Antibacterial agent for hard surface and preparation method thereof

Abstract

The invention discloses an antibacterial agent for a hard surface and a preparation method of the antibacterial agent, and relates to the technical field of disinfection and sterilization. When the antibacterial agent for the hard surface is prepared, silicon dioxide sequentially reacts with chloropropyltriethoxysilane, 2, 2 '-dimethyl pyridine amine and zinc nitrate to prepare modified silicon dioxide; the preparation method comprises the following steps: reacting phytic acid with 3-butene-1-amine to obtain modified phytic acid; the preparation method comprises the following steps: reacting polyvinyl alcohol with 4-chloropropionic acid and N-allylimidazole in sequence to prepare modified polyvinyl alcohol; and uniformly mixing the modified polyvinyl alcohol, the modified phytic acid, the modified silicon dioxide, azodiisobutyronitrile, absolute ethyl alcohol and deionized water to prepare the antibacterial agent for the hard surface. The prepared antibacterial agent for the hard surface has excellent antibacterial performance and wear resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of disinfection and sterilization, in particular to an antibacterial agent for hard surfaces and a preparation method thereof. BACKGROUND

[0002] With the improvement of people's living standards, the health requirements for the environment, especially public transportation, are becoming higher and higher. In daily life, elevator buttons, ceramic tiles, floors, elevator handrails, bus seats, door handles, office desks and chairs, hospital surgical instruments, bed handrails and other facilities are in frequent contact with the human body for a long time, which can easily accumulate pathogens and breed bacteria, posing a threat to people's health. Using an antibacterial agent to disinfect the surface of these facilities is a common method.

[0003] However, these facilities are often subjected to various scratches and wear during use and cleaning, resulting in the loss of antibacterial agents on the surface and poor long-term antibacterial effect. Therefore, it is necessary to invent an antibacterial agent for hard surfaces with excellent wear resistance. SUMMARY

[0004] The present application aims to provide an antibacterial agent for hard surfaces and a preparation method thereof to solve the problems in the prior art.

[0005] To solve the above technical problems, the present application provides the following technical solutions: An antibacterial agent for hard surfaces, by mass fraction, comprising: 50-54 parts of modified polyvinyl alcohol, 6-7 parts of modified phytic acid, 3-4 parts of modified silicon dioxide, 1-1.5 parts of azobisdimethyl nitrile, 40-44 parts of anhydrous ethanol, and 100-110 parts of deionized water. The modified polyvinyl alcohol is prepared by reacting pre-modified polyvinyl alcohol and N-allyl imidazole; The pre-modified polyvinyl alcohol is prepared by reacting polyvinyl alcohol and 4-chloropropionic acid; The modified phytic acid is prepared by reacting phytic acid and 3-buten-1-amine; The modified silicon dioxide is prepared by sequentially reacting silicon dioxide with chloropropyl triethoxysilane, 2,2'-dimethylpyridine amine, and zinc nitrate.

[0006] A preparation method of an antibacterial agent for hard surfaces, the preparation method of the antibacterial agent for hard surfaces comprising the following preparation steps: (1) The pretreated silicon dioxide, 2,2'-dimethylpyridine amine, potassium carbonate, acetonitrile are mixed uniformly according to the mass ratio of 1:(3-4):(0.5-0.7):(40-50), under the protection of nitrogen, 80-82℃, 300-500r / min stirring reflux for 24-26h, filtration, washing with anhydrous ethanol and deionized water for 5 times, drying at 50-60℃ under vacuum for 10-12h, to obtain the pre-modified silicon dioxide; the pre-modified silicon dioxide, zinc nitrate, methanol are mixed uniformly according to the mass ratio of 1:(4-5):(30-32), stirring at 40-50℃ for 10-12h, filtration, drying at 50-60℃ under vacuum for 10-12h, to obtain the modified silicon dioxide; (2) The 3-buten-1-amine, anhydrous ethanol are mixed uniformly according to the mass ratio of 1:(7-8) to prepare 3-buten-1-amine solution; the phytic acid, anhydrous ethanol, deionized water are mixed uniformly according to the mass ratio of 1:(4-5):(10-12), under the condition of 60-62℃, 300-500r / min stirring, the 3-buten-1-amine solution is added uniformly within 20min, after the addition is completed, continue to stir for 10-12h, drying at 50-60℃ under vacuum for 10-12h, to obtain the modified phytic acid; (3) The pre-modified polyvinyl alcohol, N-allyl imidazole, dimethyl sulfoxide are mixed uniformly according to the mass ratio of 1:(0.6-0.8):(14-16), stirring at 60-70℃ for 12-14h, cooling to room temperature, the product is precipitated in anhydrous ethanol, washing with anhydrous ethanol for 3 times, drying at 50-60℃ under vacuum for 18-20h, to obtain the modified polyvinyl alcohol; (4) The modified polyvinyl alcohol, modified phytic acid, modified silicon dioxide, azobis isobutyronitrile, anhydrous ethanol, deionized water are mixed uniformly to prepare the antibacterial agent for hard surface.

[0007] As an optimization, the preparation method of the pretreated silicon dioxide in step (1) is as follows: the silicon dioxide, deionized water, anhydrous ethanol are mixed uniformly according to the mass ratio of 1:(24-26):(36-38), ultrasonic dispersion for 60-70min, adding 4-5 times of the mass of the silicon dioxide of 10% hydrochloric acid aqueous solution, adding 7-8 times of the mass of the silicon dioxide of chloropropyl triethoxysilane, under the protection of nitrogen, 60-70℃, 300-500r / min stirring for 8-10h, filtration, washing with anhydrous ethanol and deionized water for 5 times, drying at 60-70℃ under vacuum for 12-14h, to obtain the pretreated silicon dioxide.

[0008] As an optimization, the particle size of the silicon dioxide is 2000 mesh.

[0009] As optimization, the molar ratio of phytic acid and 3-buten-1-amine in step (2) is 1:4.

[0010] As optimization, the preparation method of the pre-modified polyvinyl alcohol in step (3) is as follows: polyvinyl alcohol and dimethyl sulfoxide are uniformly mixed at a mass ratio of 1:(20-22), stirring at 50 DEG C and 200-300 r / min for 15-17 min, 4-chloropropionic acid is added in an amount of 1-3 times of the molar amount of polyvinyl alcohol, concentrated sulfuric acid is added in an amount of 0.3-0.5 times of the mass of polyvinyl alcohol, and the reaction is continued at 50-70 DEG C for 5-7 h, and then the product is precipitated in anhydrous ethanol, washed with anhydrous ethanol for 3 times, and dried at 50-60 DEG C under vacuum for 18-20 h to obtain the pre-modified polyvinyl alcohol.

[0011] As optimization, the type of the polyvinyl alcohol is PVA-0599.

[0012] As optimization, the amounts of the modified polyvinyl alcohol, the modified phytic acid, the modified silicon dioxide, the azobisisobutyronitrile, the anhydrous ethanol and the deionized water in step (4) are as follows: the modified polyvinyl alcohol is 50-54 parts by mass, the modified phytic acid is 6-7 parts by mass, the modified silicon dioxide is 3-4 parts by mass, the azobisisobutyronitrile is 1-1.5 parts by mass, the anhydrous ethanol is 40-44 parts by mass, and the deionized water is 100-110 parts by mass.

[0013] Compared with the prior art, the present application has the following beneficial effects: In the preparation of the antibacterial agent for hard surface, the present application reacts silicon dioxide and chloropropyl triethoxysilane to obtain pretreated silicon dioxide, reacts the pretreated silicon dioxide and 2,2'-dimethylpyridine amine to obtain pre-modified silicon dioxide, reacts the pre-modified silicon dioxide and zinc nitrate to obtain modified silicon dioxide, reacts phytic acid and 3-buten-1-amine to obtain modified phytic acid, reacts polyvinyl alcohol and 4-chloropropionic acid to obtain pre-modified polyvinyl alcohol, reacts the pre-modified polyvinyl alcohol and N-allyl imidazole to obtain modified polyvinyl alcohol, and uniformly mixes the modified polyvinyl alcohol, the modified phytic acid, the modified silicon dioxide, the azobisisobutyronitrile, the anhydrous ethanol and the deionized water to obtain the antibacterial agent for hard surface.

[0014] Firstly, the silica is prepared by reacting with chloropropyl triethoxysilane, the chlorine atom is introduced on the pretreated silica, the chlorine atom introduced on the pretreated silica is reacted with 2,2'-dimethylpyridine amine to prepare the pre-modified silica, and the dimethylpyridine amine ligand structure is grafted on the pre-modified silica; the dimethylpyridine amine ligand structure grafted on the pre-modified silica is reacted with zinc nitrate to generate dimethylpyridine amine zinc complex; the dimethylpyridine amine zinc complex belongs to an organic zinc antibacterial agent, can destroy the bacterial cell membrane, interfere with the enzyme activity of the bacterial cell electron transport system, react with the thio group / carboxyl group / hydroxyl group of the protein, destroy the spatial structure, and achieve the purpose of antibiosis; the antibacterial agent prepared by the application is mainly applied to places such as ceramic tiles, floors, elevator handrails, bus seats, door handles, tables and chairs, which are easy to be subjected to various friction forces, causing abrasion and failure of the antibacterial agent; the silica is a high-hardness inorganic material, and existing researches prove that adding the silica in an organic resin material can improve the wear resistance of the material and prolong the antibacterial effect.

[0015] Secondly, the modified phytic acid is prepared by reacting the part of phosphoric acid groups on the phytic acid with the amino group on 3-butene-1-amine, and the carbon-carbon double bond is introduced on the modified phytic acid; the negatively charged phytic acid molecule can be combined with the positive charge on the surface of bacteria to change the membrane permeability and cause the content to leak, thereby improving the antibacterial ability of the hard-surface antibacterial agent; meanwhile, the carbon-carbon double bond introduced on the modified phytic acid can react with the carbon-carbon double bond introduced on the side chain of the modified polyvinyl alcohol under the action of a catalyst, and a three-dimensional crosslinked network structure is formed after solidification, so that the material is not easy to be torn by external shearing force, thereby improving the wear resistance of the hard-surface antibacterial agent, reducing the abrasion of the antibacterial agent, and prolonging the antibacterial effect.

[0016] Finally, the pre-modified polyvinyl alcohol is prepared by reacting polyvinyl alcohol with 4-chloropropionic acid through esterification, and the chlorine atom is grafted on the pre-modified polyvinyl alcohol; the modified polyvinyl alcohol is prepared by reacting the chlorine atom grafted on the pre-modified polyvinyl alcohol with N-allyl imidazole, and the imidazole salt is generated on the modified polyvinyl alcohol, and the carbon-carbon double bond is introduced; the imidazole salt belongs to a cationic antibacterial agent, which can further improve the antibacterial performance of the hard-surface antibacterial agent, and the carbon-carbon double bond introduced on the side chain of the modified polyvinyl alcohol can react with the carbon-carbon double bond introduced on the modified phytic acid to form a three-dimensional crosslinked network, thereby improving the wear resistance of the hard-surface antibacterial agent, reducing the abrasion of the antibacterial agent, and prolonging the antibacterial effect. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments of the present application, all other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the scope of the present application.

[0018] In the following examples and comparative examples, the polyvinyl alcohol used is PVA-0599; the particle size of the silica used is 2000 mesh.

[0019] Example 1:

[0020] A preparation method of a hard-surface antibacterial agent, the preparation method of the hard-surface antibacterial agent comprising the following preparation steps: (1) uniformly mix silica, deionized water and anhydrous ethanol in a mass ratio of 1:24:36, ultrasonically disperse for 60 min, add a 10% hydrochloric acid aqueous solution with a mass fraction of 4 times the mass of the silica, add chloropropyl triethoxysilane with 7 times the mass of the silica, stir at 60°C and 300 r / min for 10 h under nitrogen protection, filter, wash with anhydrous ethanol and deionized water for 5 times respectively, and dry at 60°C under vacuum conditions for 14 h to obtain pretreated silica; uniformly mix the pretreated silica, 2,2'-dimethylpyridine amine, potassium carbonate and acetonitrile in a mass ratio of 1:3:0.5:40, stir at 80°C and 300 r / min for 26 h under reflux in nitrogen protection, filter, wash with anhydrous ethanol and deionized water for 5 times respectively, and dry at 50°C under vacuum conditions for 12 h to obtain pretreated modified silica; uniformly mix the pretreated modified silica, zinc nitrate and methanol in a mass ratio of 1:4:30, stir at 40°C and 300 r / min for 12 h, filter, and dry at 50°C under vacuum conditions for 12 h to obtain modified silica; (2) weigh phytic acid and 3-buten-1-amine in a molar ratio of 1:4; uniformly mix 3-buten-1-amine and anhydrous ethanol in a mass ratio of 1:7 to prepare a 3-buten-1-amine solution; uniformly mix phytic acid, anhydrous ethanol and deionized water in a mass ratio of 1:4:10, uniformly drop the 3-buten-1-amine solution at 60°C and 300 r / min within 20 min, continue to stir for 12 h after the dropping is completed, and dry at 50°C under vacuum conditions for 12 h to obtain modified phytic acid; (3) mixing polyvinyl alcohol and dimethyl sulfoxide uniformly according to a mass ratio of 1:20, stirring at 50°C and 200 r / min for 15 min, adding 4-chloropropionic acid with a molar amount of 1 times that of polyvinyl alcohol, adding concentrated sulfuric acid with a mass of 0.3 times that of polyvinyl alcohol, continuing to stir at 50°C for 7 h, cooling to room temperature, precipitating the product in anhydrous ethanol, washing with anhydrous ethanol for 3 times, and drying at 50°C under vacuum for 20 h to prepare pre-modified polyvinyl alcohol; mixing the pre-modified polyvinyl alcohol, N-allyl imidazole and dimethyl sulfoxide uniformly according to a mass ratio of 1:0.6:14, stirring at 60°C and 300 r / min for 14 h, cooling to room temperature, precipitating the product in anhydrous ethanol, washing with anhydrous ethanol for 3 times, and drying at 50°C under vacuum for 20 h to prepare modified polyvinyl alcohol; (4) taking modified polyvinyl alcohol 50 parts, modified phytic acid 6 parts, modified silicon dioxide 3 parts, azobisisobutyronitrile 1 part, anhydrous ethanol 40 parts and deionized water 100 parts by mass fraction; mixing the modified polyvinyl alcohol, modified phytic acid, modified silicon dioxide, azobisisobutyronitrile, anhydrous ethanol and deionized water uniformly to prepare an antibacterial agent for hard surface.

[0021] Example 2:

[0022] A preparation method of an antibacterial agent for hard surface, the preparation method of the antibacterial agent for hard surface comprising the following preparation steps: (1) mixing silicon dioxide, deionized water and anhydrous ethanol uniformly according to a mass ratio of 1:25:37, ultrasonic dispersion for 65 min, adding hydrochloric acid aqueous solution with a mass fraction of 10% with a mass of 4.5 times that of silicon dioxide, adding chloropropyl triethoxysilane with a mass of 7.5 times that of silicon dioxide, stirring at 65°C and 400 r / min for 9 h under nitrogen protection, filtering, washing with anhydrous ethanol and deionized water for 5 times respectively, and drying at 65°C under vacuum for 13 h to prepare pretreated silicon dioxide; mixing the pretreated silicon dioxide, 2,2'-dimethylpyridine amine, potassium carbonate and acetonitrile uniformly according to a mass ratio of 1:3.5:0.6:45, stirring at 81°C and 400 r / min for 25 h under nitrogen protection, filtering, washing with anhydrous ethanol and deionized water for 5 times respectively, and drying at 55°C under vacuum for 11 h to prepare pre-modified silicon dioxide; mixing the pre-modified silicon dioxide, zinc nitrate and methanol uniformly according to a mass ratio of 1:4.5:31, stirring at 45°C and 400 r / min for 11 h, filtering, and drying at 55°C under vacuum for 11 h to prepare modified silicon dioxide; (2) phytic acid and 3-buten-1-amine were weighed according to a molar ratio of 1:4; 3-buten-1-amine and anhydrous ethanol were mixed uniformly according to a mass ratio of 1:7.5 to prepare a 3-buten-1-amine solution; phytic acid, anhydrous ethanol and deionized water were mixed uniformly according to a mass ratio of 1:4.5:11, and the 3-buten-1-amine solution was added uniformly at a speed of 400 r / min for 20 min at 61 ℃, and then the reaction was continued for 11 h after the addition was completed; and the modified phytic acid was prepared by drying at 55 ℃ under vacuum for 11 h; (3) polyvinyl alcohol and dimethyl sulfoxide were mixed uniformly according to a mass ratio of 1:21, and then 4-chloropropionic acid was added in an amount of 2 times the molar amount of polyvinyl alcohol, and concentrated sulfuric acid was added in an amount of 0.4 times the mass of polyvinyl alcohol, and the reaction was continued for 6 h at 60 ℃ under stirring at 250 r / min for 16 min at 50 ℃, and then the product was precipitated in anhydrous ethanol, washed with anhydrous ethanol for 3 times, and dried at 55 ℃ under vacuum for 19 h to prepare a pre-modified polyvinyl alcohol; the pre-modified polyvinyl alcohol, N-allyl imidazole and dimethyl sulfoxide were mixed uniformly according to a mass ratio of 1:0.7:15, and the reaction was continued for 13 h at 65 ℃ under stirring at 400 r / min, and then the product was precipitated in anhydrous ethanol, washed with anhydrous ethanol for 3 times, and dried at 55 ℃ under vacuum for 19 h to prepare a modified polyvinyl alcohol; (4) 52 parts of modified polyvinyl alcohol, 6.5 parts of modified phytic acid, 3.5 parts of modified silicon dioxide, 1.25 parts of azobisisobutyronitrile, 42 parts of anhydrous ethanol and 105 parts of deionized water were weighed according to the mass fraction, and then mixed uniformly to prepare a hard-surface antibacterial agent.

[0023] Example 3

[0024] A preparation method of a hard-surface antibacterial agent, the preparation method of the hard-surface antibacterial agent comprising the following preparation steps: (1) The silica, deionized water, and anhydrous ethanol are mixed uniformly in a mass ratio of 1:26:38, ultrasonic dispersion is performed for 70 min, 5 times the mass of the silica of 10% hydrochloric acid aqueous solution is added, 8 times the mass of the silica of chloropropyl triethoxysilane is added, stirring is performed at 70°C and 500 r / min under nitrogen protection for 8 h, filtration is performed, washing is performed with anhydrous ethanol and deionized water for 5 times each, and drying is performed under vacuum conditions at 70°C for 12 h to obtain pretreated silica; the pretreated silica, 2,2'-dimethylpyridine amine, potassium carbonate, and acetonitrile are mixed uniformly in a mass ratio of 1:4:0.7:50, stirring is performed at 82°C and 500 r / min under nitrogen protection for 24 h, filtration is performed, washing is performed with anhydrous ethanol and deionized water for 5 times each, and drying is performed under vacuum conditions at 60°C for 10 h to obtain pretreated modified silica; the pretreated modified silica, zinc nitrate, and methanol are mixed uniformly in a mass ratio of 1:5:32, stirring is performed at 50°C and 500 r / min for 10 h, filtration is performed, and drying is performed under vacuum conditions at 60°C for 10 h to obtain modified silica; (2) Phytic acid and 3-buten-1-amine are weighed in a molar ratio of 1:4; 3-buten-1-amine and anhydrous ethanol are mixed uniformly in a mass ratio of 1:8 to prepare a 3-buten-1-amine solution; phytic acid, anhydrous ethanol, and deionized water are mixed uniformly in a mass ratio of 1:5:12, the 3-buten-1-amine solution is added at a constant speed under stirring conditions at 62°C and 500 r / min for 20 min, stirring is continued for 10 h after the addition is completed, and drying is performed under vacuum conditions at 60°C for 10 h to obtain modified phytic acid; (3) Polyvinyl alcohol and dimethyl sulfoxide are mixed uniformly in a mass ratio of 1:22, stirring is performed at 50°C and 300 r / min for 15 min, 3 times the molar amount of the polyvinyl alcohol of 4-chloropropionic acid is added, 0.5 times the mass of the polyvinyl alcohol of concentrated sulfuric acid is added, stirring is continued at 70°C for 5 h, the product is precipitated in anhydrous ethanol, washing is performed with anhydrous ethanol for 3 times, and drying is performed under vacuum conditions at 60°C for 18 h to obtain pretreated modified polyvinyl alcohol; the pretreated modified polyvinyl alcohol, N-allyl imidazole, and dimethyl sulfoxide are mixed uniformly in a mass ratio of 1:0.8:16, stirring is performed at 70°C and 500 r / min for 12 h, the product is precipitated in anhydrous ethanol, washing is performed with anhydrous ethanol for 3 times, and drying is performed under vacuum conditions at 60°C for 18 h to obtain modified polyvinyl alcohol; (4) Modified polyvinyl alcohol 54 parts, modified phytic acid 7 parts, modified silica 4 parts, azobisisobutyronitrile 1.5 parts, anhydrous ethanol 44 parts, and deionized water 110 parts are weighed in mass parts; the modified polyvinyl alcohol, the modified phytic acid, the modified silica, the azobisisobutyronitrile, the anhydrous ethanol, and the deionized water are mixed uniformly to prepare an antibacterial agent for a hard surface.

[0025] Comparative Example 1 The difference between Comparative Example 1 and Example 2 is that step (1) is not performed, and step (4) is modified as follows: 52 parts by mass of modified polyvinyl alcohol, 6.5 parts by mass of modified phytic acid, 3.5 parts by mass of silicon dioxide, 1.25 parts by mass of azobisisobutyronitrile, 42 parts by mass of anhydrous ethanol, and 105 parts by mass of deionized water are weighed; and the modified polyvinyl alcohol, modified phytic acid, silicon dioxide, azobisisobutyronitrile, anhydrous ethanol, and deionized water are mixed uniformly to prepare an antibacterial agent for hard surfaces.

[0026] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that step (1) is not performed, and step (4) is modified as follows: 52 parts by mass of modified polyvinyl alcohol, 6.5 parts by mass of modified phytic acid, 3.5 parts by mass of silicon dioxide, 1.25 parts by mass of azobisisobutyronitrile, 42 parts by mass of anhydrous ethanol, and 105 parts by mass of deionized water are weighed; and the modified polyvinyl alcohol, modified phytic acid, silicon dioxide, azobisisobutyronitrile, anhydrous ethanol, and deionized water are mixed uniformly to prepare an antibacterial agent for hard surfaces.

[0027] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that step (2) is not performed, and step (4) is modified as follows: 52 parts by mass of modified polyvinyl alcohol, 6.5 parts by mass of phytic acid, 3.5 parts by mass of modified silicon dioxide, 1.25 parts by mass of azobisisobutyronitrile, 42 parts by mass of anhydrous ethanol, and 105 parts by mass of deionized water are weighed; and the modified polyvinyl alcohol, phytic acid, modified silicon dioxide, azobisisobutyronitrile, anhydrous ethanol, and deionized water are mixed uniformly to prepare an antibacterial agent for hard surfaces.

[0028] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that step (2) is not performed, and step (4) is modified as follows: 52 parts by mass of modified polyvinyl alcohol, 3.5 parts by mass of modified silicon dioxide, 1.25 parts by mass of azobisisobutyronitrile, 42 parts by mass of anhydrous ethanol, and 105 parts by mass of deionized water are weighed; and the modified polyvinyl alcohol, modified silicon dioxide, azobisisobutyronitrile, anhydrous ethanol, and deionized water are mixed uniformly to prepare an antibacterial agent for hard surfaces.

[0029] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that step (3) is not performed, and step (4) is modified as follows: 52 parts by mass of polyvinyl alcohol, 6.5 parts by mass of modified phytic acid, 3.5 parts by mass of modified silicon dioxide, 1.25 parts by mass of azobisisobutyronitrile, 42 parts by mass of anhydrous ethanol, and 105 parts by mass of deionized water are weighed; and the polyvinyl alcohol, modified phytic acid, modified silicon dioxide, azobisisobutyronitrile, anhydrous ethanol, and deionized water are mixed uniformly to prepare an antibacterial agent for hard surfaces.

[0030] Test Example 1 Test of antibacterial performance and wear resistance Test method: The examples and comparative examples are coated on the surface of a dry and clean stainless steel plate with a size of 30 cm x 30 cm, and the coating amount is 0.2 g / cm 2 After drying at 70 DEG C for 1 h, cooling to 50 DEG C for 2 h, and standing at room temperature for 20 h, the coating sample is prepared; The E. coli strain is activated and prepared into a bacterial suspension with a concentration of 3 x 10 4 2 ml of the bacterial suspension is diluted by 10 times, inoculated on the coating sample, and cultured at 37 DEG C for 16 h, and then colony counting is performed to calculate the antibacterial rate M.

[0031] The abrasion resistance is tested by using a water washing and rubbing instrument, a standard sponge rubbing head (135 g) is selected, the sponge rubbing head is wetted with 4 g of cleaning agent, and back and forth rubbing is performed for 500 times; the coating sample after rubbing is subjected to antibacterial testing by using the above method to obtain the antibacterial rate N after abrasion, and the antibacterial retention rate is calculated, and the antibacterial retention rate = N / M x 100%.

[0032] Table 1

[0033] From the comparison of the experimental data of examples 1-3 and comparative examples 1-5 in table 1, it can be found that the antibacterial agent for hard surface prepared by the present application has good antibacterial performance and abrasion resistance.

[0034] By comparison, the antibacterial rate of examples 1-3 is greater than that of comparative examples 1-2, which shows that the pretreated silicon dioxide is prepared by the reaction of silicon dioxide and chloropropyl triethoxysilane, the chlorine atom is introduced on the pretreated silicon dioxide, the pretreated silicon dioxide is reacted with 2,2'-dimethylpyridine amine to prepare the pretreated silicon dioxide, and the dimethylpyridine amine ligand structure is grafted on the pretreated silicon dioxide; the dimethylpyridine amine ligand structure grafted on the pretreated silicon dioxide is reacted with zinc nitrate to generate dimethylpyridine amine zinc complex; the dimethylpyridine amine zinc complex belongs to an organic zinc antibacterial agent, which can destroy the bacterial cell membrane, interfere with the enzyme activity of the bacterial cell electron transport system, react with the thio group / carboxyl group / hydroxyl group of the protein, destroy the spatial structure, and achieve the purpose of antibacterial.

[0035] By comparison, the antibacterial rate of examples 1-3 is greater than that of comparative example 4, which shows that the negatively charged phytic acid molecules can be combined with the positive charge on the surface of the bacteria, change the membrane permeability to cause the leakage of the contents, and improve the antibacterial ability of the antibacterial agent for hard surface.

[0036] By comparison, the bacteriostasis retention rate of examples 1~3 is greater than that of comparative example 2, which shows that silicon dioxide is a high-hardness inorganic material, and adding silicon dioxide in the antibacterial agent can improve the wear resistance of the antibacterial agent, reduce the wear of the antibacterial agent, and prolong the antibacterial effect.

[0037] By comparison, the bacteriostasis retention rate of examples 1~3 is greater than that of comparative example 2, which shows that silicon dioxide is a high-hardness inorganic material, and adding silicon dioxide in the antibacterial agent can improve the wear resistance of the antibacterial agent, reduce the wear of the antibacterial agent, and prolong the antibacterial effect.

[0038] By comparison, the bacteriostasis retention rate of examples 1~3 is greater than that of comparative example 2, which shows that silicon dioxide is a high-hardness inorganic material, and adding silicon dioxide in the antibacterial agent can improve the wear resistance of the antibacterial agent, reduce the wear of the antibacterial agent, and prolong the antibacterial effect.

[0039] By comparison, the bacteriostasis retention rate of examples 1~3 is greater than that of comparative example 2, which shows that silicon dioxide is a high-hardness inorganic material, and adding silicon dioxide in the antibacterial agent can improve the wear resistance of the antibacterial agent, reduce the wear of the antibacterial agent, and prolong the antibacterial effect.

[0040] The above specific embodiments further illustrate the purpose, technical solutions and beneficial effects of the present application. It should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An antibacterial agent for hard surfaces, characterized in that, By mass parts, it includes: 50-54 parts modified polyvinyl alcohol, 6-7 parts modified phytic acid, 3-4 parts modified silica, 1-1.5 parts azobisisobutyronitrile, 40-44 parts anhydrous ethanol, and 100-110 parts deionized water. The modified polyvinyl alcohol is prepared by reacting pre-modified polyvinyl alcohol with N-allyl imidazole. The pre-modified polyvinyl alcohol is prepared by reacting polyvinyl alcohol and 4-chloropropionic acid. The modified phytic acid is prepared by reacting phytic acid with 3-buten-1-amine. The modified silica is prepared by reacting silica sequentially with chloropropyltriethoxysilane, 2,2'-dimethylpyridineamine, and zinc nitrate.

2. A method for preparing an antibacterial agent for hard surfaces, characterized in that, The preparation method of the antibacterial agent for hard surfaces includes the following preparation steps: (1) Pretreated silica, 2,2'-dimethylpyridinium chloride, potassium carbonate and acetonitrile are mixed in a mass ratio of 1:(3~4):(0.5~0.7):(40~50) and stirred and refluxed at 80~82℃ for 24~26h under nitrogen protection to obtain pre-modified silica; pre-modified silica, zinc nitrate and methanol are mixed in a mass ratio of 1:(4~5):(30~32) and reacted at 40~50℃ for 10~12h to obtain modified silica; (2) Mix 3-buten-1-amine and anhydrous ethanol to prepare a 3-buten-1-amine solution; mix phytic acid, anhydrous ethanol and deionized water, and add the 3-buten-1-amine solution dropwise at a constant rate over 20 min under stirring conditions of 300-500 r / min at 60-62℃. After the addition is complete, continue stirring for 10-12 h to obtain modified phytic acid. (3) Mix pre-modified polyvinyl alcohol, N-allyl imidazole and dimethyl sulfoxide in a mass ratio of 1:(0.6~0.8):(14~16) and react at 60~70℃ for 12~14h to obtain modified polyvinyl alcohol. (4) Mix the modified polyvinyl alcohol, modified phytic acid, modified silica, azobisisobutyronitrile, anhydrous ethanol and deionized water evenly to prepare an antibacterial agent for hard surfaces.

3. The method for preparing an antibacterial agent for hard surfaces according to claim 2, characterized in that, The preparation method of the pretreated silica in step (1) is as follows: silica, deionized water and anhydrous ethanol are mixed and ultrasonically dispersed. A 10% hydrochloric acid aqueous solution with a mass fraction of 4-5 times the mass of silica is added, and chloropropyltriethoxysilane with a mass fraction of 7-8 times the mass of silica is added. The mixture is reacted at 60-70°C for 8-10 hours under nitrogen protection to obtain pretreated silica.

4. The method for preparing an antibacterial agent for hard surfaces according to claim 3, characterized in that, The silica has a particle size of 2000 mesh.

5. The method for preparing an antibacterial agent for hard surfaces according to claim 2, characterized in that, The molar ratio of phytic acid and 3-butene-1-amine in step (2) is 1:

4.

6. The method for preparing an antibacterial agent for hard surfaces according to claim 2, characterized in that, The preparation method of the pre-modified polyvinyl alcohol in step (3) is as follows: polyvinyl alcohol and dimethyl sulfoxide are mixed and stirred at 50°C for 15-17 min. 4-chloropropionic acid with a molar amount of 1-3 times that of polyvinyl alcohol is added, and concentrated sulfuric acid with a mass of 0.3-0.5 times that of polyvinyl alcohol is added. The reaction is continued at 50-70°C for 5-7 h to obtain pre-modified polyvinyl alcohol.

7. The method for preparing an antibacterial agent for hard surfaces according to claim 6, characterized in that, The polyvinyl alcohol is designated as PVA-0599.

8. The method for preparing an antibacterial agent for hard surfaces according to claim 6, characterized in that, The concentrated sulfuric acid has a mass fraction of 98%.

9. The method for preparing an antibacterial agent for hard surfaces according to claim 2, characterized in that, The amounts of modified polyvinyl alcohol, modified phytic acid, modified silica, azobisisobutyronitrile, anhydrous ethanol, and deionized water used in step (4) are as follows: by mass parts, 50-54 parts of modified polyvinyl alcohol, 6-7 parts of modified phytic acid, 3-4 parts of modified silica, 1-1.5 parts of azobisisobutyronitrile, 40-44 parts of anhydrous ethanol, and 100-110 parts of deionized water.

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