Anti-mildew antibacterial PVC printing film and preparation method thereof

Abstract

The invention discloses an anti-mildew antibacterial PVC printing film and a preparation method thereof, and relates to the technical field of printing films. When the anti-mildew and antibacterial PVC printing film is prepared, firstly, polyvinyl chloride reacts with paranitroaniline, a palladium-carbon catalyst is used for reduction, then the product reacts with 2, 3-bis (4-chlorphenyl)-2-cyclopropylene-1-ketone, then the product reacts with polyether amine, and modified polyvinyl chloride is obtained; secondly, enabling talcum powder pretreated by p-(triethoxysilyl) acetophenone to react with methyl tribenzoate phosphine to obtain modified talcum powder; finally, the modified polyvinyl chloride, the modified talcum powder and sodium methoxide are mixed and subjected to film casting, and the anti-mildew and antibacterial PVC printing film is prepared. The anti-mildew and antibacterial PVC printing film prepared by the invention has good flame retardance, mildew-proof and antibacterial properties, mechanical properties and ultraviolet aging resistance.

Description

Technical Field

[0001] The invention relates to the technical field of printing films, in particular to a mildew-proof and antibacterial PVC printing film and a preparation method thereof. Background Art

[0002] PVC printing film is a printing film with polyvinyl chloride as the substrate. This printing film has good weather resistance, chemical corrosion resistance and heat insulation performance, and its surface is flat and smooth, suitable for a variety of printing processes. Therefore, it is widely used in packaging, construction, medical treatment, advertising signs and other fields.

[0003] In the field of food and medical packaging, traditional polyvinyl chloride film is prone to breeding bacteria and mold, which not only affects the hygiene performance and service life of the product, but also may pose a potential threat to people's health; for outdoor use scenarios such as advertising signs, traditional polyvinyl chloride film is prone to aging during long-term use, such as discoloration and cracking; in addition, its flame retardant performance is also poor. Once it encounters fire, it is easy to burn and may release harmful gases, posing a threat to the safety of people and property. Flame retardant performance is particularly critical in application fields such as building materials; therefore, in order to meet the market demand for high-quality, high-performance printed films, the research and development and application of PVC printed films should focus on improving anti-mildew, anti-bacterial, anti-aging, flame retardant and other properties. Summary of the invention

[0004] The object of the present invention is to provide a mildew-proof and antibacterial PVC printed film and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0006] The invention discloses an anti-mildew and antibacterial PVC printing film, which is prepared by mixing modified polyvinyl chloride, modified talcum powder and sodium methoxide and casting the mixed film.

[0007] As an optimization, the modified polyvinyl chloride is obtained by reacting polyvinyl chloride with p-nitroaniline, reducing it using a palladium-carbon catalyst, reacting it with 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, and then reacting it with polyetheramine.

[0008] As an optimization, the modified talc is obtained by reacting talc pretreated with (triethoxysilyl)acetophenone and methyl tribenzoate phosphine.

[0009] A method for preparing a mildew-proof and antibacterial PVC printed film comprises the following preparation steps:

[0010] (1) polyvinyl chloride, p-nitroaniline, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(0.3-0.5):(50-60), heated to 70-80° C. and stirred for 2 hours, then cooled to room temperature and stirred for 3-4 hours, and vacuum-dried at 50-60° C. to remove N,N-dimethylformamide, and dried in vacuo at 50-60° C. for 6-8 hours to obtain pretreated polyvinyl chloride;

[0011] (2) pretreated polyvinyl chloride, N,N-dimethylformamide, and 3% palladium carbon catalyst are mixed in a mass ratio of 1:(50-60):(0.02-0.03), reacted in an argon atmosphere, 0.4 MPa, 30-40° C. for 4-5 h, vacuum evaporated to remove N,N-dimethylformamide, and vacuum dried at 50-60° C. for 6-8 h to obtain amino polyvinyl chloride;

[0012] (3) Aminated polyvinyl chloride, 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, sulfur, iron (III) trifluoromethanesulfonate, trifluoromethanesulfonic anhydride, and dimethyl sulfoxide are mixed, the temperature is raised to 140° C. for reaction for 4-5 hours, ethyl acetate in an amount equal to the volume of dimethyl sulfoxide is added for extraction, the organic phase is retained, washed with a saturated potassium carbonate solution for 4 times, and dried with anhydrous magnesium sulfate, the anhydrous magnesium sulfate is removed by filtration, the filtrate is retained, and vacuum distillation is performed to obtain pre-modified polyvinyl chloride;

[0013] (4) Pre-modified polyvinyl chloride, polyetheramine, sodium tert-butoxide, and N,N-dimethylformamide are mixed in a mass ratio of 1:(2-3):(0.8-0.9):(50-60), heated to 70-80° C., reacted for 1-2 hours, and vacuum rotary evaporation to remove N,N-dimethylformamide to obtain modified polyvinyl chloride;

[0014] (5) Pretreated talc, methyl tribenzoate phosphine, sodium hydride, and tetrahydrofuran were mixed in a mass ratio of 1:(2-3):(1.2-1.3):(10-12), reacted at 30° C. for 90-100 min, filtered, washed with pure water for 3-4 times, and vacuum dried at 50-60° C. for 12 h to obtain modified talc;

[0015] (6) Modified polyvinyl chloride, modified talc, sodium methoxide, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(0.03-0.05):0.01:(10-12), then poured onto a glass plate to form a film, and dried at 60-70° C. for 5-6 h to obtain an anti-mildew and antibacterial PVC printed film.

[0016] As an optimization, the polyvinyl chloride model in step (1) is SG-8.

[0017] As an optimization, the mass ratio of the amino polyvinyl chloride, 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, sulfur, iron (III) trifluoromethanesulfonate, trifluoromethanesulfonic anhydride, and dimethyl sulfoxide in step (3) is 1:(0.3-0.5):(0.4-0.6):(0.02-0.03):(0.1-0.2):(20-30); the particle size of the sulfur is 400-600 mesh.

[0018] As an optimization, the preparation method of the polyetheramine in step (4) is as follows: ethanolamine, 3-pentanone and aluminum chloride are mixed in a mass ratio of 1: (1.4-1.6): (0.03-0.05), heated to 120-130° C. under a nitrogen atmosphere, refluxed for 5 hours, and distilled under reduced pressure to obtain an imine monomer; the imine monomer and boron trifluoride ether are mixed in a mass ratio of 1: (0.02-0.03), heated at 110° C. for 30 minutes, and propylene oxide in an amount of 20-30 times the mass of the imine monomer is added at 0.3 MPa to obtain a polyetheramine precursor; the polyetheramine precursor and a 10wt% acetic acid aqueous solution are mixed in a mass ratio of 1: (20-30), heated to 70° C. for 1 hour, and allowed to stand for 50-60 minutes after the reaction is completed, the liquids are separated and the oil phase is retained, and the oil phase is distilled under reduced pressure to obtain the polyetheramine.

[0019] As an optimization, the preparation method of the pretreated talc powder in step (5) is: p-(triethoxysilyl)acetophenone, talc powder, pure water, and anhydrous ethanol are mixed in a mass ratio of 1:0.3:1.2:10, stirred at 70°C for 40 minutes, filtered and washed with ethanol 4 times, and vacuum dried at 60°C for 8 hours to obtain pretreated talc powder.

[0020] As an optimization, the talc powder has a particle size of 325 meshes.

[0021] As an optimization, the preparation method of the trimethyl benzoate phosphine in step (5) is as follows: tri(trimethylsilyl)phosphine, methyl p-fluorobenzoate, and cesium fluoride are weighed in a molar ratio of 1:3.1:2.1, cesium fluoride and N,N-dimethylformamide are mixed in a mass ratio of 1:5, and then methyl p-fluorobenzoate is added, and then tri(trimethylsilyl)phosphine is added dropwise at a drop rate of 1 mL / min. After the addition is completed, the reaction is carried out at room temperature for 6 hours. After the reaction is completed, pure water with an equal volume of N,N-dimethylformamide and dichloromethane with an equal volume of N,N-dimethylformamide are added and mixed for 5 minutes, the organic phase is separated and dried with anhydrous magnesium sulfate, the anhydrous magnesium sulfate is filtered out and the filtrate is retained, and the trimethyl benzoate phosphine is obtained by vacuum rotary evaporation.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] When preparing the mildew-proof and antibacterial PVC printing film, the present invention comprises the following steps: firstly, polyvinyl chloride is reacted with p-nitroaniline, and then reduced by using a palladium-carbon catalyst, and then reacted with 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, and then reacted with polyetheramine to obtain modified polyvinyl chloride; secondly, talcum powder pretreated with p-(triethoxysilyl)acetophenone is reacted with methyl tribenzoate phosphine to obtain modified talcum powder; and finally, the modified polyvinyl chloride, the modified talcum powder and sodium methoxide are mixed and cast to form a film to obtain the mildew-proof and antibacterial PVC printing film.

[0024] First, polyvinyl chloride is reacted with p-nitroaniline, and the chlorine and amino groups on the polyvinyl chloride undergo affinity substitution, so that nitrobenzene is grafted onto the side chain of the polyvinyl chloride. The nitro group is reduced to an amino group using a palladium-carbon catalyst, and the amino group reacts with 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one to generate an isothiazolinone structure. The isothiazolinone structure has high activity, strong bactericidal properties, and has a broad-spectrum antibacterial property, and can give the PVC printed film good mildew and antibacterial properties; the chlorophenyl group on 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one reacts with the amino group at one end of the polyetheramine, so that the polyvinyl chloride is grafted onto the polyetheramine structure. The ether bond in the polyetheramine and the terminal hydroxyl group have good hydrophilicity, and can give the PVC printed film good antistatic properties;

[0025] Secondly, the talc powder pretreated with (triethoxysilyl)acetophenone and methyl tribenzoate phosphine are reacted to obtain modified talc powder. The surface of the talc powder pretreated with (triethoxysilyl)acetophenone contains an acetophenone structure. The acetophenone structure and the methyl benzoate group of the methyl tribenzoate phosphine are condensed to generate a dibenzoylmethane structure. There is a tautomeric equilibrium between keto and enol forms in the dibenzoylmethane structure. The tautomerism process between the two structures can convert light energy into heat energy or harmless low-energy radiation, thereby effectively absorbing ultraviolet rays and giving the PVC printed film good anti-ultraviolet aging performance; the phosphorus element in the methyl tribenzoate phosphine can give the PVC printed film good flame retardant performance.

[0026] Finally, modified polyvinyl chloride, modified talc and sodium methoxide were mixed and cast to prepare mildew-proof and antibacterial PVC printed film. The modified polyvinyl chloride grafted with polyetheramine underwent ester exchange with methyl benzoate on the surface of modified talc through the alcohol hydroxyl group at the end of the polyetheramine in the presence of sodium methoxide to form a cross-linked structure, which can further enhance the mechanical properties of the PVC printed film. DETAILED DESCRIPTION

[0027] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0028] The polyvinyl chloride used in the following examples and comparative examples is of type SG-8; the talc used has a particle size of 325 mesh; and the sulfur used has a particle size of 400-600 mesh.

[0029] Embodiment 1:

[0030] A method for preparing a mildew-proof and antibacterial PVC printed film, the method for preparing the mildew-proof and antibacterial PVC printed film comprising the following preparation steps:

[0031] (1) polyvinyl chloride, p-nitroaniline, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:0.3:50, heated to 80° C. and stirred for 2 h, then cooled to room temperature and stirred for 4 h, and N,N-dimethylformamide is removed by vacuum evaporation, and vacuum dried at 60° C. for 8 h to obtain pretreated polyvinyl chloride;

[0032] (2) pretreated polyvinyl chloride, N,N-dimethylformamide, and 3% palladium carbon catalyst were mixed in a mass ratio of 1:50:0.02, reacted under argon atmosphere, 0.4 MPa, 40° C. for 5 h, and vacuum evaporated to remove N,N-dimethylformamide, and dried under vacuum at 60° C. for 8 h to obtain amino polyvinyl chloride;

[0033] (3) Weighing amino polyvinyl chloride, 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, sulfur, iron (III) trifluoromethanesulfonate, trifluoromethanesulfonic anhydride, and dimethyl sulfoxide in a mass ratio of 1:0.3:0.4:0.02:0.1:20, then mixing, heating to 140° C. for reaction for 5 h, adding ethyl acetate in an equal volume to dimethyl sulfoxide for extraction, retaining the organic phase, washing it with a saturated potassium carbonate solution for 4 times, and drying it with anhydrous magnesium sulfate, filtering to remove the anhydrous magnesium sulfate, retaining the filtrate and distilling it under reduced pressure to obtain pre-modified polyvinyl chloride;

[0034] (4) Ethanolamine, 3-pentanone, and aluminum chloride are mixed in a mass ratio of 1:1.4:0.03, heated to 130° C. under a nitrogen atmosphere, refluxed for 5 hours, and distilled under reduced pressure to obtain an imine monomer; the imine monomer and boron trifluoride ether are mixed in a mass ratio of 1:0.02, heated at 110° C. for 30 minutes, and propylene oxide 20 times the mass of the imine monomer is added at 0.3 MPa to obtain a polyetheramine precursor; the polyetheramine precursor and a 10 wt % acetic acid aqueous solution are mixed in a mass ratio of 1:20, heated to 70° C. for 1 hour, and allowed to stand for 60 minutes after the reaction is completed, the liquids are separated and the oil phase is retained, and the oil phase is distilled under reduced pressure to obtain a polyetheramine; pre-modified polyvinyl chloride, polyetheramine, sodium tert-butoxide, and N,N-dimethylformamide are mixed in a mass ratio of 1:2:0.8:50, heated to 80° C., reacted for 2 hours, and N,N-dimethylformamide is removed by rotary distillation under reduced pressure to obtain modified polyvinyl chloride;

[0035] (5) p-(triethoxysilyl)acetophenone, talc, pure water and anhydrous ethanol were mixed in a mass ratio of 1:0.3:1.2:10, stirred at 70°C for 40 minutes, filtered and washed with ethanol four times, and vacuum dried at 60°C for 8 hours to obtain pretreated talc; tri(trimethylsilyl)phosphine, methyl p-fluorobenzoate and cesium fluoride were weighed in a molar ratio of 1:3.1:2.1, cesium fluoride and N,N-dimethylformamide were mixed in a mass ratio of 1:5, and then methyl p-fluorobenzoate was added, and then tri(trimethylsilyl)phosphine was added dropwise at a rate of 1 mL / min, and the resultant solution was added dropwise. After the reaction is completed, react at room temperature for 6 hours. After the reaction is completed, add pure water with an equal volume of N,N-dimethylformamide and dichloromethane with an equal volume of N,N-dimethylformamide and mix for 5 minutes, separate the organic phase, dry it with anhydrous magnesium sulfate, filter out the anhydrous magnesium sulfate and retain the filtrate, and evaporate under reduced pressure to obtain methyl tribenzoate phosphine; mix the pretreated talc powder, methyl tribenzoate phosphine, sodium hydride, and tetrahydrofuran in a mass ratio of 1:2:1.2:10, react at 30°C for 100 minutes, filter and wash with pure water 4 times, and vacuum dry at 60°C for 12 hours to obtain modified talc powder;

[0036] (6) Modified polyvinyl chloride, modified talc, sodium methoxide, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.03:0.01:10, then poured onto a glass plate to form a film, and dried at 70°C for 6 hours to obtain an anti-mildew and antibacterial PVC printed film.

[0037] Embodiment 2:

[0038] A method for preparing a mildew-proof and antibacterial PVC printed film, the method for preparing the mildew-proof and antibacterial PVC printed film comprising the following preparation steps:

[0039] (1) polyvinyl chloride, p-nitroaniline, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:0.4:55, heated to 75° C. and stirred for 2 hours, cooled to room temperature and stirred for 3.5 hours, and N,N-dimethylformamide is removed by vacuum evaporation, and vacuum dried at 55° C. for 7 hours to obtain pretreated polyvinyl chloride;

[0040] (2) pretreated polyvinyl chloride, N,N-dimethylformamide, and 3% palladium carbon catalyst were mixed in a mass ratio of 1:55:0.025, reacted under argon atmosphere, 0.4 MPa, 35° C. for 4.5 h, and vacuum evaporated to remove N,N-dimethylformamide, and dried under vacuum at 55° C. for 7 h to obtain amino polyvinyl chloride;

[0041] (3) Weighing amino polyvinyl chloride, 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, sulfur, iron (III) trifluoromethanesulfonate, trifluoromethanesulfonic anhydride, and dimethyl sulfoxide in a mass ratio of 1:0.4:0.5:0.025:0.15:25, then mixing, heating to 140° C. for reaction for 4.5 h, adding ethyl acetate in an amount equal to the volume of dimethyl sulfoxide for extraction, retaining the organic phase, washing it four times with a saturated potassium carbonate solution, and drying it with anhydrous magnesium sulfate, filtering to remove the anhydrous magnesium sulfate, retaining the filtrate and distilling it under reduced pressure to obtain pre-modified polyvinyl chloride;

[0042] (4) Ethanolamine, 3-pentanone, and aluminum chloride were mixed in a mass ratio of 1:1:0.04, heated to 125° C. under a nitrogen atmosphere, refluxed for 5 h, and distilled under reduced pressure to obtain an imine monomer; the imine monomer and boron trifluoride ether were mixed in a mass ratio of 1:0.025, heated at 110° C. for 30 min, and propylene oxide in an amount 25 times the mass of the imine monomer was added at 0.3 MPa to obtain a polyetheramine precursor; the polyetheramine precursor and 10 wt % The pre-modified polyvinyl chloride, polyetheramine, sodium tert-butoxide and N,N-dimethylformamide were mixed in a mass ratio of 1:2.5:0.85:55, heated to 75°C, reacted for 1.5 hours, and vacuum distilled to remove N,N-dimethylformamide to obtain modified polyvinyl chloride;

[0043] (5) p-(triethoxysilyl)acetophenone, talc, pure water and anhydrous ethanol were mixed in a mass ratio of 1:0.3:1.2:10, stirred at 70°C for 40 minutes, filtered and washed with ethanol 4 times, and vacuum dried at 60°C for 8 hours to obtain pretreated talc; tri(trimethylsilyl)phosphine, methyl p-fluorobenzoate and cesium fluoride were weighed in a molar ratio of 1:3.1:2.1, cesium fluoride and N,N-dimethylformamide were mixed in a mass ratio of 1:5, and then methyl p-fluorobenzoate was added, and then tri(trimethylsilyl)phosphine was added dropwise at a drop rate of 1 mL / min until the addition was completed. After that, react at room temperature for 6 hours. After the reaction is completed, add pure water with an equal volume of N,N-dimethylformamide and dichloromethane with an equal volume of N,N-dimethylformamide and mix for 5 minutes, separate the organic phase, dry it with anhydrous magnesium sulfate, filter out the anhydrous magnesium sulfate and retain the filtrate, and evaporate under reduced pressure to obtain methyl tribenzoate phosphine; mix the pretreated talcum powder, methyl tribenzoate phosphine, sodium hydride and tetrahydrofuran in a mass ratio of 1:2.5:1.25:11, react at 30°C for 95 minutes, filter and wash with pure water 3 times, and vacuum dry at 55°C for 12 hours to obtain modified talcum powder;

[0044] (6) Modified polyvinyl chloride, modified talc, sodium methoxide, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.04:0.01:11, then poured onto a glass plate to form a film, and dried at 65°C for 5.5 hours to obtain an anti-mildew and antibacterial PVC printed film.

[0045] Embodiment 3:

[0046] A method for preparing a mildew-proof and antibacterial PVC printed film, the method for preparing the mildew-proof and antibacterial PVC printed film comprising the following preparation steps:

[0047] (1) polyvinyl chloride, p-nitroaniline, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:0.5:60, heated to 70° C. and stirred for 2 h, then cooled to room temperature and stirred for 3 h, and N,N-dimethylformamide is removed by vacuum evaporation, and vacuum dried at 50° C. for 6 h to obtain pretreated polyvinyl chloride;

[0048] (2) pretreated polyvinyl chloride, N,N-dimethylformamide, and 3% palladium carbon catalyst were mixed in a mass ratio of 1:60:0.03, reacted under argon atmosphere, 0.4 MPa, 30° C. for 4 h, and vacuum evaporated to remove N,N-dimethylformamide, and dried under vacuum at 50° C. for 6 h to obtain amino polyvinyl chloride;

[0049] (3) Weighing amino polyvinyl chloride, 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, sulfur, iron (III) trifluoromethanesulfonate, trifluoromethanesulfonic anhydride, and dimethyl sulfoxide in a mass ratio of 1:0.5:0.6:0.03:0.2:30, then mixing, heating to 140° C. for reaction for 4 h, adding ethyl acetate in an equal volume to dimethyl sulfoxide for extraction, retaining the organic phase, washing it with a saturated potassium carbonate solution for 4 times, and drying it with anhydrous magnesium sulfate, filtering to remove the anhydrous magnesium sulfate, retaining the filtrate and distilling it under reduced pressure to obtain pre-modified polyvinyl chloride;

[0050] (4) Ethanolamine, 3-pentanone, and aluminum chloride are mixed in a mass ratio of 1:1.6:0.05, heated to 120° C. under a nitrogen atmosphere, refluxed for 5 hours, and distilled under reduced pressure to obtain an imine monomer; the imine monomer and boron trifluoride ether are mixed in a mass ratio of 1:0.03, heated at 110° C. for 30 minutes, and propylene oxide 30 times the mass of the imine monomer is added at 0.3 MPa to obtain a polyetheramine precursor; the polyetheramine precursor and a 10 wt % acetic acid aqueous solution are mixed in a mass ratio of 1:30, heated to 70° C. for 1 hour, and allowed to stand for 50 minutes after the reaction is completed, the liquids are separated and the oil phase is retained, and the oil phase is distilled under reduced pressure to obtain a polyetheramine; pre-modified polyvinyl chloride, polyetheramine, sodium tert-butoxide, and N,N-dimethylformamide are mixed in a mass ratio of 1:3:0.9:60, heated to 70° C., reacted for 1 hour, and N,N-dimethylformamide is removed by rotary distillation under reduced pressure to obtain modified polyvinyl chloride;

[0051] (5) p-(triethoxysilyl)acetophenone, talc, pure water and anhydrous ethanol were mixed in a mass ratio of 1:0.3:1.2:10, stirred at 70°C for 40 minutes, filtered and washed with ethanol four times, and vacuum dried at 60°C for 8 hours to obtain pretreated talc; tri(trimethylsilyl)phosphine, methyl p-fluorobenzoate and cesium fluoride were weighed in a molar ratio of 1:3.1:2.1, cesium fluoride and N,N-dimethylformamide were mixed in a mass ratio of 1:5, and then methyl p-fluorobenzoate was added, and then tri(trimethylsilyl)phosphine was added dropwise at a rate of 1 mL / min, and the resultant solution was added dropwise. After the reaction was completed, the mixture was reacted at room temperature for 6 hours. After the reaction was completed, pure water having an equal volume to N,N-dimethylformamide and dichloromethane having an equal volume to N,N-dimethylformamide were added and mixed for 5 minutes. The organic phase was separated and dried over anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered out and the filtrate was retained. The tribenzoic acid methyl ester phosphine was obtained by rotary evaporation under reduced pressure. The pretreated talc powder, tribenzoic acid methyl ester phosphine, sodium hydride and tetrahydrofuran were mixed in a mass ratio of 1:3:1.3:12, reacted at 30°C for 90 minutes, filtered and washed with pure water for 3 times, and vacuum dried at 50°C for 12 hours to obtain modified talc powder.

[0052] (6) Modified polyvinyl chloride, modified talc, sodium methoxide, and N,N-dimethylformamide were mixed evenly in a mass ratio of 1:0.05:0.01:12, then poured onto a glass plate to form a film, and dried at 60°C for 5 hours to obtain an anti-mildew and antibacterial PVC printed film.

[0053] Comparative Example 1:

[0054] The preparation method of the mildew-proof and antibacterial PVC printed film of Comparative Example 1 differs from that of Example 2 in that it does not contain steps (1) to (4), and step (6) is modified as follows: polyvinyl chloride, modified talc, sodium methoxide, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:0.04:0.01:11, and then poured onto a glass plate to cast a film, and dried at 65°C for 5.5h to obtain a mildew-proof and antibacterial PVC printed film.

[0055] Comparative Example 2:

[0056] The preparation method of the mildew-proof and antibacterial PVC printed film of Comparative Example 2 differs from that of Example 2 in that step (5) is not included, and step (6) is modified as follows: modified polyvinyl chloride, talcum powder, sodium methoxide, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:0.04:0.01:11, and then poured onto a glass plate to cast a film, and dried at 65°C for 5.5 hours to obtain a mildew-proof and antibacterial PVC printed film.

[0057] Comparative Example 3:

[0058] The preparation method of the mildew-proof and antibacterial PVC printed film of Comparative Example 3 is different from that of Example 2 in that step (5) is modified as follows: tri(trimethylsilyl)phosphine, methyl p-fluorobenzoate, and cesium fluoride are weighed in a molar ratio of 1:3.1:2.1, cesium fluoride and N,N-dimethylformamide are mixed in a mass ratio of 1:5, and then methyl p-fluorobenzoate is added, and then tri(trimethylsilyl)phosphine is added dropwise at a drop rate of 1 mL / min. After the addition is completed, the mixture is reacted at room temperature for 6 h. After the reaction is completed, pure water having an equal volume to that of N,N-dimethylformamide and dichloromethane having an equal volume to that of N,N-dimethylformamide are added and mixed for 5 min, the organic phase is separated and dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate is removed by filtration, and the filtrate is retained, and tribenzoic acid methyl ester phosphine is obtained by vacuum rotary evaporation; the pretreated talc powder and tribenzoic acid methyl ester phosphine are mixed in a mass ratio of 1:2.5 to obtain modified talc powder.

[0059] Test Example 1:

[0060] Flame retardant performance test:

[0061] Test method: The mildew-proof and antibacterial PVC films prepared in the examples and comparative examples were tested for limiting oxygen index using a JF-3 instrument. The results are shown in Table 1.

[0062] Table 1

[0063] Limiting oxygen index (%) Limiting oxygen index (%) Example 1 32.7 Comparative Example 1 30.4 Example 2 32.9 Comparative Example 2 25.4 Example 3 33.2 Comparative Example 3 32.6

[0064] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 1, it can be found that the mildew-proof and antibacterial PVC printed film prepared by the present invention has good flame retardant properties.

[0065] By comparison, the limiting oxygen index of Examples 1 to 3 is greater than that of Comparative Example 2, indicating that the modified talc is obtained by reacting talc pretreated with (triethoxysilyl)acetophenone with methyl tribenzoate phosphine, and the phosphorus element in methyl tribenzoate phosphine can give the PVC printed film good flame retardant properties.

[0066] Test Example 2:

[0067] Test of anti-mildew and antibacterial properties:

[0068] Test method: Referring to the standard QB / T 2591-2003, the antibacterial properties of the mildew-proof and antibacterial PVC printed films prepared in the examples and comparative examples were tested by the film laminating method, and the mold used in the test was Aspergillus niger. The results are shown in Table 2.

[0069] Table 2

[0070] Antibacterial rate (%) Antibacterial rate (%) Example 1 97.57 Comparative Example 1 23.14 Example 2 97.55 Comparative Example 2 97.43 Example 3 97.61 Comparative Example 3 97.51

[0071] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 3 in Table 2, it can be found that the mildew-proof and antibacterial PVC printed film prepared by the present invention has good antibacterial properties.

[0072] By comparison, the antibacterial rates of Examples 1 to 3 are greater than that of Comparative Example 2, indicating that polyvinyl chloride is reacted with p-nitroaniline, chlorine and amino groups on polyvinyl chloride undergo affinity substitution, so that nitrobenzene is grafted onto the side chains of polyvinyl chloride, and the nitro group is reduced to amino group using a palladium-carbon catalyst, and the amino group reacts with 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one to generate an isothiazolinone structure. The isothiazolinone structure has high activity, strong bactericidal property, and broad-spectrum antibacterial property, and can give the PVC printed film good mildew and antibacterial properties.

[0073] Test Example 3:

[0074] Mechanical properties test:

[0075] Test method: According to the standard GB / T1040.2-2006, the tensile properties of the mildew-proof and antibacterial PVC printed films prepared in the examples and comparative examples were tested on a tensile testing machine, with a gauge length of 20 mm and a tensile speed of 5 mm / min, and the tensile strength was recorded. The results are shown in Table 3.

[0076] Test of anti-ultraviolet aging performance:

[0077] Test method: The mildew-proof and antibacterial PVC printed films prepared in the examples and comparative examples were placed in a UV light box. There were 4 Q-LabUVA340 UV lamps in the light box. The distance between the lamps was 10 cm. The distance between the mildew-proof and antibacterial PVC printed films and the lamps was 5 cm. The central wavelength of the ultraviolet rays was 340 nm and the intensity was 13 mW / cm 2 The size of the light box is 130cm*45cm*20cm, and the irradiation time is 720h. After the irradiation, the tensile strength is tested according to the mechanical property test method and the tensile strength retention rate before and after ultraviolet irradiation is calculated. The results are shown in Table 3.

[0078] Table 3

[0079] Tensile strength(MPa) Tensile strength retention rate (%) Example 1 35.97 96.26 Example 2 36.23 95.97 Example 3 36.34 96.32 Comparative Example 1 26.47 96.14 Comparative Example 2 30.03 26.47 Comparative Example 3 30.57 37.43

[0080] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 4 in Table 3, it can be found that the mildew-proof and antibacterial PVC printed film prepared by the present invention has good mechanical properties and anti-ultraviolet aging properties.

[0081] The tensile strength of Examples 1 to 3 is greater than that of Comparative Examples 1 to 3, and the tensile strength retention rate of Examples 1 to 3 is greater than that of Comparative Examples 2 to 3, indicating that the talc pretreated with (triethoxysilyl)acetophenone and methyl tribenzoate phosphine are reacted to obtain modified talc, and the surface of the talc pretreated with (triethoxysilyl)acetophenone contains an acetophenone structure, and the acetophenone structure and the methyl benzoate group of the methyl tribenzoate phosphine are condensed to form a dibenzoylmethane structure, and there is a keto-enol interaction in the dibenzoylmethane structure. The tautomerism balance, the tautomerism process between the two structures can convert light energy into heat energy or harmless low-energy radiation, thereby effectively absorbing ultraviolet rays and giving the PVC printed film good anti-ultraviolet aging properties; the modified polyvinyl chloride, modified talcum powder and sodium methoxide are mixed and cast into a film to prepare the mildew-proof and antibacterial PVC printed film, and the modified polyvinyl chloride grafted with polyetheramine undergoes ester exchange with methyl benzoate on the surface of modified talcum powder through the alcohol hydroxyl group at the end of the polyetheramine in the presence of sodium methoxide to form a cross-linked structure, which can further enhance the mechanical properties of the PVC printed film.

[0082] It will be apparent to those skilled in the art that the 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 features 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, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A mildew-proof and antibacterial PVC printed film, characterized in that: The anti-mildew and antibacterial PVC printing film is prepared by mixing modified polyvinyl chloride, modified talcum powder and sodium methoxide and casting the mixed film; The modified polyvinyl chloride is obtained by reacting polyvinyl chloride with p-nitroaniline, reducing it with a palladium-carbon catalyst, reacting it with 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, and then reacting it with a polyetheramine. The modified talc is obtained by reacting talc pretreated with (triethoxysilyl)acetophenone and methyl tribenzoate phosphine.

2. A method for preparing a mildew-proof and antibacterial PVC printed film, characterized in that: The method comprises the following preparation steps: (1) polyvinyl chloride, p-nitroaniline, and N,N-dimethylformamide are uniformly mixed in a mass ratio of 1:(0.3-0.5):(50-60), heated to 70-80° C. and stirred for 2 hours, then cooled to room temperature and stirred for 3-4 hours, and vacuum-dried at 50-60° C. to remove N,N-dimethylformamide, and dried in vacuo at 50-60° C. for 6-8 hours to obtain pretreated polyvinyl chloride; (2) pretreated polyvinyl chloride, N,N-dimethylformamide, and 3% palladium carbon catalyst are mixed in a mass ratio of 1:(50-60):(0.02-0.03), reacted in an argon atmosphere, 0.4 MPa, 30-40° C. for 4-5 h, vacuum evaporated to remove N,N-dimethylformamide, and vacuum dried at 50-60° C. for 6-8 h to obtain amino polyvinyl chloride; (3) Aminated polyvinyl chloride, 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, sulfur, iron (III) trifluoromethanesulfonate, trifluoromethanesulfonic anhydride, and dimethyl sulfoxide are mixed, the temperature is raised to 140° C. for reaction for 4-5 hours, ethyl acetate in an amount equal to the volume of dimethyl sulfoxide is added for extraction, the organic phase is retained, washed with a saturated potassium carbonate solution for 4 times, and dried with anhydrous magnesium sulfate, the anhydrous magnesium sulfate is removed by filtration, the filtrate is retained, and vacuum distillation is performed to obtain pre-modified polyvinyl chloride; (4) Pre-modified polyvinyl chloride, polyetheramine, sodium tert-butoxide, and N,N-dimethylformamide are mixed in a mass ratio of 1:(2-3):(0.8-0.9):(50-60), heated to 70-80° C., reacted for 1-2 hours, and vacuum rotary evaporation to remove N,N-dimethylformamide to obtain modified polyvinyl chloride; (5) Pretreated talc, methyl tribenzoate phosphine, sodium hydride, and tetrahydrofuran were mixed in a mass ratio of 1:(2-3):(1.2-1.3):(10-12), reacted at 30° C. for 90-100 min, filtered, washed with pure water for 3-4 times, and vacuum dried at 50-60° C. for 12 h to obtain modified talc; (6) Modified polyvinyl chloride, modified talc, sodium methoxide, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(0.03-0.05):0.01:(10-12), then poured onto a glass plate to form a film, and dried at 60-70° C. for 5-6 h to obtain an anti-mildew and antibacterial PVC printed film.

3. The method for preparing a mildew-proof and antibacterial PVC printed film according to claim 2, characterized in that: The polyvinyl chloride model in step (1) is SG-8.

4. The method for preparing a mildew-proof and antibacterial PVC printed film according to claim 2, characterized in that: The mass ratio of the amino polyvinyl chloride, 2,3-bis(4-chlorophenyl)-2-cyclopropene-1-one, sulfur, iron (III) trifluoromethanesulfonate, trifluoromethanesulfonic anhydride and dimethyl sulfoxide in step (3) is 1:(0.3-0.5):(0.4-0.6):(0.02-0.03):(0.1-0.2):(20-30); the particle size of the sulfur is 400-600 mesh.

5. The method for preparing a mildew-proof and antibacterial PVC printed film according to claim 2, characterized in that: The preparation method of the polyetheramine in step (4) is as follows: ethanolamine, 3-pentanone and aluminum chloride are mixed in a mass ratio of 1:(1.4-1.6):(0.03-0.05), heated to 120-130° C. under a nitrogen atmosphere, refluxed for 5 hours, and distilled under reduced pressure to obtain an imine monomer; the imine monomer and boron trifluoride ether are mixed in a mass ratio of 1:(0.02-0.03), heated at 110° C. for 30 minutes, and propylene oxide in an amount of 20-30 times the mass of the imine monomer is added at 0.3 MPa to obtain a polyetheramine precursor; the polyetheramine precursor and a 10wt% acetic acid aqueous solution are mixed in a mass ratio of 1:(20-30), heated to 70° C. for 1 hour, and allowed to stand for 50-60 minutes after the reaction is completed, the liquids are separated and the oil phase is retained, and the oil phase is distilled under reduced pressure to obtain the polyetheramine.

6. The method for preparing a mildew-proof and antibacterial PVC printed film according to claim 2, characterized in that: The preparation method of the pretreated talc powder in step (5) is as follows: p-(triethoxysilyl)acetophenone, talc powder, pure water and anhydrous ethanol are mixed in a mass ratio of 1:0.3:1.2:10, stirred at 70°C for 40 minutes, filtered and washed with ethanol 4 times, and vacuum dried at 60°C for 8 hours to obtain pretreated talc powder.

7. The method for preparing a mildew-proof and antibacterial PVC printed film according to claim 2, characterized in that: The preparation method of the trimethyl benzoate phosphine in step (5) is as follows: tri(trimethylsilyl)phosphine, methyl p-fluorobenzoate and cesium fluoride are weighed in a molar ratio of 1:3.1:2.1, cesium fluoride and N,N-dimethylformamide are mixed in a mass ratio of 1:5, and then methyl p-fluorobenzoate is added, and then tri(trimethylsilyl)phosphine is added dropwise at a drop rate of 1 mL / min. After the addition is completed, the mixture is reacted at room temperature for 6 hours. After the reaction is completed, pure water having an equal volume to N,N-dimethylformamide and dichloromethane having an equal volume to N,N-dimethylformamide are added and mixed for 5 minutes, the organic phase is separated and dried over anhydrous magnesium sulfate, the anhydrous magnesium sulfate is removed by filtration and the filtrate is retained, and the trimethyl benzoate phosphine is obtained by vacuum rotary evaporation.

8. The method for preparing a mildew-proof and antibacterial PVC printed film according to claim 6, characterized in that: The talcum powder has a particle size of 325 meshes.