Antibacterial material and application thereof in quartz stone plate

Abstract

The application belongs to the technical field of building materials, and specifically discloses an antibacterial material and application of the antibacterial material in quartz stone plate material.The antibacterial material comprises the following components in parts by mass: 5-10 parts of mercaptopropyl modified ulan tea crystal stone, 5-12 parts of hydrolyzed chitin, 10-18 parts of vinyl modified graphene oxide, 0.5-3 parts of triethylamine, and 50-80 parts of anhydrous ethanol.The antibacterial material has excellent antibacterial performance and wear resistance, and when the antibacterial material is applied to the preparation of quartz stone plate material, the antibacterial performance and wear resistance of the quartz sand plate material can be significantly improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of building materials, in particular to an antibacterial material and application thereof in quartz stone plate. BACKGROUND

[0002] With the normalization of antibacterial, on the basis of green and environmental protection decoration requirements, antibacterial and other new technology product functions have also become the focus of increasing customer attention. With the improvement of consumers' health awareness and the increase of attention to the relationship between health and building environment, building and decoration health has gradually become the core competitiveness of the luxury product, and the production of health, antibacterial and environmentally friendly decoration products has become an inevitable trend of industry development.

[0003] Quartz stone inherits the advantages of natural granite, such as hard texture, corrosion resistance, wear resistance, and natural marble, which is exquisite and high-grade, and is widely used in indoor decoration and decoration fields such as kitchen, bathroom, window sill and dining table. The current quartz stone plate mainly focuses on its mechanical properties, so how to provide a quartz stone plate with antibacterial performance has become a technical problem to be solved by the technical personnel in the field. SUMMARY

[0004] The present application provides an antibacterial material and application thereof in quartz stone plate, which has excellent antibacterial performance and wear resistance, and can significantly improve the antibacterial performance and wear resistance of quartz sand plate when applied to prepare quartz stone plate.

[0005] The technical problem of the present application is solved by the following technical scheme:

[0006] An antibacterial material, comprising the following components by mass: 5-10 parts of mercaptopropyl modified ulan tea crystal stone, 5-12 parts of hydrolyzed chitin, 10-18 parts of vinyl modified graphene oxide, 0.5-3 parts of triethylamine, 50-80 parts of anhydrous ethanol.

[0007] As a preferred embodiment of the present application, it comprises the following components by mass: 6-10 parts of mercaptopropyl modified ulan tea crystal stone, 8-12 parts of hydrolyzed chitin, 12-18 parts of vinyl modified graphene oxide, 1-3 parts of triethylamine, 60-70 parts of anhydrous ethanol.

[0008] As a preferred embodiment of the present application, it comprises the following components by mass: 8 parts of mercaptopropyl modified ulan tea crystal stone, 10 parts of hydrolyzed chitin, 15 parts of vinyl modified graphene oxide, 2 parts of triethylamine, 65 parts of anhydrous ethanol.

[0009] As a preferred embodiment of the present application, the preparation method of the mercaptopropyl modified ulan tea crystal stone comprises the following steps:

[0010] (1) pulverize the ulan chrysolite to 50-200 mesh to obtain ulan chrysolite powder;

[0011] (2) add the ulan chrysolite powder and citric acid into concentrated hydrochloric acid, and ultrasonically treat to obtain a mixed solution;

[0012] (3) add γ-mercaptopropyl trimethoxysilane into the mixed solution, stir uniformly, vacuum dry, and grind to 500-2000 mesh to obtain mercaptopropyl modified ulan chrysolite.

[0013] As a preferred embodiment of the present application, the mass ratio of the ulan chrysolite powder, citric acid, concentrated hydrochloric acid, and γ-mercaptopropyl trimethoxysilane is 1:(0.01-0.1):(2-10):(0.01-0.1).

[0014] As a preferred embodiment of the present application, the preparation method of the vinyl modified graphene oxide comprises the following steps:

[0015] (1) disperse graphene oxide in deionized water, add dopamine hydrochloride, and then adjust the pH to 8.4-8.6 with Tris buffer solution, and stir uniformly to obtain a precursor solution;

[0016] (2) add methyl vinyl dimethoxysilane into the precursor solution, ultrasonically treat, vacuum dry, and grind to 1000-2000 mesh to obtain vinyl modified graphene oxide.

[0017] As a preferred embodiment of the present application, the mass ratio of the graphene oxide, deionized water, dopamine hydrochloride, and methyl vinyl dimethoxysilane is 1:(2-10):(0.5-2):(0.01-0.1).

[0018] The present application also provides a quartz stone plate, which comprises a quartz stone substrate and an antibacterial film layer on the surface of the quartz stone substrate.

[0019] The antibacterial film layer comprises the following components: 10-20 parts of antibacterial material, 2-10 parts of film forming agent, 0.5-2 parts of sodium tripolyphosphate, 0.5-4 parts of cetyltrimethylammonium bromide, and 60-100 parts of water.

[0020] The antibacterial material is the antibacterial material described above.

[0021] As a preferred embodiment of the present application, the film forming agent comprises hexylene glycol butyl ether acetate and hydrolyzed arthrobotrys gum.

[0022] The mass ratio of the hexylene glycol butyl ether acetate and hydrolyzed arthrobotrys gum is (2-10):1.

[0023] The present application also provides a preparation method of the quartz stone plate, which comprises the following steps:

[0024] The antibacterial material, the film forming agent, the sodium tripolyphosphate, the cetyltrimethylammonium bromide and the water are uniformly mixed to obtain a coating liquid;

[0025] The coating liquid is sprayed on the surface of the quartz stone substrate, dried, and an antibacterial film layer is formed, thereby obtaining the quartz stone plate.

[0026] The antibacterial material has excellent antibacterial performance and wear resistance, and the application of the antibacterial material in the preparation of the quartz stone plate can significantly improve the antibacterial performance and wear resistance of the quartz sand plate. (2) The mercaptopropyl modified ulan tea crystal, the hydrolyzed chitin and the vinyl modified graphene oxide are combined, wherein the mercaptopropyl modified ulan tea crystal and the vinyl modified graphene oxide can undergo a click reaction in the presence of triethylamine and anhydrous ethanol, that is, the mercaptopropyl modified ulan tea crystal and the vinyl modified graphene oxide are connected by a chemical bond, which improves the compatibility of the overall formula, and the compatibility and dispersibility of the overall formula are significantly improved. Compared with simple physical blending, the combination of the two has better performance, and the addition of the hydrolyzed chitin further improves the stability of the system. The hydrolyzed chitin is dispersed in the interstices of the propyl modified ulan tea crystal and the vinyl modified graphene oxide, so that the hydrolyzed chitin is dispersed in the propyl modified ulan tea crystal and the vinyl modified graphene oxide while being chemically connected and physically bonded, and a stable scaffold structure is formed to ensure that the performance of the active substance is fully utilized. At the same time, the mercaptopropyl modified ulan tea crystal, the hydrolyzed chitin and the vinyl modified graphene oxide have a barrier effect, which further blocks microorganisms. DETAILED DESCRIPTION

[0027] To make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0028] In the present application, the technical features described in an open manner include both closed technical solutions composed of listed features and open technical solutions containing listed features.

[0029] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0030] In this invention, there are no particular limitations on the specific dispersion and stirring methods.

[0031] Unless otherwise specified, all reagents or instruments used in this invention are commercially available products.

[0032] This invention provides an antibacterial material comprising the following components in parts by weight: 5-10 parts mercaptopropyl modified Ulan tea crystal, 5-12 parts hydrolyzed chitosan, 10-18 parts vinyl modified graphene oxide, 0.5-3 parts triethylamine, and 50-80 parts anhydrous ethanol.

[0033] This invention combines the above-mentioned raw materials in specific mass proportions to obtain an antibacterial material with excellent antibacterial and wear-resistant properties. When the antibacterial material is applied to the preparation of quartz stone slabs, it can significantly improve the wear resistance and antibacterial properties of the quartz stone slabs.

[0034] This invention creatively combines mercaptopropyl-modified Ulan tea crystals, hydrolyzed chitosan, and vinyl-modified graphene oxide. In the presence of triethylamine and anhydrous ethanol, the mercaptopropyl-modified Ulan tea crystals and vinyl-modified graphene oxide undergo a click reaction, meaning they are chemically bonded together. This improves the overall compatibility and dispersibility of the formulation, significantly enhancing its properties. Compared to simple physical blending, this chemical bonding provides superior performance. The addition of hydrolyzed chitosan further improves the stability of the system. The hydrolyzed chitosan is dispersed in the gaps between propyl-modified Wulan tea crystal and vinyl-modified graphene oxide, so that the hydrolyzed chitosan dispersed in propyl-modified Wulan tea crystal and vinyl-modified graphene oxide undergoes physical bonding while being chemically linked, forming a stable scaffold structure to ensure that the performance of the active substances is fully utilized. At the same time, the propyl-modified Wulan tea crystal, hydrolyzed chitosan, and vinyl-modified graphene oxide exhibit a fence-like effect, thereby blocking microorganisms.

[0035] In some embodiments, the components include the following mass parts: 6~10 parts of mercaptopropyl modified ulanite, 8~12 parts of hydrolyzed chitin, 12~18 parts of vinyl modified graphene oxide, 1~3 parts of triethylamine, 60~70 parts of anhydrous ethanol.

[0036] In some embodiments, the components include the following mass parts: 8 parts of mercaptopropyl modified ulanite, 10 parts of hydrolyzed chitin, 15 parts of vinyl modified graphene oxide, 2 parts of triethylamine, 65 parts of anhydrous ethanol.

[0037] In some embodiments, the preparation method of the mercaptopropyl modified ulanite includes the following steps:

[0038] (1) The ulanite is crushed to 50~200 mesh to obtain ulanite powder;

[0039] (2) The ulanite powder and citric acid are added to concentrated hydrochloric acid, and ultrasonic treatment is performed to obtain a mixed solution;

[0040] (3) γ-Mercaptopropyl trimethoxysilane is added to the mixed solution, stirred uniformly, vacuum dried, and ground to 500~2000 mesh to obtain mercaptopropyl modified ulanite.

[0041] The present application modifies the ulanite by first activating it with acid and then adding a silane coupling agent containing mercaptopropyl groups to the mixed solution. The inventors have found that different coupling agents have a significant impact on the results. By using a silane coupling agent containing mercaptopropyl groups, the antibacterial effect and wear resistance can be significantly improved compared to other coupling agents. The modification method of ulanite also contributes to the results. The modification method of the present application can significantly improve the wear resistance and antibacterial properties compared to other modification methods.

[0042] In some embodiments, the mass ratio of the ulanite powder, citric acid, concentrated hydrochloric acid, and γ-mercaptopropyl trimethoxysilane is 1: (0.01~0.1): (2~10): (0.01~0.1).

[0043] In some embodiments, the preparation method of the vinyl modified graphene oxide includes the following steps:

[0044] (1) The graphene oxide is dispersed in deionized water, hydrochloric acid dopamine is added, and the pH is adjusted to 8.4~8.6 with Tris buffer solution, and stirred uniformly to obtain a precursor solution;

[0045] (2) Methyl vinyl dimethoxysilane is added to the precursor solution, ultrasonic treatment is performed, vacuum dried, and ground to 1000~2000 mesh to obtain vinyl modified graphene oxide.

[0046] The graphene oxide of the present application is graphene oxide prepared by the conventional Hummers method, and the graphene oxide prepared by the Hummers method has a large number of active functional groups on the surface and excellent performance.

[0047] The inventors have found that the modification method of the graphene oxide also contributes to the effect, and the graphene oxide modified by the method of the present application can more significantly improve the wear resistance and antibacterial performance compared with other modification methods.

[0048] In some embodiments, the mass ratio of the graphene oxide, deionized water, dopamine hydrochloride and methyl vinyl dimethoxysilane is 1: (2-10): (0.5-2): (0.01-0.1).

[0049] An embodiment of the present application provides a quartz stone plate, comprising a quartz stone substrate and an antibacterial film layer on the surface of the quartz stone substrate.

[0050] The antibacterial film layer comprises the following components: 10-20 parts of antibacterial material, 2-10 parts of film forming agent, 0.5-2 parts of sodium tripolyphosphate, 0.5-4 parts of cetyltrimethylammonium bromide, and 60-100 parts of water.

[0051] The antibacterial material is the antibacterial material described above.

[0052] In some embodiments, the film forming agent comprises hexylene glycol butyl ether acetate and hydrolyzed sordarium gum.

[0053] The mass ratio of the hexylene glycol butyl ether acetate and the hydrolyzed sordarium gum is (2-10): 1.

[0054] The hexylene glycol butyl ether acetate and the hydrolyzed sordarium gum are used as the film forming agent in the present application, and have excellent film forming effect under the system of the present application.

[0055] An embodiment of the present application provides a preparation method of a quartz stone plate, comprising the following steps:

[0056] Mixing the antibacterial material, the film forming agent, the sodium tripolyphosphate, the cetyltrimethylammonium bromide and the water uniformly to obtain a coating liquid.

[0057] Spraying the coating liquid on the surface of the quartz stone substrate, drying, and forming an antibacterial film layer to obtain the quartz stone plate.

[0058] The preparation method of the present application is simple, only needs to spray the coating liquid on the surface of the quartz stone substrate, does not need to use specific equipment, and has wide application prospect.

[0059] The spraying amount of the coating liquid can be 10-50 g / m 2 .

[0060] The present application is further described below with specific examples: Example 1

[0061] A preparation method of a quartz stone plate, comprising the following steps:

[0062] (1) The graphene oxide is prepared by using the conventional Hummers method: 100 g of concentrated sulfuric acid is added to a reaction bottle under ice water bath condition, then 5 g of graphite, 3 g of sodium nitrate and 15 g of potassium permanganate are added and stirred uniformly, 20 g of deionized water is added and stirred uniformly, 80 v / v% hydrogen peroxide is added until it turns light yellow and no more bubbles are generated, centrifuged, washed with deionized water until neutral, and dried to obtain the graphene oxide.

[0063] 10 g of the graphene oxide is dispersed in 50 g of deionized water, 6 g of dopamine hydrochloride is added, the pH is adjusted to 8.5 by using Tris buffer, stirred uniformly to obtain a precursor solution, 0.5 g of methyl vinyl dimethoxy silane is added to the precursor solution, ultrasonic treatment is carried out at 500 W for 30 min, vacuum drying is carried out, and grinding is carried out to 2000 meshes to obtain the vinyl modified graphene oxide.

[0064] (2) The ulan tea crystal stone powder is ground to 100 meshes to obtain the ulan tea crystal stone powder;

[0065] 10 g of the ulan tea crystal stone powder and 0.5 g of citric acid are added to 50 g of concentrated hydrochloric acid, ultrasonic treatment is carried out at 500 W for 30 min to obtain a mixed solution, 0.5 g of gamma-mercaptopropyl trimethoxy silane is added to the mixed solution, stirred uniformly, vacuum drying is carried out, and grinding is carried out to 1000 meshes to obtain the mercaptopropyl modified ulan tea crystal stone.

[0066] (3) The following raw materials are weighed: 8 parts of the mercaptopropyl modified ulan tea crystal stone, 10 parts of the hydrolyzed chitin, 15 parts of the vinyl modified graphene oxide, 2 parts of triethylamine, and 65 parts of anhydrous ethanol;

[0067] The mercaptopropyl modified ulan tea crystal stone, the vinyl modified graphene oxide and the triethylamine are added to the anhydrous ethanol, reaction is carried out in a 50℃ water bath for 10 h, the hydrolyzed chitin is added, ultrasonic treatment is carried out at 500 W for 30 min to obtain the antibacterial material;

[0068] (4) Take the following mass parts of raw materials: 18 parts of antibacterial material, 5 parts of hexylene glycol butyl ether acetate, 1 part of hydrolyzed sclerotium glucosum gum, 1 part of sodium tripolyphosphate, 2 parts of cetyltrimethylammonium bromide, 73 parts of water;

[0069] Mix the antibacterial material, hexylene glycol butyl ether acetate, hydrolyzed sclerotium glucosum gum, sodium tripolyphosphate, cetyltrimethylammonium bromide, and water uniformly to obtain a coating liquid;

[0070] Spray the coating liquid on the surface of the quartz stone substrate at a spraying amount of 25 g / m 2 to form an antibacterial film layer, thereby obtaining a quartz stone plate.

[0071] Example 2

[0072] A preparation method of a quartz stone plate comprises the following steps:

[0073] (1) Prepare graphene oxide by using a conventional Hummers method: under ice water bath conditions, add 100 g of concentrated sulfuric acid into a reaction bottle, then add 5 g of graphite, 3 g of sodium nitrate, and 15 g of potassium permanganate, stir uniformly, then add 20 g of deionized water, stir uniformly, add 80 v / v% hydrogen peroxide until it turns light yellow and no more bubbles are generated, centrifuge, wash with deionized water until neutral, and dry to obtain graphene oxide.

[0074] Disperse 10 g of graphene oxide in 100 g of deionized water, add 5 g of dopamine hydrochloride, then adjust the pH to 8.5 with a Tris buffer, stir uniformly to obtain a precursor liquid, then add 0.6 g of methyl vinyl dimethoxy silane to the precursor liquid, ultrasonically treat at 500 W for 30 min, vacuum dry, and grind to 2000 mesh to obtain vinyl-modified graphene oxide.

[0075] (2) Grind the ulanite crystal to 100 mesh to obtain ulanite crystal powder;

[0076] Add 10 g of ulanite crystal powder and 0.8 g of citric acid to 100 g of concentrated hydrochloric acid, ultrasonically treat at 500 W for 30 min to obtain a mixed liquid, add 0.8 g of γ-mercaptopropyl trimethoxysilane to the mixed liquid, stir uniformly, vacuum dry, and grind to 1000 mesh to obtain mercaptopropyl-modified ulanite crystal.

[0077] (3) Take the following mass parts of raw materials: 5 parts of mercaptopropyl-modified ulanite crystal, 12 parts of hydrolyzed chitin, 18 parts of vinyl-modified graphene oxide, 1 part of triethylamine, and 64 parts of anhydrous ethanol;

[0078] The mercaptopropyl modified ulan chrysolite, the vinyl modified graphene oxide and triethylamine are added into anhydrous ethanol, and reacted in a 50℃ water bath for 10h, then the hydrolyzed chitin is added, and ultrasonic treatment is carried out at 500W for 30min to obtain the antibacterial material;

[0079] (4) The following mass parts of raw materials are weighed: 18 parts of the antibacterial material, 5 parts of hexylene glycol butyl ether acetate, 1 part of hydrolyzed sclerotinia gum, 1 part of sodium tripolyphosphate, 2 parts of cetyltrimethylammonium bromide, and 73 parts of water;

[0080] The antibacterial material, hexylene glycol butyl ether acetate, hydrolyzed sclerotinia gum, sodium tripolyphosphate, cetyltrimethylammonium bromide and water are uniformly mixed to obtain a coating liquid.

[0081] The coating liquid is sprayed on the surface of the quartz stone substrate at a spraying amount of 15g / m 2 , dried, and an antibacterial film layer is formed, thereby obtaining a quartz stone plate.

[0082] Example 3

[0083] A preparation method of a quartz stone plate comprises the following steps:

[0084] (1) The graphene oxide is prepared by using a conventional Hummers method: 100g of concentrated sulfuric acid is added into a reaction bottle under the condition of an ice water bath, then 5g of graphite, 3g of sodium nitrate and 15g of potassium permanganate are added and stirred uniformly, 20g of deionized water is added and stirred uniformly, 80v / v% of hydrogen peroxide is added until it turns light yellow and no more bubbles are generated, centrifugation is performed, deionized water is used for washing until neutral, and drying is performed to obtain the graphene oxide.

[0085] 10g of the graphene oxide is dispersed in 100g of deionized water, 4g of dopamine hydrochloride is added, a Tris buffer solution is used for adjusting the pH to 8.5, stirring is uniformly performed, a precursor liquid is obtained, 0.4g of methyl vinyl dimethoxy silane is added into the precursor liquid, ultrasonic treatment is carried out at 500W for 30min, vacuum drying is performed, and grinding is performed to 2000 meshes to obtain the vinyl modified graphene oxide.

[0086] (2) The ulan chrysolite is crushed to 100 meshes to obtain ulan chrysolite powder;

[0087] 10g of the ulan chrysolite powder and 0.4g of citric acid are added into 30g of concentrated hydrochloric acid, ultrasonic treatment is carried out at 500W for 30min to obtain a mixed liquid, 0.4g of γ-mercaptopropyl trimethoxy silane is added into the mixed liquid, stirring is uniformly performed, vacuum drying is performed, and grinding is performed to 1000 meshes to obtain the mercaptopropyl modified ulan chrysolite.

[0088] (3) Take the following mass parts of raw materials: 10 parts of mercaptopropyl modified ulan tea crystal stone, 10 parts of hydrolyzed chitin, 12 parts of vinyl modified graphene oxide, 3 parts of triethylamine, 65 parts of anhydrous ethanol;

[0089] The mercaptopropyl modified ulan tea crystal stone, the vinyl modified graphene oxide, the triethylamine are added to the anhydrous ethanol, reacted in a 50℃ water bath for 10h, then the hydrolyzed chitin is added, ultrasonic treated for 30min at 500W, to obtain the antibacterial material;

[0090] (4) Take the following mass parts of raw materials: 18 parts of the antibacterial material, 5 parts of hexylene glycol butyl ether acetate, 1 part of hydrolyzed sclerotinia gum, 1 part of sodium tripolyphosphate, 2 parts of cetyltrimethylammonium bromide, 73 parts of water;

[0091] The antibacterial material, the hexylene glycol butyl ether acetate, the hydrolyzed sclerotinia gum, the sodium tripolyphosphate, the cetyltrimethylammonium bromide and the water are mixed uniformly to obtain a coating liquid;

[0092] The coating liquid is sprayed on the surface of the quartz stone substrate at a spraying amount of 15g / m 2 , dried to form an antibacterial film layer, thereby obtaining a quartz stone plate.

[0093] Comparative Example 1

[0094] Comparative Example 1 is different from Example 1 in that the antibacterial material is different from Example 1, and Comparative Example 1 does not contain mercaptopropyl modified ulan tea crystal stone (the total amount of mercaptopropyl modified ulan tea crystal stone, hydrolyzed chitin and vinyl modified graphene oxide is unchanged), and the others are the same.

[0095] The preparation of the antibacterial material of the present comparative example comprises the following steps:

[0096] Take the following mass parts of raw materials: 14 parts of hydrolyzed chitin, 19 parts of vinyl modified graphene oxide, 2 parts of triethylamine, 65 parts of anhydrous ethanol;

[0097] The vinyl modified graphene oxide and the triethylamine are added to the anhydrous ethanol, reacted in a 50℃ water bath for 10h, then the hydrolyzed chitin is added, ultrasonic treated for 30min at 500W, to obtain the antibacterial material.

[0098] Comparative Example 2

[0099] Comparative Example 2 is different from Example 1 in that the antibacterial material is different from Example 1, and Comparative Example 1 does not contain hydrolyzed chitin (the total amount of mercaptopropyl modified ulan tea crystal stone, hydrolyzed chitin and vinyl modified graphene oxide is unchanged), and the others are the same.

[0100] The preparation of the antibacterial material of the present comparative example comprises the following steps:

[0101] Take the following mass parts of raw materials: 13 parts of mercaptopropyl modified ulan tea crystal stone, 20 parts of vinyl modified graphene oxide, 2 parts of triethylamine, 65 parts of anhydrous ethanol;

[0102] The mercaptopropyl modified ulan tea crystal stone, the vinyl modified graphene oxide and the triethylamine are added to the anhydrous ethanol, reacted in a 50℃ water bath for 10h, then the hydrolyzed chitin is added, ultrasonic treated at 500W for 30min, to obtain the antibacterial material.

[0103] Comparative Example 3

[0104] Comparative Example 3 is different from Example 1 in that the antibacterial material is different from Example 1, Comparative Example 1 does not contain vinyl modified graphene oxide (the total amount of mercaptopropyl modified ulan tea crystal stone, hydrolyzed chitin and vinyl modified graphene oxide is unchanged), and the others are the same.

[0105] The preparation of the antibacterial material of the present comparative example comprises the following steps:

[0106] Take the following mass parts of raw materials: 15.5 parts of mercaptopropyl modified ulan tea crystal stone, 17.5 parts of hydrolyzed chitin, 2 parts of triethylamine, 65 parts of anhydrous ethanol;

[0107] The mercaptopropyl modified ulan tea crystal stone and the triethylamine are added to the anhydrous ethanol, reacted in a 50℃ water bath for 10h, then the hydrolyzed chitin is added, ultrasonic treated at 500W for 30min, to obtain the antibacterial material.

[0108] Comparative Example 4

[0109] Comparative Example 4 is different from Example 1 in that Comparative Example 4 uses graphene oxide instead of modified graphene oxide, and the others are the same.

[0110] Comparative Example 5

[0111] Comparative Example 5 is different from Example 1 in that the preparation method of the modified graphene oxide of Comparative Example 5 is different from Example 1, and the others are the same.

[0112] The preparation method of the modified graphene oxide of the present comparative example comprises the following steps:

[0113] 10g of graphene oxide is dispersed in 100g of deionized water, 4g of dopamine hydrochloride is added, then the pH is adjusted to 8.5 with Tris buffer, stirred uniformly to obtain a precursor solution, then 0.4g of γ-aminopropyl triethoxysilane is added to the precursor solution, ultrasonic treated at 500W for 30min, vacuum dried, and ground to 2000 meshes to obtain the modified graphene oxide.

[0114] Comparative Example 6

[0115] The difference between the comparative example 6 and the example 1 is that the preparation method of the modified graphene oxide in the comparative example 6 is different from that in the example 1, and the others are the same.

[0116] The 10 g graphene oxide was dispersed in 50 g deionized water, 0.5 g methyl vinyl dimethoxy silane was added, ultrasonic treatment was carried out at 500 W for 30 min, vacuum drying was carried out, and grinding was carried out to 2000 meshes to obtain the vinyl modified graphene oxide.

[0117] Comparative example 7

[0118] The difference between the comparative example 7 and the example 1 is that the 2000 mesh ulan tea crystal stone powder is used to replace the mercapto propyl modified ulan tea crystal stone in the comparative example 7, and the others are the same.

[0119] Comparative example 8

[0120] The difference between the comparative example 8 and the example 1 is that the preparation method of the modified ulan tea crystal stone in the comparative example 8 is different from that in the example 1, and the others are the same.

[0121] The preparation method of the modified ulan tea crystal stone in the comparative example is as follows:

[0122] The 10 g ulan tea crystal stone powder and 0.5 g citric acid were added into 50 g concentrated hydrochloric acid, ultrasonic treatment was carried out at 500 W for 30 min to obtain a mixed solution, 0.5 g γ-aminopropyl triethoxysilane was added into the mixed solution, stirring was carried out uniformly, vacuum drying was carried out, and grinding was carried out to 1000 meshes to obtain the mercapto propyl modified ulan tea crystal stone.

[0123] Test example

[0124] 1. The bacteriostatic rate was tested according to JC / T897-2014.

[0125] 2. The wear resistance of the antibacterial film layer was evaluated according to GB / T1768-2006 “Determination of abrasion resistance of paints and varnishes-Rotary rubber wheel method”, the mass loss (mg) of the sample was measured after 500 rotations, and the test results are shown in Table 1.

[0126] Table 1

[0127]

[0128] It can be seen from Table 1 that the antibacterial material described in the application can not only significantly improve the antibacterial performance, but also significantly improve the wear resistance.

[0129] It can be seen from the comparative examples 1 to 3 that the example 1 is the best embodiment of the application, and has the best antibacterial performance and wear resistance.

[0130] As can be seen from the comparative example 1 and the comparative examples 1-3, in the present application, the mercaptopropyl modified ulanite, the hydrolyzed chitin and the vinyl modified graphene oxide have a significant synergistic effect on the wear resistance and the antibacterial property, and the absence of any one of them will result in a significant decrease in the antibacterial property and the wear resistance.

[0131] As can be seen from the comparative example 1 and the comparative examples 4-6, by modifying the graphene oxide, the present application significantly improves the wear resistance and the antibacterial property, and the experimental data shows that the modification method of the graphene oxide also contributes to the effect, and by modifying the graphene oxide by the method of the present application, compared with other modification methods, the wear resistance and the antibacterial property can be more significantly improved.

[0132] As can be seen from the comparative example 1 and the comparative examples 7-8, by modifying the ulanite, the present application significantly improves the wear resistance and the antibacterial property, and the experimental data shows that the modification method of the ulanite also contributes to the effect, and by modifying the ulanite by the method of the present application, compared with other modification methods, the wear resistance and the antibacterial property can be more significantly improved.

[0133] Based on the above ideal embodiments according to the present application, through the above description, relevant personnel can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the content of the specification, and must be determined according to the scope of the claims.

Claims

1. An antibacterial material, characterized by, Components comprising the following parts by mass: 5~10 parts of mercapto propyl modified ulan crystal stone, 5~12 parts of hydrolyzed chitin, 10~18 parts of vinyl modified graphene oxide, 0.5~3 parts of triethylamine, 50~80 parts of anhydrous ethanol; The preparation method of the mercapto propyl modified ulan crystal stone comprises the following steps: (1) Pulverize the ulan crystal stone to 50~200 mesh to obtain ulan crystal stone powder; (2) Add the ulan crystal stone powder and citric acid to concentrated hydrochloric acid, and ultrasonically treat to obtain a mixed solution; (3) Add γ-mercaptopropyl trimethoxysilane to the mixed solution, stir uniformly, vacuum dry, and grind to 500~2000 mesh to obtain the mercapto propyl modified ulan crystal stone; The preparation method of the vinyl modified graphene oxide comprises the following steps: (1) Disperse the graphene oxide in deionized water, add dopamine hydrochloride, and then adjust the pH to 8.4~8.6 with Tris buffer solution, and stir uniformly to obtain a precursor solution; (2) Add methyl vinyl dimethoxysilane to the precursor solution, ultrasonically treat, vacuum dry, and grind to 1000~2000 mesh to obtain the vinyl modified graphene oxide.

2. The antimicrobial material of claim 1, wherein, Components comprising the following parts by mass: 6~10 parts of mercapto propyl modified ulan crystal stone, 8~12 parts of hydrolyzed chitin, 12~18 parts of vinyl modified graphene oxide, 1~3 parts of triethylamine, 60~70 parts of anhydrous ethanol.

3. The antimicrobial material of claim 1, wherein, Components comprising the following parts by mass: 8 parts of mercapto propyl modified ulan crystal stone, 10 parts of hydrolyzed chitin, 15 parts of vinyl modified graphene oxide, 2 parts of triethylamine, 65 parts of anhydrous ethanol.

4. The antimicrobial material of claim 1, wherein, The mass ratio of the ulan crystal stone powder, citric acid, concentrated hydrochloric acid, and γ-mercaptopropyl trimethoxysilane is 1:(0.01~0.1):(2~10):(0.01~0.1).

5. The antimicrobial material of claim 1, wherein, The mass ratio of the graphene oxide, deionized water, dopamine hydrochloride, and methyl vinyl dimethoxysilane is 1:(2~10):(0.5~2):(0.01~0.1).

6. A quartzite slab, characterized by, It comprises a quartz stone substrate and an antibacterial film layer on the surface of the quartz stone substrate; The antibacterial film layer comprises the following components: 10~20 parts of antibacterial material, 2~10 parts of film forming agent, 0.5~2 parts of sodium tripolyphosphate, 0.5~4 parts of cetyltrimethylammonium bromide, and 60~100 parts of water; The antibacterial material is the antibacterial material according to any one of claims 1~5.

7. The quartzite slab of claim 6, wherein, The film forming agent comprises hexylene glycol butyl ether acetate and hydrolyzed syncephalastrum. The mass ratio of the hexylene glycol butyl ether acetate and hydrolyzed syncephalastrum is (2~10):

1.

8. The method of manufacturing a quartzite slab according to any one of claims 6-7, characterized in that, It comprises the following steps: Mix the antibacterial material, film forming agent, sodium tripolyphosphate, cetyltrimethylammonium bromide, and water uniformly to obtain a coating liquid; Spray the coating liquid on the surface of the quartz stone substrate, dry, and form an antibacterial film layer to obtain a quartz stone plate.

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