[0005] In view of the deficiencies of the prior art, the purpose of this invention is to provide a graphene-containing antibacterial and heat-generating architectural decorative wall covering and its preparation method, so as to solve the problems mentioned in the background art.

[0006] The present invention solves the technical problem by adopting the following technical solution: This invention provides a graphene-containing antibacterial and heat-generating architectural decorative wall covering, comprising a base fabric layer, an antibacterial and heat-generating functional layer, and a surface protective layer; the raw materials of the antibacterial and heat-generating functional layer, by weight, include 5-12 parts of modified graphene, 30-50 parts of waterborne polyurethane emulsion, 3-8 parts of antibacterial additives, 1-3 parts of dispersant, 2-5 parts of film-forming agent, 1-4 parts of toughening agent, and 20-40 parts of deionized water; the modified graphene is obtained by modification with a modifying liquid and ball milling with ball milling material.

[0007] Furthermore, the preparation method of the modified graphene includes the following steps: S1. Preparation of modified solution: Mix 2-5 parts of carbon nanofibers, 1-4 parts of aluminum borate whiskers and 5-8 parts of 5% lanthanum chloride solution evenly to obtain a mixed conditioning solution; mix 3-5 parts of nano-attapulgite clay, 2-5 parts of nano-cellulose and 5-8 parts of silane solution thoroughly to obtain a conditioning agent; stir the conditioning agent and mixed conditioning solution evenly at a weight ratio of 2:(3-5) to obtain the modified solution; the silane solution is prepared by mixing silane coupling agent KH560 and ethanol aqueous solution at a weight ratio of 2:(7-9); S2. Graphene Modification Treatment: Graphene is first modified by stirring in a modification liquid at a ratio of 3-5 times the total amount of graphene at a stirring speed of 450-500 r / min for 1 hour. After stirring, a modified graphene liquid is obtained. 15-20% of the total amount of ball milling material is added to the modified graphene liquid and ball milled at a speed of 1000-1500 r / min for 2 hours. After ball milling, the mixture is filtered and dried to obtain modified graphene. The ball milling material is prepared by mixing 3-5 parts of silicon carbide, 2-4 parts of 5% chitosan solution, 5-8 parts of nano-titanium dioxide, and 2-4 parts of 3-5% sodium citrate solution evenly to obtain the ball milling material.

[0008] In this invention, the formulation design of the modified liquid has a synergistic effect: the carbon nanofibers in the conditioning liquid can form a three-dimensional conductive network with graphene, improving heat generation and thermal conductivity; aluminum borate whiskers can enhance the mechanical properties of graphene and simultaneously improve the antibacterial effect; lanthanum chloride solution can regulate the surface charge distribution of graphene and reduce agglomeration. The nano-attapulgite in the conditioning agent has excellent adsorption properties, can adsorb antibacterial components and release them slowly, prolonging the antibacterial effect; nanocellulose can improve the compatibility between the modified liquid and graphene, while enhancing the film-forming properties of the functional layer; the silane coupling agent KH560 can further improve the compatibility between graphene and waterborne polyurethane emulsion, and enhance the bonding force between the functional layer and the base fabric layer.

[0009] In the ball milling material formulation, silicon carbide, as the milling medium, can fully disperse graphene and improve its thermal conductivity; chitosan itself has excellent antibacterial properties and can work synergistically with graphene and antibacterial additives to enhance the antibacterial effect; nano-titanium dioxide is a photocatalytic antibacterial material that can generate free radicals under light conditions, destroying bacterial structures and achieving long-lasting antibacterial effects; sodium citrate solution can adjust the stability of the ball milling system and prevent secondary agglomeration of graphene.

[0010] Furthermore, the antibacterial adjuvant is a compound of nano zinc oxide and nano silver particles in a weight ratio of (3-5):1, with a particle size of 50-100 nm. The synergistic effect of nano zinc oxide and nano silver particles can expand the antibacterial range and improve the antibacterial efficiency. At the same time, the addition of nano silver particles can reduce the amount of nano zinc oxide used, reduce costs, and avoid its impact on the appearance of the wallpaper.

[0011] Furthermore, the dispersant is a polycarboxylate dispersant, the film-forming agent is polyvinyl alcohol, and the toughening agent is dibutyl phthalate; the base fabric layer is a blend of flax fiber and polyester fiber with a blend weight ratio of (2-3):1. Flax fiber has good breathability and moisture absorption, while polyester fiber has excellent mechanical properties and abrasion resistance. The blend can balance the comfort and service life of the wallpaper; the surface protective layer is a water-based polyvinyl fluoride coating with a thickness of 5-10 μm. Water-based polyvinyl fluoride has excellent stain resistance, water resistance, and abrasion resistance, which can protect the functional layer, extend the service life of the wallpaper, and at the same time not affect the breathability of the wallpaper.

[0012] The present invention also provides a method for preparing the above-mentioned graphene-containing antibacterial and heat-generating architectural decorative wall covering, comprising the following steps: Step 1: Preparation of modified graphene: Prepare modified graphene according to the method described above; Step 2: Preparation of antibacterial and heat-generating functional slurry: Add aqueous polyurethane emulsion and deionized water to a mixing tank, stir at 200-300 r / min for 10-15 min to fully disperse the aqueous polyurethane emulsion; add dispersant and modified graphene sequentially, heat to 40-50℃, adjust the speed to 600-800 r / min, and stir for 30-40 min to ensure uniform dispersion of the modified graphene; then add antibacterial additives, film-forming agents, and toughening agents, and continue stirring for 20-30 min to obtain the antibacterial and heat-generating functional slurry; Step 3, Pretreatment of base fabric: Immerse the base fabric layer in a 2-3% sodium hydroxide aqueous solution at 40-50℃ for 20-30 minutes to remove impurities and grease from the surface of the base fabric, improve the hydrophilicity of the base fabric, and facilitate the adhesion of functional paste; after taking it out, rinse it with deionized water until neutral, and dry it until the moisture content is ≤5% to avoid moisture affecting the film-forming effect of the functional layer. Step 4, Functional Layer Coating: Apply the antibacterial and heat-generating functional slurry to the surface of the pretreated base fabric layer using a doctor blade coating method. The coating thickness is 20-30 μm. After coating, place it in an oven and pre-bake at 80-90℃ for 15-20 minutes to remove moisture from the slurry and prevent air bubbles from forming during the curing process. Then, raise the temperature to 120-130℃ and cure for 30-40 minutes to fully cure the functional layer and improve its adhesion to the base fabric layer. The base fabric-functional layer composite is obtained. Step 5, Surface protection treatment: Dilute the water-based polyvinyl fluoride coating and apply it to the surface of the functional layer by spraying. The spray thickness is 5-10μm. After drying at room temperature, dry it at 100-110℃ for 10-15 minutes to fully cure the surface protective layer and obtain graphene-containing antibacterial and heat-generating architectural decorative wall covering.

[0013] Furthermore, in step 2, the viscosity of the antibacterial and heat-generating functional slurry is adjusted to 2000-3000 mPa·s. This viscosity range ensures that the slurry has good coating performance, preventing sagging due to too low a viscosity and uneven coating due to too high a viscosity. In step 4, the scraper speed for scraper coating is 1-2 m / min, which ensures uniform coating thickness and improves the appearance quality of the functional layer. In step 5, the dilution ratio of the water-based polyvinyl fluoride coating is coating:deionized water = 1:(0.8-1.2). The diluted coating has good spraying performance and can form a uniform protective layer.

[0014] Compared with the prior art, the present invention has the following beneficial effects: This invention modifies graphene through a specific modification process, solving the problems of easy agglomeration and poor dispersibility of original graphene sheets. This allows graphene to be uniformly dispersed in the antibacterial and heat-generating functional layer, fully leveraging its excellent thermal and electrical conductivity and antibacterial properties. The synergistic effect of the modification liquid and the ball milling material not only improves the dispersibility of graphene but also synergistically enhances its antibacterial and heat-generating properties, giving the wall covering both highly efficient antibacterial and rapid heat-generating functions.

[0015] The antibacterial and heat-generating functional layer of this invention uses modified graphene and antibacterial additives for synergistic antibacterial action. It has a wide antibacterial range and high antibacterial efficiency, and can effectively inhibit the growth and reproduction of common bacteria such as Escherichia coli and Staphylococcus aureus. The antibacterial rate can reach more than 99%, and it has a long-lasting antibacterial effect. At the same time, the three-dimensional conductive network formed by the modified graphene can achieve efficient heat generation. After being energized, it can heat up rapidly, with a heating rate of 3-5℃ / min, and the temperature distribution is uniform, which can improve indoor comfort.

[0016] The preparation method of this invention has a reasonable process. The bonding force between the functional layer and the base fabric layer is improved by pre-treatment of the base fabric. The mechanical properties, stain resistance, water resistance and wear resistance of the wall covering are improved by step curing and surface protection treatment, and the service life of the wall covering is extended. The whole preparation process is environmentally friendly and pollution-free, which is in line with the development trend of green building materials. Detailed Implementation

[0017] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to specific examples. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Example 1 An antibacterial and heat-generating architectural decorative wall covering containing graphene includes a base fabric layer, an antibacterial and heat-generating functional layer, and a surface protective layer. The raw materials of the antibacterial and heat-generating functional layer, by weight, include 5 parts modified graphene, 30 parts waterborne polyurethane emulsion, 3 parts antibacterial additives, 1 part polycarboxylate dispersant, 2 parts polyvinyl alcohol, 1 part dibutyl phthalate, and 20 parts deionized water. The base fabric layer is a blend of flax fiber and polyester fiber in a weight ratio of 2:1. The surface protective layer is a waterborne polyvinyl fluoride coating with a thickness of 5 μm. The antibacterial additives are nano-zinc oxide and nano-silver particles compounded in a weight ratio of 3:1, with a particle size of 50 nm.

[0019] The preparation method of the above-mentioned graphene-containing antibacterial and heat-generating architectural decorative wall covering includes the following steps: Step 1: Preparation of modified graphene: S1. Preparation of the modified solution: 2 parts carbon nanofibers, 1 part aluminum borate whiskers and 5 parts lanthanum chloride solution (5% by mass) are mixed evenly to obtain a mixed conditioning solution; 3 parts nano-attapulgite clay, 2 parts nano-cellulose and 5 parts silane solution are mixed thoroughly to obtain a conditioning agent; the conditioning agent and the mixed conditioning solution are stirred evenly at a weight ratio of 2:3 to obtain the modified solution; the silane solution is prepared by mixing silane coupling agent KH560 and ethanol aqueous solution at a weight ratio of 2:7. S2. Graphene Modification Treatment: Graphene is first modified by stirring in a modification liquid with a total volume of 3 times the total graphene volume at a stirring speed of 450 r / min for 1 h to obtain a modified graphene liquid. Then, 15% of the total volume of the modified graphene liquid is added to the modified graphene liquid and ball-milled at a speed of 1000 r / min for 2 h. After ball milling, the mixture is filtered and dried to obtain modified graphene. The ball-milling material is prepared by mixing 3 parts silicon carbide, 2 parts 5% chitosan solution, 5 parts nano-titanium dioxide, and 2 parts 3% sodium citrate solution evenly to obtain the ball-milling material. Step 2: Preparation of antibacterial and heat-generating functional slurry: Add waterborne polyurethane emulsion and deionized water to a mixing tank, stir at 200 r / min for 10 min, add polycarboxylate dispersant and modified graphene in sequence, heat to 40℃, adjust the speed to 600 r / min, stir for 30 min, then add antibacterial additive, polyvinyl alcohol and dibutyl phthalate, continue stirring for 20 min, adjust the viscosity to 2000 mPa·s, and obtain antibacterial and heat-generating functional slurry; Step 3, Pretreatment of base fabric: Immerse the base fabric layer in a 2% sodium hydroxide aqueous solution at 40°C for 20 minutes, then rinse with deionized water until neutral, and dry until the moisture content is ≤5%; Step 4, Functional layer coating: The antibacterial and heat-generating functional slurry is coated onto the surface of the pretreated base fabric layer using a doctor blade coating method. The coating thickness is 20μm and the doctor blade speed is 1m / min. After coating, it is placed in an oven and pre-baked at 80℃ for 15min, then heated to 120℃ and cured for 30min to obtain the base fabric-functional layer composite. Step 5, Surface protection treatment: Dilute the water-based polyvinyl fluoride coating at a ratio of coating to deionized water of 1:0.8, apply it to the surface of the functional layer by spraying, with a spray thickness of 5μm, let it dry at room temperature, and then dry it at 100℃ for 10 minutes to obtain graphene-containing antibacterial and heat-generating architectural decorative wall covering.

[0020] Example 2 An antibacterial and heat-generating architectural decorative wall covering containing graphene includes a base fabric layer, an antibacterial and heat-generating functional layer, and a surface protective layer. The raw materials of the antibacterial and heat-generating functional layer, by weight, include 8 parts modified graphene, 40 parts waterborne polyurethane emulsion, 5 parts antibacterial additives, 2 parts polycarboxylate dispersant, 3 parts polyvinyl alcohol, 2 parts dibutyl phthalate, and 30 parts deionized water. The base fabric layer is a blend of flax fiber and polyester fiber in a weight ratio of 2.5:1. The surface protective layer is a waterborne polyvinyl fluoride coating with a thickness of 8 μm. The antibacterial additives are nano-zinc oxide and nano-silver particles compounded in a weight ratio of 4:1, with a particle size of 80 nm.

[0021] The preparation method of the above-mentioned graphene-containing antibacterial and heat-generating architectural decorative wall covering includes the following steps: Step 1: Preparation of modified graphene: S1. Preparation of the modified solution: 3 parts carbon nanofibers, 2 parts aluminum borate whiskers and 6 parts 5% lanthanum chloride solution are mixed evenly to obtain a mixed conditioning solution; 4 parts nano-attapulgite clay, 3 parts nano-cellulose and 6 parts silane solution are mixed thoroughly to obtain a conditioning agent; the conditioning agent and the mixed conditioning solution are stirred evenly at a weight ratio of 2:4 to obtain the modified solution; the silane solution is prepared by mixing silane coupling agent KH560 and ethanol aqueous solution at a weight ratio of 2:8. S2. Graphene Modification Treatment: Graphene is first modified by stirring in a modification solution with a total volume of 4 times the total graphene volume at a stirring speed of 480 r / min for 1 h to obtain a modified graphene solution. Then, 18% of the total volume of the modified graphene solution is added to the modified graphene solution and ball-milled at a speed of 1200 r / min for 2 h. After ball milling, the mixture is filtered and dried to obtain modified graphene. The ball-milling material is prepared by mixing 4 parts silicon carbide, 3 parts chitosan solution (5% by mass), 6 parts nano-titanium dioxide, and 3 parts sodium citrate solution (4% by mass) evenly to obtain the ball-milling material. Step 2: Preparation of antibacterial and heat-generating functional slurry: Add waterborne polyurethane emulsion and deionized water to a mixing tank, stir at 250 r / min for 12 min, add polycarboxylate dispersant and modified graphene in sequence, heat to 45℃, adjust the speed to 700 r / min, stir for 35 min, then add antibacterial additive, polyvinyl alcohol and dibutyl phthalate, continue stirring for 25 min, adjust the viscosity to 2500 mPa·s, and obtain antibacterial and heat-generating functional slurry; Step 3, Pretreatment of base fabric: Immerse the base fabric layer in a 2.5% sodium hydroxide aqueous solution at 45°C for 25 minutes, then rinse with deionized water until neutral, and dry until the moisture content is ≤5%; Step 4, Functional layer coating: The antibacterial and heat-generating functional slurry is coated onto the surface of the pretreated base fabric layer using a doctor blade coating method. The coating thickness is 25μm and the doctor blade speed is 1.5m / min. After coating, it is placed in an oven and pre-baked at 85℃ for 18min, then heated to 125℃ and cured for 35min to obtain the base fabric-functional layer composite. Step 5, Surface protection treatment: Dilute the water-based polyvinyl fluoride coating at a ratio of coating to deionized water of 1:1, apply it to the surface of the functional layer by spraying, with a spray thickness of 8μm, let it dry at room temperature, and then dry it at 105℃ for 12 minutes to obtain graphene-containing antibacterial and heat-generating architectural decorative wall covering.

[0022] Example 3 An antibacterial and heat-generating architectural decorative wall covering containing graphene includes a base fabric layer, an antibacterial and heat-generating functional layer, and a surface protective layer. The raw materials of the antibacterial and heat-generating functional layer, by weight, include 12 parts modified graphene, 50 parts waterborne polyurethane emulsion, 8 parts antibacterial additives, 3 parts polycarboxylate dispersant, 5 parts polyvinyl alcohol, 4 parts dibutyl phthalate, and 40 parts deionized water. The base fabric layer is a blend of flax fiber and polyester fiber in a weight ratio of 3:1. The surface protective layer is a waterborne polyvinyl fluoride coating with a thickness of 10 μm. The antibacterial additives are nano-zinc oxide and nano-silver particles compounded in a weight ratio of 5:1, with a particle size of 100 nm.

[0023] The preparation method of the above-mentioned graphene-containing antibacterial and heat-generating architectural decorative wall covering includes the following steps: Step 1: Preparation of modified graphene: S1. Preparation of the modified solution: 5 parts carbon nanofibers, 4 parts aluminum borate whiskers and 8 parts 5% lanthanum chloride solution are mixed evenly to obtain a mixed conditioning solution; 5 parts nano-attapulgite clay, 5 parts nano-cellulose and 8 parts silane solution are mixed thoroughly to obtain a conditioning agent; the conditioning agent and the mixed conditioning solution are stirred evenly at a weight ratio of 2:5 to obtain the modified solution; the silane solution is prepared by mixing silane coupling agent KH560 and ethanol aqueous solution at a weight ratio of 2:9. S2. Graphene Modification Treatment: Graphene is first modified by stirring in a modification liquid with a total volume of 5 times the total graphene volume at a stirring speed of 500 r / min for 1 h to obtain a modified graphene liquid. Then, 20% of the total volume of the modified graphene liquid is added to the modified graphene liquid and ball-milled at a speed of 1500 r / min for 2 h. After ball milling, the mixture is filtered and dried to obtain modified graphene. The ball-milling material is prepared by mixing 5 parts silicon carbide, 4 parts chitosan solution (5% by mass), 8 parts nano-titanium dioxide, and 4 parts sodium citrate solution (5% by mass) evenly to obtain the ball-milling material. Step 2: Preparation of antibacterial and heat-generating functional slurry: Add waterborne polyurethane emulsion and deionized water to a mixing tank, stir at 300 r / min for 15 min, add polycarboxylate dispersant and modified graphene in sequence, heat to 50℃, adjust the speed to 800 r / min, stir for 40 min, then add antibacterial additive, polyvinyl alcohol and dibutyl phthalate, continue stirring for 30 min, adjust the viscosity to 3000 mPa·s, and obtain antibacterial and heat-generating functional slurry; Step 3, Pretreatment of base fabric: Immerse the base fabric layer in a 3% sodium hydroxide aqueous solution at 50°C for 30 minutes, then rinse with deionized water until neutral, and dry until the moisture content is ≤5%; Step 4, Functional layer coating: The antibacterial and heat-generating functional slurry is coated onto the surface of the pretreated base fabric layer using a doctor blade coating method. The coating thickness is 30μm and the doctor blade speed is 2m / min. After coating, it is placed in an oven and pre-baked at 90℃ for 20min, then heated to 130℃ and cured for 40min to obtain the base fabric-functional layer composite. Step 5, Surface protection treatment: Dilute the water-based polyvinyl fluoride coating at a ratio of coating to deionized water of 1:1.2, apply it to the surface of the functional layer by spraying, with a spray thickness of 10μm, let it dry at room temperature, and then dry it at 110℃ for 15min to obtain graphene-containing antibacterial and heat-generating architectural decorative wall covering.

[0024] Comparative Design and Performance Testing To verify the inventiveness and superiority of the modified graphene and formulation design of the present invention, the following five comparative examples were set up. Except for the differences described below, the raw materials and preparation methods of each comparative example are the same as those in Example 2.

[0025] Comparative Example 1: The graphene was not modified and the original graphene was used directly to replace the modified graphene in Example 2.

[0026] Comparative Example 2: No modifying liquid was added in the graphene modification, that is, in step 1, the graphene was directly mixed with the ball milling material and ball milled, and the other steps remained unchanged.

[0027] Comparative Example 3: No impurities were added during the preparation of the modified solution, that is, only a modifier was prepared in step 1. The modifier was used to replace the modified solution to modify the graphene, and the other steps remained unchanged.

[0028] Comparative Example 4: No ball milling material was added in the graphene modification, that is, in step 1, only the graphene was modified by stirring the modification liquid, without ball milling, and the other steps remained unchanged.

[0029] Comparative Example 5: The antibacterial adjuvant used only nano zinc oxide, without the addition of nano silver particles, and the other steps remained unchanged.

[0030] II. Performance Testing Methods 1. Antibacterial properties: The antibacterial properties of antibacterial coatings (films) were tested according to GB / T 21866-2008 "Determination of antibacterial properties and antibacterial effects of antibacterial coatings (films)". Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 6538) were selected to test the antibacterial rate of the samples. The test time was 24 hours.

[0031] 2. Heat generation performance: The sample was cut into 10cm×10cm specimens, a 50V voltage was applied, and the heating rate (time to heat from room temperature 25℃ to 40℃) and steady-state temperature (temperature after 30 minutes of power-on) of the specimen were tested using a thermocouple tester.

[0032] 3. Dispersion: The dispersion of graphene in the antibacterial and heat-generating functional layer was observed using an optical microscope and divided into three levels: excellent (no obvious agglomeration, uniform dispersion), good (a small amount of agglomeration, relatively uniform dispersion), and poor (a large amount of agglomeration, uneven dispersion).

[0033] 4. Adhesion: The adhesion between the functional layer and the base fabric layer is tested according to GB / T 9286-1998 "Cross-cut test of paint and varnish film". It is divided into 0-5 grades, with grade 0 being the best (the cut edge is completely smooth and there is no peeling) and grade 5 being the worst (large area of ​​the cut area peels off).

[0034] 5. Wear resistance: Tested according to GB / T 1768-2006 "Determination of abrasion resistance of paints and varnishes - Rotating rubber grinding wheel method", with a load of 1000g and a rotation of 5000 revolutions. The wear amount (mg) of the test sample is measured. The smaller the wear amount, the better the wear resistance.

[0035] Performance tests were conducted on the products of Examples 1-3 and Comparative Examples 1-5, and the test results are as follows: ; The performance test results above show that the wall coverings of Examples 1-3 of this invention are significantly superior to the comparative examples in terms of antibacterial properties, heat generation properties, graphene dispersibility, adhesion, and wear resistance. Furthermore, as the amount of modified graphene increases, the antibacterial, heat generation, and wear resistance properties of the wall covering gradually improve. This fully demonstrates the outstanding inventiveness and superiority of the modification process and formulation design of this invention, as specifically demonstrated below: Compared with Comparative Example 1 (unmodified graphene), Examples 1-3 showed an antibacterial rate increase of over 16%, a heating rate increase of over 94%, a steady-state temperature increase of over 29%, graphene dispersibility improved from poor to excellent, adhesion improved from level 3 to level 0, and wear was reduced by over 43%. Example 3, with the highest amount of modified graphene, exhibited the best performance, achieving an E. coli antibacterial rate of 99.9%, a heating rate of 4.8℃ / min, a steady-state temperature of 48.5℃, and a wear of only 1.8mg. This is because unmodified graphene is prone to agglomeration, failing to fully utilize its antibacterial and thermal conductivity properties, and exhibiting poor compatibility with the substrate. The modification process of this invention effectively solves the graphene agglomeration problem, improves its dispersibility and compatibility with the substrate, and synergistically enhances its antibacterial and thermal properties. Furthermore, increasing the amount of modified graphene further strengthens these effects.

[0036] Compared with Comparative Example 2 (without modified liquid), Comparative Example 3 (without mixed conditioning liquid), and Comparative Example 4 (without ball milling material), the performance of Example 2 is significantly improved in all aspects. Specifically, Comparative Example 2, lacking the modifying effect of the modified liquid, did not optimize the surface properties of graphene, resulting in insufficient dispersibility and compatibility. Comparative Example 3, lacking the mixed conditioning liquid, did not receive auxiliary enhancement of the mechanical, antibacterial, and thermal properties of graphene. Comparative Example 4, lacking the ball milling dispersion effect of the ball milling material, was prone to secondary agglomeration of graphene, failing to achieve sufficient dispersion. This indicates that the combined use of the modified liquid (mixed conditioning liquid and blending agent synergistically) and the ball milling material of this invention is key to optimizing graphene performance and improving the overall performance of the wall covering; the two work synergistically and are indispensable.

[0037] Compared with Comparative Example 5 (single antibacterial adjuvant), Example 2 has better antibacterial performance, indicating that the combined use of nano zinc oxide and nano silver particles can achieve synergistic antibacterial effect, expand the antibacterial range, and improve antibacterial efficiency, further proving the rationality and inventiveness of the formulation design of the present invention.

[0038] In summary, this invention modifies graphene through a specific modification process and combines it with a reasonable formulation design to prepare architectural decorative wall coverings that possess excellent antibacterial, heat-generating, dispersible, adhesive, and wear-resistant properties. Compared with existing technologies, it represents a significant improvement, possesses outstanding substantive features and significant progress, and meets the inventiveness requirements of an invention patent.

[0039] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0040] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A graphene-containing antibacterial and heat-generating architectural decorative wall covering, characterized in that, It includes a base fabric layer, an antibacterial and heat-generating functional layer, and a surface protective layer; the raw materials of the antibacterial and heat-generating functional layer, by weight, include 5-12 parts of modified graphene, 30-50 parts of waterborne polyurethane emulsion, 3-8 parts of antibacterial additives, 1-3 parts of dispersant, 2-5 parts of film-forming agent, 1-4 parts of toughening agent, and 20-40 parts of deionized water; the modified graphene is obtained by modification with a modifying liquid and ball milling with ball milling material.

2. The graphene-containing antibacterial and heat-generating architectural decorative wall covering according to claim 1, characterized in that, The method for preparing the modified graphene includes the following steps: S1. Preparation of modified solution: Mix 2-5 parts of carbon nanofibers, 1-4 parts of aluminum borate whiskers and 5-8 parts of 5% lanthanum chloride solution evenly to obtain a mixed conditioning solution; mix 3-5 parts of nano-attapulgite clay, 2-5 parts of nano-cellulose and 5-8 parts of silane solution thoroughly to obtain a conditioning agent; stir the conditioning agent and mixed conditioning solution evenly at a weight ratio of 2:(3-5) to obtain the modified solution; S2. Graphene Modification Treatment: First, add graphene to a modification liquid with a total volume of 3-5 times the total graphene volume and stir at a stirring speed of 450-500 r / min for 1 hour. After stirring, a modified graphene liquid is obtained. Then, add 15-20% of the total volume of the modified graphene liquid ball milling material to the modified graphene liquid and ball mill at a speed of 1000-1500 r / min for 2 hours. After ball milling, filter and dry to obtain modified graphene.

3. The graphene-containing antibacterial and heat-generating architectural decorative wall covering according to claim 1, characterized in that, The antibacterial adjuvant is a compound of nano zinc oxide and nano silver particles in a weight ratio of (3-5):1, with a particle size of 50-100nm.

4. The graphene-containing antibacterial and heat-generating architectural decorative wall covering according to claim 1, characterized in that, The dispersant is a polycarboxylate dispersant, the film-forming agent is polyvinyl alcohol, and the toughening agent is dibutyl phthalate; the base fabric layer is a blend of flax fiber and polyester fiber with a blending weight ratio of (2-3):1; the surface protective layer is a water-based polyvinyl fluoride coating with a thickness of 5-10 μm.

5. The graphene-containing antibacterial and heat-generating architectural decorative wall covering according to claim 2, characterized in that, The silane solution is prepared by mixing silane coupling agent KH560 and an aqueous ethanol solution in a weight ratio of 2:(7-9).

6. The graphene-containing antibacterial and heat-generating architectural decorative wall covering according to claim 2, characterized in that, The method for preparing the ball milling material is as follows: 3-5 parts of silicon carbide, 2-4 parts of chitosan solution with a mass fraction of 5%, 5-8 parts of nano titanium dioxide and 2-4 parts of sodium citrate solution with a mass fraction of 3-5% are mixed evenly to obtain the ball milling material.

7. A method for preparing a graphene-containing antibacterial and heat-generating architectural decorative wall covering as described in any one of claims 1-6, characterized in that, Includes the following steps: Step 1: Preparation of modified graphene: Prepare modified graphene according to the method described in claim 2; Step 2: Preparation of antibacterial and heat-generating functional slurry: Add waterborne polyurethane emulsion and deionized water to a mixing tank, stir at 200-300 r / min for 10-15 min, add dispersant and modified graphene in sequence, heat to 40-50℃, adjust the speed to 600-800 r / min, stir for 30-40 min, then add antibacterial additives, film-forming agent and toughening agent, and continue stirring for 20-30 min to obtain antibacterial and heat-generating functional slurry; Step 3, Pretreatment of base fabric: Immerse the base fabric layer in a 2-3% sodium hydroxide aqueous solution at 40-50℃ for 20-30 minutes, then rinse with deionized water until neutral, and dry until the moisture content is ≤5%; Step 4, Functional layer coating: Apply the antibacterial and heat-generating functional slurry to the surface of the pretreated base fabric layer using a doctor blade coating method. The coating thickness is 20-30μm. After coating, place it in an oven and pre-bake at 80-90℃ for 15-20min. Then raise the temperature to 120-130℃ and cure for 30-40min to obtain the base fabric-functional layer composite. Step 5, Surface protection treatment: Dilute the water-based polyvinyl fluoride coating and apply it to the surface of the functional layer by spraying. The spray thickness is 5-10μm. After drying at room temperature, dry it at 100-110℃ for 10-15 minutes to obtain graphene-containing antibacterial and heat-generating architectural decorative wall covering.

8. The preparation method according to claim 7, characterized in that, In step 2, the viscosity of the antibacterial and heat-generating functional slurry is adjusted to 2000-3000 mPa·s; in step 4, the scraper speed for scraper coating is 1-2 m / min; in step 5, the dilution ratio of the water-based polyvinyl fluoride coating is coating:deionized water = 1:(0.8-1.2).