A fluorine-free antibacterial TPU protective film and preparation method thereof

Abstract

The present invention relates to the technical field of TPU protective films, and specifically to a fluorine-free antibacterial TPU protective film and a preparation method thereof: comprising the following raw materials in parts by weight: 35-40 parts of TPU particles, 10-15 parts of a balancing agent, 8-12 parts of an antibacterial agent, 3-6 parts of an antioxidant, 3-5 parts of a thermal stabilizer, and 2-3 parts of a lubricant. The TPU protective film of the present invention uses TPU particles in combination with an antibacterial agent, an antioxidant, a thermal stabilizer, and a lubricant as functional additives, and by adding a balancing agent and a filler doped with flaky boron nitride, the two are coordinated and coordinated, and the product raw material interface compatibility is excellent, the product antibacterial property, barrier and mechanical properties are coordinated and balanced, and the product weather resistance and acid corrosion resistance stability are remarkable.

Description

Technical Field

[0001] The invention relates to the technical field of TPU protective films, and in particular to a fluorine-free antibacterial TPU protective film and a preparation method thereof. Background Art

[0002] TPU is becoming increasingly popular due to its superior performance and environmental protection concept. TPU not only has excellent high tension, high tensile strength, toughness and aging resistance, but is also a mature environmentally friendly material. The existing TPU film uses inorganic nano materials to enhance the antibacterial properties of the product, which easily leads to poor interface between the raw materials, which makes it difficult to balance and improve the antibacterial, barrier and mechanical properties of the product, and the product has poor weather resistance and acid corrosion resistance, which further limits the efficiency of product use. Summary of the invention

[0003] In view of the defects of the prior art, the purpose of the present invention is to provide a fluorine-free antibacterial TPU protective film and a preparation method thereof, so as to solve the problems raised in the above background technology.

[0004] The present invention solves the technical problem by adopting the following technical solution:

[0005] The present invention provides a fluorine-free antibacterial TPU protective film, comprising the following raw materials in parts by weight:

[0006] 35-40 parts of TPU particles, 10-15 parts of balancing agent, 8-12 parts of antibacterial agent, 3-6 parts of antioxidant, 3-5 parts of heat stabilizer, 2-3 parts of lubricant and 4-7 parts by weight of filler doped with flake boron nitride;

[0007] The preparation method of the balance regulator is as follows:

[0008] S01: soaking the nano-attapulgite in a sufficient amount of acid solution at a soaking temperature of 55-60°C for 1 hour, washing, filtering and drying after soaking to obtain dry nano-attapulgite;

[0009] S02: heat treating the halloysite nanotubes at 60-65° C. for 10-15 min, and then heat-insulating to obtain heat-insulated halloysite nanotubes;

[0010] 5-8 parts of the heat-insulated halloysite nanotubes, 2-5 parts of the silane coupling agent KH560, 1-3 parts of ethanol and 4-6 parts of a 2-5% by weight aqueous solution of sodium dodecylbenzene sulfonate are fully mixed to obtain a silane coupling blended halloysite nanotube agent;

[0011] S03: adding 2 to 5 parts of silane coupling and halloysite nanotube agent and 1 to 3 parts of stearic acid to 5 to 8 parts of chitosan solution by weight, and then adding 1 to 2 parts of carboxymethyl cellulose, and mixing well to obtain a leveling agent;

[0012] S04: Mix the dried nano-attapulgite and the balance agent in a weight ratio of 5:3 and perform ball milling at a ball milling speed of 1000 r / min for 2 h. After the ball milling is completed, wash with water, filter and dry to obtain a balance agent;

[0013] The preparation method of the filler doped with flake boron nitride is as follows:

[0014] S101: Stir and mix the flaky boron nitride in a sufficient amount of a potassium permanganate solution having a mass fraction of 2-5%, and then wash, filter and dry to obtain dry flaky boron nitride;

[0015] S102: 3-5 parts of dry flaky boron nitride, 1-3 parts of lanthanum chloride solution, 2-4 parts of sodium alginate solution, and 2-3 parts of zirconium silicate fiber agent are mixed and ball-milled by weight at a ball-milling speed of 1500 r / min for 2 hours. After the ball-milling is completed, the mixture is washed with water, filtered, and dried to obtain a filler doped with flaky boron nitride.

[0016] Preferably, the fluorine-free antibacterial TPU protective film comprises the following raw materials in parts by weight:

[0017] 37.5 parts of TPU particles, 12.5 parts of balancing agent, 10 parts of antibacterial agent, 4.5 parts of antioxidant, 4 parts of heat stabilizer, and 2.5 parts of lubricant.

[0018] Preferably, the lubricant is oleamide; the heat stabilizer is calcium stearate; the antioxidant is antioxidant 1010; and the antibacterial agent is nano silver powder.

[0019] Preferably, the acid solution is a sulfuric acid solution with a mass fraction of 2-5%; and the mass fraction of the chitosan solution is 3-5%.

[0020] Preferably, the mass fraction of the lanthanum chloride solution is 2-4%; the mass fraction of the sodium alginate solution is 3-6%.

[0021] Preferably, the preparation method of the zirconium silicate fiber agent is:

[0022] 3-5 parts of zirconium silicate fiber and 0.2-0.4 parts of nano magnesium oxide are added to 4-7 parts of sodium lignin sulfonate solution with a mass fraction of 4-7%, and then 2-3 parts of silicon carbide whiskers and 1-2 parts of yttrium nitrate solution with a mass fraction of 2-5% are added and mixed and stirred. After the stirring is completed, the mixture is filtered and dried to obtain a zirconium silicate fiber agent.

[0023] Preferably, the stirring speed of the blending and stirring process is 550-750 r / min, and the stirring time is 20-30 min.

[0024] The present invention also provides a method for preparing a fluorine-free antibacterial TPU protective film, which is used to prepare the fluorine-free antibacterial TPU protective film, comprising the following steps:

[0025] Step 1: Weigh the raw materials according to weight;

[0026] Step 2: Stir and blend the balancing agent, antioxidant, heat stabilizer, filler doped with flake boron nitride, antibacterial agent and lubricant to obtain a premix;

[0027] Step 3: Feed the premix and TPU particles into the film blowing machine for plasticization and extrusion. The feeding section temperature of the film blowing machine is 135°C, the plasticizing section temperature is 170°C, and the die head temperature is 150°C. Then, the plasticized extruded material is inflated and pulled to obtain a film body, which is then cooled and pulled. The blowing ratio is 2.5, the pulling ratio is 4, and finally rolled up to obtain a fluorine-free antibacterial TPU protective film.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The TPU protective film of the present invention adopts TPU particles, antibacterial agent, antioxidant, heat stabilizer and lubricant as functional additives, and coordinates and cooperates with the addition of a balancing agent and a filler doped with flake boron nitride to obtain a product with excellent raw material interface compatibility, coordinated and balanced improvement of the product's antibacterial property, barrier and mechanical properties, and significant weather resistance and acid corrosion resistance stability effects;

[0030] The balancing agent is prepared by soaking nano-attapulgite in a sufficient amount of acid solution to optimize the dispersibility and activity of the nano-attapulgite. The halloysite nanotubes are first heat-treated at 60-65°C for 10-15 minutes, and then mixed with silane coupling agent KH560, ethanol and 2-5% by mass of sodium dodecylbenzene sulfonate aqueous solution to obtain a silane coupling balancing halloysite nanotube agent. Through the coordination and matching of the raw materials, the halloysite nanotubes are used as the matrix to enhance the interface effect between the raw materials of the system. At the same time, stearic acid, chitosan solution and carboxymethyl cellulose are mixed and fully obtained to obtain a balancing agent. Through the coordination and matching of the raw materials, the balancing agent obtained by the synergistic effect further improves the nano-attapulgite, and then coordinates and improves the performance effect of the product in the system, and optimizes the performance of the product. Stability; the filler doped with flaky boron nitride is prepared by stirring and mixing the flaky boron nitride in a potassium permanganate solution to optimize the activity of the boron nitride, and then blending and ball-milling the lanthanum chloride solution, sodium alginate solution and zirconium silicate fiber agent. The synergistic effect of the filler doped with flaky boron nitride and the balancing agent obtained by the coordination between the raw materials is enhanced, and the performance of the product is further improved; the zirconium silicate fiber agent uses zirconium silicate fiber as a matrix material, and is blended and stirred by adding nano-magnesium oxide, a sodium lignin sulfonate solution with a mass fraction of 4-7%, silicon carbide whiskers and a yttrium nitrate solution with a mass fraction of 2-5%, and the silicon carbide whiskers are used to coordinate and blend the zirconium silicate fiber, and then the raw materials in the zirconium silicate fiber agent are mutually coordinated and synergistic, thereby further improving the performance of the obtained product. DETAILED DESCRIPTION

[0031] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. 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 creative work are within the scope of protection of the present invention.

[0032] A fluorine-free antibacterial TPU protective film of this embodiment includes the following raw materials in parts by weight:

[0033] 35-40 parts of TPU particles, 10-15 parts of balancing agent, 8-12 parts of antibacterial agent, 3-6 parts of antioxidant, 3-5 parts of heat stabilizer, and 2-3 parts of lubricant.

[0034] The fluorine-free antibacterial TPU protective film of this embodiment includes the following raw materials in parts by weight:

[0035] 37.5 parts of TPU particles, 12.5 parts of balancing agent, 10 parts of antibacterial agent, 4.5 parts of antioxidant, 4 parts of heat stabilizer, and 2.5 parts of lubricant.

[0036] The lubricant in this embodiment is oleamide; the heat stabilizer is calcium stearate; the antioxidant is antioxidant 1010; and the antibacterial agent is nano silver powder.

[0037] The preparation method of the balanced performance regulator of this embodiment is:

[0038] S01: soaking the nano-attapulgite in a sufficient amount of acid solution at a soaking temperature of 55-60°C for 1 hour, washing, filtering and drying after soaking to obtain dry nano-attapulgite;

[0039] S02: heat treating the halloysite nanotubes at 60-65° C. for 10-15 min, and then heat-insulating to obtain heat-insulated halloysite nanotubes;

[0040] 5-8 parts of the heat-insulated halloysite nanotubes, 2-5 parts of the silane coupling agent KH560, 1-3 parts of ethanol and 4-6 parts of a 2-5% by weight aqueous solution of sodium dodecylbenzene sulfonate are fully mixed to obtain a silane coupling blended halloysite nanotube agent;

[0041] S03: adding 2 to 5 parts of silane coupling and halloysite nanotube agent and 1 to 3 parts of stearic acid to 5 to 8 parts of chitosan solution by weight, and then adding 1 to 2 parts of carboxymethyl cellulose, and mixing well to obtain a leveling agent;

[0042] S04: The dried nano-attapulgite and the balancing agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 2 h. After the ball milling is completed, the mixture is washed with water, filtered and dried to obtain the balancing agent.

[0043] The acid solution in this embodiment is a sulfuric acid solution with a mass fraction of 2-5%; the mass fraction of the chitosan solution is 3-5%.

[0044] The fluorine-free antibacterial TPU protective film of this embodiment further includes 4 to 7 parts by weight of a filler doped with flake boron nitride;

[0045] The preparation method of the filler doped with flake boron nitride is as follows:

[0046] S101: Stir and mix the flaky boron nitride in a sufficient amount of a potassium permanganate solution having a mass fraction of 2-5%, and then wash, filter and dry to obtain dry flaky boron nitride;

[0047] S102: 3-5 parts of dry flaky boron nitride, 1-3 parts of lanthanum chloride solution, 2-4 parts of sodium alginate solution, and 2-3 parts of zirconium silicate fiber agent are mixed and ball-milled by weight at a ball-milling speed of 1500 r / min for 2 hours. After the ball-milling is completed, the mixture is washed with water, filtered, and dried to obtain a filler doped with flaky boron nitride.

[0048] The mass fraction of the lanthanum chloride solution in this embodiment is 2-4%; the mass fraction of the sodium alginate solution is 3-6%.

[0049] The preparation method of the zirconium silicate fiber agent of this embodiment is:

[0050] 3-5 parts of zirconium silicate fiber and 0.2-0.4 parts of nano magnesium oxide are added to 4-7 parts of sodium lignin sulfonate solution with a mass fraction of 4-7%, and then 2-3 parts of silicon carbide whiskers and 1-2 parts of yttrium nitrate solution with a mass fraction of 2-5% are added and mixed and stirred. After the stirring is completed, the mixture is filtered and dried to obtain a zirconium silicate fiber agent.

[0051] The stirring speed of the blending and stirring process in this embodiment is 550~750r / min, and the stirring time is 20~30min.

[0052] A method for preparing a fluorine-free antibacterial TPU protective film of this embodiment is used to prepare the above-mentioned fluorine-free antibacterial TPU protective film, comprising the following steps:

[0053] Step 1: Weigh the raw materials according to weight;

[0054] Step 2: Stir and blend the balancing agent, antioxidant, heat stabilizer, filler doped with flake boron nitride, antibacterial agent and lubricant to obtain a premix;

[0055] Step 3: Feed the premix and TPU particles into the film blowing machine for plasticization and extrusion. The feeding section temperature of the film blowing machine is 135°C, the plasticizing section temperature is 170°C, and the die head temperature is 150°C. Then, the plasticized extruded material is inflated and pulled to obtain a film body, which is then cooled and pulled. The blowing ratio is 2.5, the pulling ratio is 4, and finally rolled up to obtain a fluorine-free antibacterial TPU protective film.

[0056] Embodiment 1: A fluorine-free antibacterial TPU protective film, comprising the following raw materials in parts by weight:

[0057] 35 parts of TPU particles, 10 parts of balancing agent, 8 parts of antibacterial agent, 3 parts of antioxidant, 3 parts of heat stabilizer, and 2 parts of lubricant.

[0058] The lubricant in this embodiment is oleamide; the heat stabilizer is calcium stearate; the antioxidant is antioxidant 1010; and the antibacterial agent is nano silver powder.

[0059] The preparation method of the balanced performance regulator of this embodiment is:

[0060] S01: soaking the nano-attapulgite in a sufficient amount of acid solution at a soaking temperature of 55° C. for 1 h. After the soaking is completed, washing, filtering, and drying are performed to obtain dry nano-attapulgite;

[0061] S02: heat-treating the halloysite nanotubes at 60° C. for 10 min and then heat-keeping the halloysite nanotubes to obtain heat-treated halloysite nanotubes;

[0062] 5 parts of the heat-insulated halloysite nanotubes, 2 parts of silane coupling agent KH560, 1 part of ethanol and 4 parts of 2% by weight sodium dodecylbenzene sulfonate aqueous solution are fully mixed to obtain a silane coupling blended halloysite nanotube agent;

[0063] S03: adding 2 parts of silane coupling and halloysite nanotube agent and 1 part of stearic acid to 5 parts of chitosan solution by weight, and then adding 1 part of carboxymethyl cellulose, and mixing well to obtain a leveling agent;

[0064] S04: The dried nano-attapulgite and the balancing agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 2 h. After the ball milling is completed, the mixture is washed with water, filtered and dried to obtain the balancing agent.

[0065] The acid solution in this embodiment is a sulfuric acid solution with a mass fraction of 2%; the mass fraction of the chitosan solution is 3%.

[0066] The fluorine-free antibacterial TPU protective film of this embodiment further includes 4 parts by weight of a filler doped with flake boron nitride;

[0067] The preparation method of the filler doped with flake boron nitride is as follows:

[0068] S101: Stir and mix the flaky boron nitride in a sufficient amount of 2% by mass potassium permanganate solution, then wash, filter and dry to obtain dry flaky boron nitride;

[0069] S102: 3 parts of dry flaky boron nitride, 1 part of lanthanum chloride solution, 2 parts of sodium alginate solution, and 2 parts of zirconium silicate fiber agent are mixed and ball-milled by weight at a ball-milling speed of 1500 r / min for 2 hours. After the ball-milling is completed, the mixture is washed with water, filtered, and dried to obtain a filler doped with flaky boron nitride.

[0070] The mass fraction of the lanthanum chloride solution in this embodiment is 2%; the mass fraction of the sodium alginate solution is 3%.

[0071] The preparation method of the zirconium silicate fiber agent of this embodiment is:

[0072] 3 parts of zirconium silicate fiber and 0.2 parts of nano-magnesium oxide are added by weight to 4 parts of 4% sodium lignin sulfonate solution, and then 2 parts of silicon carbide whiskers and 1 part of 2% yttrium nitrate solution are added and mixed and stirred. After stirring, the mixture is filtered and dried to obtain a zirconium silicate fiber agent.

[0073] The stirring speed of the blending and stirring process in this embodiment is 550r / min, and the stirring time is 20min.

[0074] A method for preparing a fluorine-free antibacterial TPU protective film of this embodiment is used to prepare the above-mentioned fluorine-free antibacterial TPU protective film, comprising the following steps:

[0075] Step 1: Weigh the raw materials according to weight;

[0076] Step 2: Stir and blend the balancing agent, antioxidant, heat stabilizer, filler doped with flake boron nitride, antibacterial agent and lubricant to obtain a premix;

[0077] Step 3: Feed the premix and TPU particles into the film blowing machine for plasticization and extrusion. The feeding section temperature of the film blowing machine is 135°C, the plasticizing section temperature is 170°C, and the die head temperature is 150°C. Then, the plasticized extruded material is inflated and pulled to obtain a film body, which is then cooled and pulled. The blowing ratio is 2.5, the pulling ratio is 4, and finally rolled up to obtain a fluorine-free antibacterial TPU protective film.

[0078] Embodiment 2: A fluorine-free antibacterial TPU protective film, comprising the following raw materials in parts by weight:

[0079] 40 parts of TPU particles, 15 parts of balancing agent, 12 parts of antibacterial agent, 6 parts of antioxidant, 5 parts of heat stabilizer, and 3 parts of lubricant.

[0080] The lubricant in this embodiment is oleamide; the heat stabilizer is calcium stearate; the antioxidant is antioxidant 1010; and the antibacterial agent is nano silver powder.

[0081] The preparation method of the balanced performance regulator of this embodiment is:

[0082] S01: soaking the nano-attapulgite in a sufficient amount of acid solution at a soaking temperature of 60° C. for 1 h. After the soaking is completed, washing, filtering, and drying are performed to obtain dry nano-attapulgite;

[0083] S02: heat-treating the halloysite nanotubes at 65° C. for 15 min and then heat-keeping the halloysite nanotubes to obtain heat-treated halloysite nanotubes;

[0084] 8 parts of the heat-insulated halloysite nanotubes, 5 parts of the silane coupling agent KH560, 3 parts of ethanol and 6 parts of a 5% by weight aqueous solution of sodium dodecylbenzene sulfonate are fully mixed to obtain a silane coupling-adjusted halloysite nanotube agent;

[0085] S03: adding 5 parts of silane coupling and halloysite nanotube agent and 3 parts of stearic acid to 8 parts of chitosan solution by weight, and then adding 2 parts of carboxymethyl cellulose, and mixing well to obtain a leveling agent;

[0086] S04: The dried nano-attapulgite and the balancing agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 2 h. After the ball milling is completed, the mixture is washed with water, filtered and dried to obtain the balancing agent.

[0087] The acid solution in this embodiment is a sulfuric acid solution with a mass fraction of 5%; the mass fraction of the chitosan solution is 5%.

[0088] The fluorine-free antibacterial TPU protective film of this embodiment further includes 4 parts by weight of a filler doped with flake boron nitride;

[0089] The preparation method of the filler doped with flake boron nitride is as follows:

[0090] S101: Stir and mix the flaky boron nitride in a sufficient amount of 5% by mass potassium permanganate solution, then wash, filter and dry to obtain dry flaky boron nitride;

[0091] S102: 5 parts of dry flaky boron nitride, 3 parts of lanthanum chloride solution, 4 parts of sodium alginate solution and 3 parts of zirconium silicate fiber agent are mixed and ball-milled by weight at a ball-milling speed of 1500 r / min for 2 hours. After the ball-milling is completed, the mixture is washed with water, filtered and dried to obtain a filler doped with flaky boron nitride.

[0092] The mass fraction of the lanthanum chloride solution in this embodiment is 4%; the mass fraction of the sodium alginate solution is 6%.

[0093] The preparation method of the zirconium silicate fiber agent of this embodiment is:

[0094] 5 parts of zirconium silicate fiber and 0.4 parts of nano-magnesium oxide are added by weight to 7 parts of 7% sodium lignin sulfonate solution, and then 3 parts of silicon carbide whiskers and 2 parts of 5% yttrium nitrate solution are added and mixed and stirred. After stirring, the mixture is filtered and dried to obtain a zirconium silicate fiber agent.

[0095] The stirring speed of the blending and stirring process in this embodiment is 750r / min, and the stirring time is 30min.

[0096] A method for preparing a fluorine-free antibacterial TPU protective film of this embodiment is used to prepare the above-mentioned fluorine-free antibacterial TPU protective film, comprising the following steps:

[0097] Step 1: Weigh the raw materials according to weight;

[0098] Step 2: Stir and blend the balancing agent, antioxidant, heat stabilizer, filler doped with flake boron nitride, antibacterial agent and lubricant to obtain a premix;

[0099] Step 3: Feed the premix and TPU particles into the film blowing machine for plasticization and extrusion. The feeding section temperature of the film blowing machine is 135°C, the plasticizing section temperature is 170°C, and the die head temperature is 150°C. Then, the plasticized extruded material is inflated and pulled to obtain a film body, which is then cooled and pulled. The blowing ratio is 2.5, the pulling ratio is 4, and finally rolled up to obtain a fluorine-free antibacterial TPU protective film.

[0100] Embodiment 3: A fluorine-free antibacterial TPU protective film, comprising the following raw materials in parts by weight:

[0101] 37.5 parts of TPU particles, 12.5 parts of balancing agent, 10 parts of antibacterial agent, 4.5 parts of antioxidant, 4 parts of heat stabilizer, and 2.5 parts of lubricant.

[0102] The lubricant in this embodiment is oleamide; the heat stabilizer is calcium stearate; the antioxidant is antioxidant 1010; and the antibacterial agent is nano silver powder.

[0103] The preparation method of the balanced performance regulator of this embodiment is:

[0104] S01: soaking the nano-attapulgite in a sufficient amount of acid solution at a soaking temperature of 57.5°C for 1 hour. After the soaking is completed, washing, filtering and drying are performed to obtain dry nano-attapulgite.

[0105] S02: heat-treating the halloysite nanotubes at 62.5° C. for 12.5 min and then heat-keeping the halloysite nanotubes to obtain heat-keeping halloysite nanotubes;

[0106] 6.5 parts of the heat-insulated halloysite nanotubes, 3.5 parts of the silane coupling agent KH560, 2 parts of ethanol and 5 parts of a 3.5% by weight aqueous solution of sodium dodecylbenzene sulfonate are fully mixed to obtain a silane coupling blended halloysite nanotube agent;

[0107] S03: adding 3.5 parts of silane coupling and halloysite nanotube agent and 2 parts of stearic acid to 6.5 parts of chitosan solution by weight, and then adding 1.5 parts of carboxymethyl cellulose, and mixing well to obtain a leveling agent;

[0108] S04: The dried nano-attapulgite and the balancing agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 2 h. After the ball milling is completed, the mixture is washed with water, filtered and dried to obtain the balancing agent.

[0109] The acid solution in this embodiment is a sulfuric acid solution with a mass fraction of 3.5%; the mass fraction of the chitosan solution is 4%.

[0110] The fluorine-free antibacterial TPU protective film of this embodiment further includes 5.5 parts by weight of a filler doped with flake boron nitride;

[0111] The preparation method of the filler doped with flake boron nitride is as follows:

[0112] S101: Stir and mix the flaky boron nitride in a sufficient amount of 3.5% by mass potassium permanganate solution, then wash, filter and dry to obtain dry flaky boron nitride;

[0113] S102: 4 parts of dry flaky boron nitride, 2 parts of lanthanum chloride solution, 3 parts of sodium alginate solution, and 2.5 parts of zirconium silicate fiber agent are mixed and ball-milled by weight at a ball-milling speed of 1500 r / min for 2 hours. After the ball-milling is completed, the mixture is washed with water, filtered, and dried to obtain a filler doped with flaky boron nitride.

[0114] The mass fraction of the lanthanum chloride solution in this embodiment is 3%; the mass fraction of the sodium alginate solution is 4.5%.

[0115] The preparation method of the zirconium silicate fiber agent of this embodiment is:

[0116] 4 parts of zirconium silicate fiber and 0.3 parts of nano-magnesium oxide were added to 5.5 parts of sodium lignin sulfonate solution with a mass fraction of 5.5%, and then 2.5 parts of silicon carbide whiskers and 1.5 parts of yttrium nitrate solution with a mass fraction of 3.5% were added and mixed and stirred. After the stirring was completed, the mixture was filtered and dried to obtain a zirconium silicate fiber agent.

[0117] The stirring speed of the blending and stirring process in this embodiment is 600 r / min, and the stirring time is 25 min.

[0118] A method for preparing a fluorine-free antibacterial TPU protective film of this embodiment is used to prepare the above-mentioned fluorine-free antibacterial TPU protective film, comprising the following steps:

[0119] Step 1: Weigh the raw materials according to weight;

[0120] Step 2: Stir and blend the balancing agent, antioxidant, heat stabilizer, filler doped with flake boron nitride, antibacterial agent and lubricant to obtain a premix;

[0121] Step 3: Feed the premix and TPU particles into the film blowing machine for plasticization and extrusion. The feeding section temperature of the film blowing machine is 135°C, the plasticizing section temperature is 170°C, and the die head temperature is 150°C. Then, the plasticized extruded material is inflated and pulled to obtain a film body, which is then cooled and pulled. The blowing ratio is 2.5, the pulling ratio is 4, and finally rolled up to obtain a fluorine-free antibacterial TPU protective film.

[0122] Comparative Example 1:

[0123] The difference from Example 3 is that no balancing agent is added.

[0124] Comparative Example 2:

[0125] The difference from Example 3 is that no leveling agent treatment is used in the preparation of the balancing agent.

[0126] Comparative Example 3:

[0127] The difference from Example 3 is that no silane coupling and halloysite nanotube agent is added to the leveling agent.

[0128] Comparative Example 4:

[0129] The difference from Example 3 is that the heat-insulated halloysite nanotubes are not added in the preparation of the silane coupling blending halloysite nanotube agent.

[0130] Comparative Example 5:

[0131] The difference from Example 3 is that the silane coupling agent KH560 and the sodium dodecylbenzene sulfonate aqueous solution are not added in the preparation of the silane coupling blending halloysite nanotube agent.

[0132] Comparative Example 6:

[0133] The difference from Example 3 is that the nano-attapulgite treated with S01 was not added in the preparation of the balanced efficiency regulator.

[0134] Comparative Example 7:

[0135] The difference from Example 3 is that no filler doped with flake boron nitride is added.

[0136] Comparative Example 8:

[0137] The difference from Example 3 is that the flake boron nitride of S101 is not added to the filler doped with flake boron nitride.

[0138] Comparative Example 9:

[0139] The difference from Example 3 is that no lanthanum chloride solution is added to the filler doped with flake boron nitride, and the sodium alginate solution is replaced by water.

[0140] Comparative Example 10:

[0141] The difference from Example 3 is that no zirconium silicate fiber agent is added in the preparation of the filler doped with flake boron nitride.

[0142] The products of Examples 1 to 3 and Comparative Examples 1 to 10 were tested for antibacterial, barrier and mechanical properties under normal conditions, and the products were placed in 5% hydrochloric acid mist for 10 hours and then in 0.5 W / m 2 The product was irradiated under ultraviolet radiation intensity of 10 hours, and the above was one cycle. The cycle was repeated 10 times to test the acid corrosion resistance and weathering stability of the product. The test results are shown in Table 1.

[0143] Table 1 Product performance test results of Examples 1 to 3 and Comparative Examples 1 to 10:

[0144]

[0145] It can be seen from Comparative Examples 1 to 10 and Examples 1 to 3 that the product of Example 3 has excellent antibacterial, barrier and mechanical properties, and the product can achieve coordinated improvement in antibacterial, barrier and mechanical properties. In addition, the product has excellent acid and corrosion resistance and weather resistance stability;

[0146] It can be seen from Comparative Examples 1 to 10 and Example 3 that the product performance has a significant deterioration trend when neither the balancing agent nor the filler doped with flake boron nitride is added. The performance effect of the product is significant when the two are coordinated and work together.

[0147] The performance of the products showed a trend of deterioration when the balanced conditioning agent was not treated with a balanced conditioning agent, the balanced conditioning agent was not added with a silane coupling and halloysite nanotube agent, the heat-insulated halloysite nanotubes were not added in the preparation of the silane coupling and halloysite nanotube agent, the silane coupling agent KH560 and the sodium dodecylbenzene sulfonate aqueous solution were not added in the preparation of the silane coupling and halloysite nanotube agent, and the nano-attapulgite treated with S01 was not added in the preparation of the balanced conditioning agent. The balanced conditioning agent prepared by the silane coupling and halloysite nanotube agent obtained by the specific method of the present invention and the nano-attapulgite treated with S01 had the most significant product performance effect.

[0148] The performance of the products tended to deteriorate when S101 was not added to the filler of doped flaky boron nitride, lanthanum chloride solution was not added to the filler of doped flaky boron nitride, water was used to replace the sodium alginate solution, and zirconium silicate fiber agent was not added in the preparation of the filler of doped flaky boron nitride. The filler of doped flaky boron nitride obtained by the method of the present invention had the most obvious product performance effect, and the performance of the product deteriorated more significantly when the zirconium silicate fiber agent was not added.

[0149] The present invention finds that the zirconium silicate fiber agent has a significant improvement effect on the performance of the product. Based on this, the product performance is further explored through the preparation of the zirconium silicate fiber agent.

[0150] Experimental Example 1:

[0151] The only difference from Example 3 is that no silicon carbide whiskers are added in the preparation of the zirconium silicate fiber agent.

[0152] Experimental Example 2:

[0153] The only difference from Example 3 is that no zirconium silicate fiber is added in the preparation of the zirconium silicate fiber agent.

[0154] Experimental Example 3:

[0155] The only difference from Example 3 is that no yttrium nitrate solution is added during the preparation of the zirconium silicate fiber agent.

[0156] Experimental Example 4:

[0157] The only difference from Example 3 is that no nano magnesium oxide is added in the preparation of the zirconium silicate fiber agent.

[0158] Experimental Example 5:

[0159] The only difference from Example 3 is that no sodium lignin sulfonate solution is added during the preparation of the zirconium silicate fiber agent.

[0160] The products of Experimental Examples 1 to 5 were subjected to the above performance tests, and the test results are shown in Table 2.

[0161] Table 2 Product performance test results of Experimental Examples 1 to 5:

[0162]

[0163] It can be seen from Experimental Examples 1-5 that no zirconium silicate fiber is added in the preparation of the zirconium silicate fiber agent, and the performance of the product has a significant tendency to deteriorate. At the same time, no silicon carbide whiskers are added in the preparation of the zirconium silicate fiber agent, and no nano-magnesium oxide is added in the preparation of the zirconium silicate fiber agent, and the performance of the product is also more obvious. Silicon carbide whiskers are combined with nano-magnesium oxide to blend zirconium silicate fiber, and the performance effect of the product is significant. At the same time, no yttrium nitrate solution is added in the preparation of the zirconium silicate fiber agent, and no sodium lignin sulfonate solution is added in the preparation of the zirconium silicate fiber agent, and the performance of the product has a tendency to deteriorate. Only the zirconium silicate fiber agent prepared by the method of the present invention has the most significant product performance effect, and the effects of other methods are not as obvious as those of the present invention.

[0164] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0165] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A fluorine-free antibacterial TPU protective film, characterized in that: It includes the following raw materials in parts by weight: 35-40 parts of TPU particles, 10-15 parts of balancing agent, 8-12 parts of antibacterial agent, 3-6 parts of antioxidant, 3-5 parts of heat stabilizer, 2-3 parts of lubricant and 4-7 parts by weight of filler doped with flake boron nitride; The preparation method of the balance regulator is as follows: S01: soaking the nano-attapulgite in a sufficient amount of acid solution at a soaking temperature of 55-60°C for 1 hour, washing, filtering and drying after soaking to obtain dry nano-attapulgite; S02: heat treating the halloysite nanotubes at 60-65° C. for 10-15 min, and then heat-insulating to obtain heat-insulated halloysite nanotubes; 5-8 parts of the heat-insulated halloysite nanotubes, 2-5 parts of the silane coupling agent KH560, 1-3 parts of ethanol and 4-6 parts of a 2-5% by weight aqueous solution of sodium dodecylbenzene sulfonate are fully mixed to obtain a silane coupling blended halloysite nanotube agent; S03: adding 2 to 5 parts of silane coupling and halloysite nanotube agent and 1 to 3 parts of stearic acid to 5 to 8 parts of chitosan solution by weight, and then adding 1 to 2 parts of carboxymethyl cellulose, and mixing well to obtain a leveling agent; S04: Mix the dried nano-attapulgite and the balance agent in a weight ratio of 5:3 and perform ball milling at a ball milling speed of 1000 r / min for 2 h. After the ball milling is completed, wash with water, filter and dry to obtain a balance agent; The preparation method of the filler doped with flake boron nitride is as follows: S101: Stir and mix the flaky boron nitride in a sufficient amount of a potassium permanganate solution having a mass fraction of 2-5%, and then wash, filter and dry to obtain dry flaky boron nitride; S102: 3-5 parts of dry flaky boron nitride, 1-3 parts of lanthanum chloride solution, 2-4 parts of sodium alginate solution, and 2-3 parts of zirconium silicate fiber agent are mixed and ball-milled by weight at a ball-milling speed of 1500 r / min for 2 hours. After the ball-milling is completed, the mixture is washed with water, filtered, and dried to obtain a filler doped with flaky boron nitride; The preparation method of the zirconium silicate fiber agent is: 3-5 parts of zirconium silicate fiber and 0.2-0.4 parts of nano magnesium oxide are added to 4-7 parts of sodium lignin sulfonate solution with a mass fraction of 4-7%, and then 2-3 parts of silicon carbide whiskers and 1-2 parts of yttrium nitrate solution with a mass fraction of 2-5% are added and mixed and stirred. After the stirring is completed, the mixture is filtered and dried to obtain a zirconium silicate fiber agent.

2. A fluorine-free antibacterial TPU protective film according to claim 1, characterized in that: The fluorine-free antibacterial TPU protective film comprises the following raw materials in parts by weight: 37.5 parts of TPU particles, 12.5 parts of balancing agent, 10 parts of antibacterial agent, 4.5 parts of antioxidant, 4 parts of heat stabilizer, and 2.5 parts of lubricant.

3. The fluorine-free antibacterial TPU protective film according to claim 1, characterized in that: The lubricant is oleic acid amide; the heat stabilizer is calcium stearate; the antioxidant is antioxidant 1010; and the antibacterial agent is nano silver powder.

4. The fluorine-free antibacterial TPU protective film according to claim 1, characterized in that: The acid solution is a sulfuric acid solution with a mass fraction of 2-5%; the mass fraction of the chitosan solution is 3-5%.

5. The fluorine-free antibacterial TPU protective film according to claim 1, characterized in that: The mass fraction of the lanthanum chloride solution is 2-4%; the mass fraction of the sodium alginate solution is 3-6%.

6. The fluorine-free antibacterial TPU protective film according to claim 1, characterized in that: The stirring speed of the blending and stirring process is 550-750 r / min, and the stirring time is 20-30 min.

7. A method for preparing a fluorine-free antibacterial TPU protective film, for preparing the fluorine-free antibacterial TPU protective film as claimed in any one of claims 1 to 6, characterized in that: The following steps are involved: Step 1: Weigh the raw materials according to weight; Step 2: Stir and blend the balancing agent, antioxidant, heat stabilizer, filler doped with flake boron nitride, antibacterial agent and lubricant to obtain a premix; Step 3: Feed the premix and TPU particles into the film blowing machine for plasticization and extrusion. The feeding section temperature of the film blowing machine is 135°C, the plasticizing section temperature is 170°C, and the die head temperature is 150°C. Then, the plasticized extruded material is inflated and pulled to obtain a film body, which is then cooled and pulled. The blowing ratio is 2.5, the pulling ratio is 4, and finally rolled up to obtain a fluorine-free antibacterial TPU protective film.

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