TPU high-and-low-temperature film having optical color effect and preparation method therefor

Abstract

The present invention relates to the technical field of TPU, and specifically relates to a TPU high-and-low-temperature film having an optical color effect and a preparation method therefor. The TPU high-and-low-temperature film having an optical color effect sequentially comprises an optical coated layer, a texture layer, a TPU carrier layer and a hot melt adhesive layer from top to bottom, wherein the texture layer is made of a polyurethane UV adhesive coating. The TPU high-and-low-temperature film has a stable quality, and good tensile properties, ultraviolet aging resistance, hydrolysis resistance and boiling resistance, the optical coated layer thereof also has a good adhesive force, hydrolysis resistance, boiling resistance and aging resistance, and the TPU high-and-low-temperature film is convenient to use. The preparation method for the TPU high-and-low-temperature film is simple in terms of process, easily controllable in terms of operation, and beneficial for industrial mass production. Moreover, during the production process, waste, waste water, waste gas, etc., are not generated, thereby creating no pollution for the environment and being conducive to environmental protection by human beings.

Description

A TPU high and low temperature film with optical color effect and preparation method thereof Technical Field

[0001] The present invention relates to the technical field of TPU, and in particular to a TPU high and low temperature film with optical color effects and a preparation method thereof. Background Art

[0002] TPU high and low temperature films have been widely used. They are soft, elastic, and have excellent mechanical properties. They can be used in various fabrics such as clothing, bags, tents, shoes, and other products. The two sides of the TPU high and low temperature film have different melting points. They mainly include a high-temperature layer with a higher melting point and a low-temperature layer with a lower melting point. The low-temperature layer is mainly used for bonding with other materials, and the high-temperature layer can be used as a carrier or surface layer and applied to the surface of the product to improve the performance of the product. In order to meet the needs of consumers, the existing TPU high and low temperature films are prepared into dazzling optical film layers that are eye-catching. However, the existing optical film layers have poor adhesion after long-term use and are prone to powdering. In addition, waste gas and wastewater are generated during the production process, which will cause damage to the environment.

[0003] Summary of the Invention

[0004] In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present invention is to provide a TPU high and low temperature film with optical color effects and a TPU film with optical color effects. The TPU high and low temperature film has excellent tensile properties, UV aging resistance, hydrolysis resistance and boiling resistance. At the same time, its optical coating layer also has good adhesion, hydrolysis resistance, boiling resistance, durability and aging resistance, and is easy to use.

[0005] Another object of the present invention is to provide a method for preparing a TPU high and low temperature film with optical color effects. The method has a simple process, easy operation and control, and is conducive to large-scale industrial production. The prepared TPU high and low temperature film has excellent tensile properties, UV aging resistance and boiling resistance. At the same time, its optical coating layer also has good adhesion, hydrolysis resistance, boiling resistance, durability and aging resistance, and has excellent comprehensive performance.

[0006] The purpose of the present invention is achieved through the following technical solution: a TPU high and low temperature film with optical color effect, comprising an optical coating layer, a UV texture layer and a TPU carrier layer arranged in sequence from top to bottom, and the texture layer is made of polyurethane UV glue coating.

[0007] The TPU high and low temperature film and TPU film with optical color effects of the present invention have simple structures. The TPU carrier layer is firmly connected to the texture layer. The TPU high and low temperature film has excellent tensile properties, UV aging resistance, hydrolysis resistance and boiling resistance. At the same time, its optical coating layer also has good adhesion, hydrolysis resistance, boiling resistance, durability and aging resistance.

[0008] Furthermore, the thickness of the optical coating layer is 1-2 μm; the thickness of the texture layer is 4-6 μm; and the thickness of the TPU high and low temperature film is 0.5-1.5 cm.

[0009] Furthermore, the texture layer is a grating structure layer, and the grating structure layer includes a plurality of continuously arranged cylindrical lenses, the upper ends of the cylindrical lenses are connected to the optical coating layer, and the lower ends of the cylindrical lenses are connected to the TPU carrier layer.

[0010] Furthermore, the TPU high and low temperature film with optical color effects also includes a hot melt adhesive layer and a pattern layer arranged at the upper end of the hot melt adhesive layer, the pattern layer is located at the lower end of the UV texture layer, and the pattern layer includes a first pattern layer, a high-transparent material layer and a second pattern layer arranged in sequence from top to bottom, the first pattern layer is divided into a plurality of spaced first pattern units, a first gap is provided between adjacent first pattern units, adjacent first pattern units and the first gap are located at the lower end of a single cylindrical lens, the second pattern layer is divided into a plurality of spaced second pattern units, a second gap is provided between adjacent second pattern units, each second pattern unit is located at the lower end of the corresponding first gap, and each second gap is located at the lower end of the corresponding first pattern layer.

[0011] Furthermore, the polyurethane UV adhesive coating comprises the following raw materials in parts by weight: 30-36 parts of polyurethane prepolymer, 22-28 parts of bismaleimide resin, 45-55 parts of reactive diluent, and 4-6 parts of photoinitiator.

[0012] Furthermore, the preparation method of the polyurethane UV adhesive coating comprises the following steps: adding a polyurethane prepolymer and a bismaleimide resin into a reaction container at room temperature, and then adding a reactive diluent and a photoinitiator and mixing them evenly to prepare the polyurethane UV adhesive coating.

[0013] The present invention prepares the polyurethane UV adhesive coating by adopting the above-mentioned preparation method, and the raw materials are well matched. The TPU high and low temperature film has excellent tensile properties, UV aging resistance, hydrolysis resistance and boiling resistance. At the same time, its optical coating layer also has good adhesion, hydrolysis resistance, boiling resistance, durability and aging resistance, and has strong adhesion to the TPU carrier layer.

[0014] Furthermore, the photoinitiator is at least one of Irgacure 2959, Irgacure 1173, or Irgacure 184; the reactive diluent is a compound of 1,6-hexanediol diacrylate and 4-acryloylmorpholine, and the mass ratio of the 1,6-hexanediol diacrylate to the 4-acryloylmorpholine is 1:1-2.

[0015] Furthermore, the preparation method of the polyurethane prepolymer comprises the following steps:

[0016] (1) adding isophorone diisocyanate and catalyst A to a reaction vessel, heating to 60-80°C, adding poly(ethylene-co-1,2-butene) glycol dropwise, reacting for 2.5-3.5 hours, cooling to 20-30°C, adding dihydroxypropionic acid, heating to 85-95°C, reacting for 1-2 hours, cooling to room temperature, and slowly adding diethylamine dropwise for neutralization to obtain product A;

[0017] (2) Under nitrogen protection, the modified epoxy resin is added to the product A, the temperature is raised to 85-95° C. and the stirring is continued for 2.5-3.5 hours, and the temperature is lowered to obtain the polyurethane prepolymer.

[0018] Preferably, the poly(ethylene-co-1,2-butene) glycol needs to be dried and dehydrated at high temperature (100-110°C) or with 4A molecular sieve in vacuum for 5-10 hours before the reaction, with a vacuum degree of 0.01-0.05. Preferably, the poly(ethylene-co-1,2-butene) glycol is dehydrated and dried at 110°C and a vacuum degree of 0.01 for 5 hours.

[0019] Furthermore, the molar ratio of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate is 1:(1-2); and the added amount of the modified epoxy resin is 20-30% of the total mass of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate.

[0020] Furthermore, the added amount of the dihydroxypropionic acid is 10-14% of the total mass of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate.

[0021] Furthermore, the catalyst A is at least one of dibutyltin dilaurate and stannous octoate, and the amount of the catalyst A added is 3% of the total mass of poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate.

[0022] Furthermore, the preparation method of the modified epoxy resin comprises the following steps:

[0023] (1) dissolving epoxy resin in butyl acrylate, adding polytetramethylene glycol 250, polymerization inhibitor and catalyst B, heating to 80-100°C and reacting for 3-4 hours to obtain product C;

[0024] (2) Lower the system temperature to 90-100°C, slowly add α-methacrylic acid to the product C and continue the reaction for 1-2 hours, then continue the reaction at this temperature for 1-2 hours to obtain a modified epoxy resin.

[0025] Furthermore, the catalyst B is one of tetrabutylammonium bromide and triethylamine. The amount of the catalyst B added is 2% of the total mass of the epoxy resin and polytetramethylene glycol 250.

[0026] Furthermore, the molar ratio of the polytetramethylene ether glycol 250 to the epoxy resin is 0.3-0.4:1.

[0027] Furthermore, the polymerization inhibitor is p-hydroxyanisole, and the amount used is 0.04-0.06% of the total mass of the epoxy resin and polytetramethylene glycol 250.

[0028] Furthermore, the molar ratio of the added amount of α-methacrylic acid to the epoxy resin is 0.6-0.8:1.

[0029] Furthermore, the epoxy resin is bisphenol A epoxy resin or hydrogenated bisphenol A epoxy resin.

[0030] The present invention also provides a method for preparing the TPU high and low temperature film with optical color effects, comprising the following steps:

[0031] (1) At room temperature, a polyurethane UV adhesive coating is applied to the upper surface of the TPU carrier layer to form a UV adhesive layer;

[0032] (2) using an embossing roller to roll the UV adhesive layer at a pressure of 392-490 kPa, so that an uneven texture structure is formed on the upper surface of the UV adhesive layer to obtain a prefabricated texture layer;

[0033] (3) curing the prefabricated texture layer with ultraviolet light using a UV machine to obtain a prefabricated TPU high and low temperature film;

[0034] (4) Electron beam physical vapor deposition technology (e-beam PVD) is used to deposit a nano-metal film on the surface of the texture layer to form an optical coating layer, thereby producing a TPU high and low temperature film with optical color effects.

[0035] Furthermore, the TPU carrier layer is a transparent TPU film with a model number of ZD-135CM*85A produced by Guangdong Zhongding Technology Development Co., Ltd., with a thickness of 0.5-1.2 mm.

[0036] Furthermore, the nano-metal film includes, from top to bottom, a nano-silicon dioxide particle layer, a nano-titanium dioxide particle layer, and a nano-zinc oxide-coated silicon dioxide particle layer. The nano-silicon dioxide particle layer includes nano-silicon dioxide particles; the nano-titanium dioxide particle layer includes nano-titanium dioxide particles; and the nano-zinc oxide-coated silicon dioxide particle layer includes nano-zinc oxide-coated silicon dioxide particles.

[0037] Furthermore, the thickness ratio of the nano-silica particle layer, the nano-titanium dioxide particle layer and the nano-zinc oxide-coated silica particle layer is 0.2-0.4: (0.2-0.4): (0.5-0.7).

[0038] Furthermore, the particle size of the nano-silicon dioxide particles is 200-260 nm; the particle size of the nano-titanium dioxide particles is 150-180 nm; and the particle size of the nano-zinc oxide-coated silicon dioxide particles is 280-350 nm.

[0039] Furthermore, the method for preparing the metal film layer includes the following steps:

[0040] (1) ultrasonically clean the prefabricated TPU high and low temperature film with clean water for 3-4 hours, dehydrate with anhydrous ethanol, degrease with butyl acetate, dry in a vacuum dryer for 5-6 hours, and place it on a substrate holder and load it into a furnace;

[0041] (2) Nano-zinc oxide coated silicon dioxide particles were used as metal targets. The metal targets were placed on the target holder. The position and size of the laser beam spot were adjusted with a low-power laser beam. The coating chamber was evacuated to a vacuum degree of 6.6-6.8×10 -3 Pa, and then introduce argon to control the vacuum degree to 2.5-2.9×10 -3 Pa, heat the substrate to 160-190°C, start the laser and gradually increase the laser beam power to 350-380W, while rotating the metal target at a constant speed to make it evaporate stably, and deposit a nano-zinc oxide-coated silicon dioxide particle layer on the surface of the prefabricated TPU high and low temperature film;

[0042] (3) using nano-titanium dioxide particles as metal targets, repeating the above step (2) to deposit a nano-titanium dioxide particle layer on the surface of the nano-zinc oxide-coated silicon dioxide particle layer;

[0043] (4) Using nano-silica particles as metal targets, repeat the above step (2) to deposit a nano-silica particle layer on the surface of the nano-titanium dioxide particle layer, and finally obtain a metal film layer.

[0044] Furthermore, the preparation method of the nano zinc oxide coated silicon dioxide particles is as follows:

[0045] (1) Weigh 1-3 g of the above-mentioned nano-silica particles, disperse them in 1-2 L of ethanol and ultrasonically disperse them uniformly. Add 20-30 mL of a 2-3% volume fraction APTES ethanol solution and 45-55 mL of deionized water, and stir at low speed at room temperature for 2-3 hours. Wash the resulting product twice with deionized water and then 3-4 times with ethanol to obtain pretreated silica particles.

[0046] (2) Dispersing the pretreated silica particles in 20-30 mL of glutaraldehyde dilution solution, stirring and reacting for 3-4 hours, then washing twice with deionized water and ethanol, and then dispersing in 15-25 mL of ethanol to obtain solution A;

[0047] (3) Place the liquid A system in a 75-85°C water bath, add 7-8 mL of zinc ammonia solution to the liquid A three times every 15-25 minutes, and continue the reaction for 18-22 minutes after the last addition. Wash the solution three times with ethanol by centrifugation to obtain nano-zinc oxide-coated silica particles.

[0048] Furthermore, the preparation method of the glutaraldehyde dilution solution is as follows: dissolve 1.2g of anhydrous sodium dihydrogen phosphate and 0.156g of sodium hydroxide in water and stir evenly to prepare 0.1mol / L phosphate buffer solution, and dilute the glutaraldehyde solution with 0.1mol / L phosphate buffer solution to a volume fraction of 5% to obtain the glutaraldehyde dilution solution.

[0049] Furthermore, the zinc ammonia solution is prepared as follows: ammonia water is diluted with distilled water to a volume fraction of 2%, and solid zinc chloride is prepared with deionized water to form a 0.1 mol / L zinc chloride solution. A certain amount of the zinc chloride solution is poured into a beaker, and the diluted ammonia solution is slowly added dropwise while stirring until the precipitate disappears.

[0050] The preparation method of the TPU high and low temperature film of the present invention has a simple process and is easy to control in operation, which is conducive to large-scale industrial production. The prepared TPU high and low temperature film has stable quality and excellent tensile strength, UV aging resistance, hydrolysis resistance and boiling resistance. At the same time, its optical coating layer also has good adhesion, hydrolysis resistance, boiling resistance, durability and aging resistance, and has excellent comprehensive performance.

[0051] The beneficial effects of the present invention include: the TPU high-low temperature film with optical color effects has a simple structure, the TPU carrier layer is firmly connected to the texture layer, and the optical coating is firmly connected to the texture layer, making the TPU high-low temperature film suitable for large-scale industrial production. While exhibiting excellent tensile strength, UV aging resistance, and water boiling resistance, the optical coating layer also exhibits good adhesion, hydrolysis resistance, water boiling resistance, durability, and aging resistance. The preparation method of the TPU high-low temperature film is simple and easy to operate. Furthermore, the production process generates no wastewater or exhaust gas, causing no environmental pollution, thus significantly contributing to human environmental protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0052] FIG1 is a product diagram of the present invention. DETAILED DESCRIPTION

[0053] In order to facilitate understanding by those skilled in the art, the present invention will be further described below with reference to the embodiments. The contents mentioned in the embodiments are not intended to limit the present invention.

[0054] Example 1

[0055] In this embodiment, a TPU high and low temperature film with optical color effects includes an optical coating layer, a UV texture layer and a TPU carrier layer arranged in sequence from top to bottom; the texture layer is made of polyurethane UV adhesive coating, the TPU carrier layer is firmly connected to the texture layer, and the optical coating is firmly connected to the texture layer. The TPU high and low temperature film has excellent tensile properties, UV aging resistance, hydrolysis resistance and boiling resistance, while its optical coating layer also has good adhesion, hydrolysis resistance, boiling resistance, durability and aging resistance.

[0056] Furthermore, the texture layer is a grating structure layer, and the grating structure layer includes a plurality of continuously arranged cylindrical lenses, the upper ends of the cylindrical lenses are connected to the optical coating layer, and the lower ends of the cylindrical lenses are connected to the TPU carrier layer.

[0057] The TPU high and low temperature film with optical color effect of the present invention has a simple structure, the TPU carrier layer is firmly connected to the texture layer, the optical coating is firmly connected to the texture layer, the TPU high and low temperature film has excellent tensile properties, UV aging resistance, hydrolysis resistance and boiling resistance, while its optical coating layer also has good adhesion, hydrolysis resistance, boiling resistance, durability and aging resistance, so that the quality of the prepared TPU high and low temperature film with optical color effect is stable.

[0058] Example 2

[0059] The TPU high and low temperature film with optical color effects also includes a hot melt adhesive layer and a pattern layer arranged on the upper end of the hot melt adhesive layer, the pattern layer is located at the lower end of the UV texture layer, the pattern layer includes a first pattern layer, a high-transparent material layer and a second pattern layer arranged in sequence from top to bottom, the first pattern layer is divided into a plurality of spaced first pattern units, a first gap is provided between adjacent first pattern units, adjacent first pattern units and the first gap are located at the lower end of a single cylindrical lens, the second pattern layer is divided into a plurality of spaced second pattern units, a second gap is provided between adjacent second pattern units, each second pattern unit is located at the lower end of the corresponding first gap, and each second gap is located at the lower end of the corresponding first pattern layer.

[0060] Example 3

[0061] In this embodiment, the polyurethane UV adhesive coating includes the following raw materials in parts by weight: 30 parts of polyurethane prepolymer, 22 parts of bismaleimide resin, 48 parts of reactive diluent, and 5 parts of photoinitiator.

[0062] Furthermore, the preparation method of the polyurethane UV adhesive coating comprises the following steps: adding a polyurethane prepolymer and a bismaleimide resin into a reaction container at room temperature, and then adding a reactive diluent and a photoinitiator and mixing them evenly to prepare the polyurethane UV adhesive coating.

[0063] Furthermore, the bismaleimide resin is a bismaleimide resin with a CAS number of 13676-54-5 produced by Huaxiang Kejie.

[0064] Furthermore, the photoinitiator is Irgacure 184, and the reactive diluent is a compound of 1,6-hexanediol diacrylate and 4-acryloylmorpholine, wherein the mass ratio of the 1,6-hexanediol diacrylate to the 4-acryloylmorpholine is 1:1.

[0065] Furthermore, the preparation method of the polyurethane prepolymer comprises the following steps:

[0066] (1) Isophorone diisocyanate and catalyst A were added to a reaction vessel, heated to 75°C, poly(ethylene-co-1,2-butene) glycol was added dropwise, and the reaction was continued for 3 hours. The temperature was lowered to 25°C, dihydroxypropionic acid was added, the temperature was raised to 90°C, the reaction was continued for 1.5 hours, the temperature was lowered to room temperature, diethylamine was slowly added dropwise for neutralization, and product A was obtained.

[0067] (2) Under nitrogen protection, the modified epoxy resin was added to the product A, the temperature was raised to 90° C. and the mixture was stirred for 3 h, and the temperature was lowered to obtain the polyurethane prepolymer.

[0068] It should be further explained that poly(ethylene-co-1,2-butene) glycol was dehydrated and dried at 110° C. and a vacuum degree of 0.01 for 5 h.

[0069] Furthermore, the molar ratio of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate is 1:1, and the added amount of the modified epoxy resin is 25% of the total mass of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate.

[0070] Furthermore, the added amount of the dihydroxypropionic acid is 12% of the total mass of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate.

[0071] Furthermore, the poly(ethylene-co-1,2-butene) glycol is polytetrahydrofuran diol with a CAS number of 68954-10-9 produced by Shanghai Kaiyin Chemical.

[0072] Furthermore, the catalyst A is dibutyltin dilaurate, and the amount of the catalyst A added is 3% of the total mass of poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate.

[0073] Furthermore, the preparation method of the modified epoxy resin comprises the following steps:

[0074] (1) Hydrogenated bisphenol A epoxy resin was dissolved in butyl acrylate, and polytetramethylene glycol 250, polymerization inhibitor, and catalyst B were added. The temperature was raised to 90° C. and the reaction was carried out for 3 h to obtain product C.

[0075] (2) The system temperature was lowered to 95°C, and α-methacrylic acid was slowly added dropwise to the product C and the reaction was continued for 1 hour. The reaction was then continued at the same temperature for another 1 hour to obtain a modified epoxy resin.

[0076] Furthermore, the catalyst B is tetrabutylammonium bromide. The amount of the catalyst B added is 2% of the total mass of the hydrogenated bisphenol A epoxy resin and polytetramethylene glycol ether 250.

[0077] Furthermore, the molar ratio of the polytetramethylene ether glycol 250 to the hydrogenated bisphenol A epoxy resin is 0.4:1.

[0078] Furthermore, the polymerization inhibitor is p-hydroxyanisole, and the amount used is 0.05% of the total mass of hydrogenated bisphenol A epoxy resin and polytetramethylene ether glycol 250.

[0079] Furthermore, the molar ratio of the added amount of α-methacrylic acid to the hydrogenated bisphenol A epoxy resin is 0.7:1.

[0080] Furthermore, the hydrogenated bisphenol A epoxy resin adopts the hydrogenated bisphenol A epoxy resin with an epoxy value of 0.46 produced by Shanghai Luohe High-tech Materials Co., Ltd.

[0081] The present invention also provides a method for preparing the TPU high and low temperature film with optical color effects, comprising the following steps:

[0082] (1) At room temperature, a polyurethane UV adhesive coating is applied to the upper surface of the TPU carrier layer to form a UV adhesive layer;

[0083] (2) using an embossing roller to roll the UV adhesive layer at a pressure of 420 kPa, so that an uneven texture structure is formed on the upper surface of the UV adhesive layer to obtain a prefabricated texture layer;

[0084] (3) curing the prefabricated texture layer with ultraviolet light using a UV machine to obtain a prefabricated TPU high and low temperature film;

[0085] (4) Electron beam physical vapor deposition technology (e-beam PVD) is used to deposit a nano-metal film on the surface of the texture layer to form an optical coating layer, thereby producing a TPU high and low temperature film with optical color effects.

[0086] Furthermore, the TPU carrier layer is a transparent TPU film with a model number of ZD-135CM*85A produced by Guangdong Zhongding Technology Development Co., Ltd., and a thickness of 1.2 mm.

[0087] Furthermore, the nano-metal film includes, from top to bottom, a nano-silicon dioxide particle layer, a nano-titanium dioxide particle layer, and a nano-zinc oxide-coated silicon dioxide particle layer. The nano-silicon dioxide particle layer includes nano-silicon dioxide particles; the nano-titanium dioxide particle layer includes nano-titanium dioxide particles; and the nano-zinc oxide-coated silicon dioxide particle layer includes nano-zinc oxide-coated silicon dioxide particles.

[0088] Furthermore, the particle size of the nano-silicon dioxide particles is 230 nm; the particle size of the nano-titanium dioxide particles is 167 nm.

[0089] Furthermore, the thickness ratio of the nano-silica particle layer, the nano-titanium dioxide particle layer and the nano-zinc oxide-coated silica particle layer is 0.3:0.3:0.6.

[0090] Furthermore, the method for preparing the metal film layer includes the following steps:

[0091] (1) The prefabricated TPU high and low temperature film was ultrasonically cleaned with clean water for 4 h, dehydrated with anhydrous ethanol, degreased with butyl acetate, dried in a vacuum dryer for 6 h, and mounted on a substrate holder and loaded into a furnace;

[0092] (2) Nano-zinc oxide-coated silica particles were used as metal targets. The metal targets were placed on the target holder. The position and size of the laser beam spot were adjusted with a low-power laser beam. The coating chamber was evacuated to a vacuum degree of 6.7×10 -3 Pa, and then argon was introduced to control the vacuum degree to 2.7×10 -3 Pa, heat the substrate to 180°C, start the laser and gradually increase the laser beam power to 360W, while rotating the metal target at a constant speed to make it evaporate stably, and deposit a nano-zinc oxide-coated silicon dioxide particle layer on the surface of the prefabricated TPU high and low temperature film;

[0093] (3) using nano-titanium dioxide particles as metal targets, repeating the above step (2) to deposit a nano-titanium dioxide particle layer on the surface of the nano-zinc oxide-coated silicon dioxide particle layer;

[0094] (4) Using nano-silica particles as metal targets, repeat the above step (2) to deposit a nano-silica particle layer on the surface of the nano-titanium dioxide particle layer, and finally obtain a metal film layer.

[0095] Furthermore, the preparation method of the nano zinc oxide coated silicon dioxide particles is as follows:

[0096] (1) Weigh 2 g of the above-mentioned nano-silica particles and disperse them evenly in 2 L of ethanol by ultrasonic dispersion;

[0097] (2) adding 25 mL of a 2% volume fraction APTES ethanol solution and 50 mL of deionized water, stirring at low speed for 2 hours at room temperature, and washing the resulting product twice with deionized water and then three times with ethanol to obtain pretreated silica particles;

[0098] (3) The pretreated silica particles were dispersed in 25 mL of glutaraldehyde dilution solution, stirred for 3 h, washed twice with deionized water and ethanol, and then dispersed in 20 mL of ethanol to obtain solution A;

[0099] (4) Liquid A was placed in a water bath at 80°C, and 6 mL of zinc ammonia solution was added to liquid A three times every 20 minutes. After the last addition, the reaction was continued for 20 minutes. After washing three times with ethanol by centrifugation, nano-zinc oxide-coated silica particles were obtained.

[0100] It should be further explained that the precipitate is separated from the supernatant by differential centrifugation, and low-speed centrifugation and high-speed centrifugation are performed alternately. Nano-zinc oxide-coated silica particles with different sedimentation coefficients are settled down separately, and nano-zinc oxide-coated silica microspheres with too large or too small particle sizes in the product system are removed.

[0101] Furthermore, the particle size of the prepared nano zinc oxide-coated silicon dioxide particles was measured to be 310 nm.

[0102] Furthermore, the preparation method of the glutaraldehyde dilution solution is as follows: dissolve 1.2g of anhydrous sodium dihydrogen phosphate and 0.156g of sodium hydroxide in water and stir evenly to prepare 0.1mol / L phosphate buffer solution, and dilute the glutaraldehyde solution with 0.1mol / L phosphate buffer solution to a volume fraction of 5% to obtain the glutaraldehyde dilution solution.

[0103] Furthermore, the zinc ammonia solution is prepared as follows: ammonia water is diluted with distilled water to a volume fraction of 2%, and solid zinc chloride is prepared with deionized water to form a 0.1 mol / L zinc chloride solution. A certain amount of the zinc chloride solution is poured into a beaker, and the diluted ammonia solution is slowly added dropwise while stirring until the precipitate disappears.

[0104] It should be further explained that the precipitate is separated from the supernatant by differential centrifugation, and low-speed centrifugation and high-speed centrifugation are performed alternately. Nanoparticles with different sedimentation coefficients are settled separately, and microspheres with too large or too small particle sizes in the product system are removed.

[0105] The rest of the content of this embodiment is the same as that of embodiment 1.

[0106] Example 4

[0107] In this embodiment, the preparation method of the modified epoxy resin includes the following steps:

[0108] (1) Dissolve bisphenol A epoxy resin in butyl acrylate, add polytetramethylene glycol 250, polymerization inhibitor and catalyst B, heat to 90°C and react for 3 hours to obtain product C;

[0109] (2) The system temperature was lowered to 95°C, and α-methacrylic acid was slowly added dropwise to the product C and the reaction was continued for 1 hour. The reaction was then continued at the same temperature for another 1 hour to obtain a modified epoxy resin.

[0110] Furthermore, the molar ratio of the polytetramethylene ether glycol 250 to the bisphenol A epoxy resin is 0.4:1.

[0111] Furthermore, the molar ratio of the added amount of α-methacrylic acid to the bisphenol A epoxy resin is 0.7:1.

[0112] Furthermore, the bisphenol A epoxy resin is a bisphenol A epoxy resin with an epoxy value of 0.46 produced by Shanghai Luohe High-tech Materials Co., Ltd.

[0113] The rest of the content of this embodiment is the same as that of embodiment 3.

[0114] Example 5

[0115] In this embodiment, the polyurethane UV adhesive coating includes the following raw materials in parts by weight: 33 parts of polyurethane prepolymer, 25 parts of bismaleimide resin, 48 parts of reactive diluent, and 5 parts of photoinitiator.

[0116] Furthermore, at room temperature, polyurethane prepolymer and bismaleimide resin are added into a reaction container, and then reactive diluent and photoinitiator are added and mixed evenly to prepare polyurethane UV adhesive coating.

[0117] The rest of the content of this embodiment is the same as that of embodiment 4.

[0118] Example 6

[0119] In this embodiment, the polyurethane UV adhesive coating includes the following raw materials in parts by weight: 36 parts of polyurethane prepolymer, 28 parts of bismaleimide resin, 52 parts of reactive diluent, and 5 parts of photoinitiator.

[0120] Furthermore, at room temperature, polyurethane prepolymer and bismaleimide resin are added into a reaction container, and then reactive diluent and photoinitiator are added and mixed evenly to prepare polyurethane UV adhesive coating.

[0121] The rest of the content of this embodiment is the same as that of embodiment 4.

[0122] Comparative Example 1

[0123] The difference between this comparative example and Example 3 is that in the preparation method of the polyurethane prepolymer, hydrogenated bisphenol A epoxy resin is used to replace the modified epoxy resin.

[0124] Furthermore, the hydrogenated bisphenol A epoxy resin uses a hydrogenated bisphenol A epoxy resin with an epoxy value of 0.46 obtained from Shanghai Luohe High-tech Materials Co., Ltd.

[0125] Comparative Example 2

[0126] The difference between the comparative example and Example 3 is that the nano-zinc oxide-coated silicon dioxide particles are replaced with nano-silicon dioxide particles with the same particle size.

[0127] Performance Testing

[0128] The textured layers prepared in Examples 3-6 and Comparative Example 1 had a thickness of 6 μm, and the optical coating layer had a thickness of 1.5 μm. Performance tests were conducted on the resulting TPU high- and low-temperature films with optical color effects. The tensile strength of the TPU high- and low-temperature films and the adhesion of the corresponding optical coating layer to the textured layer surface under different conditions were tested. The test data are shown in Table 1 below:

[0129] Table 1

[0130] The tensile strength test was carried out according to GB / T1040.3-2006, and the tensile rate was 100 mm / min.

[0131] Adhesion test adopts GB / T9286-1998;

[0132] The hydrolysis resistance test adopts QB / T2888: soak in 10% sodium hydroxide solution at 30°C for 24 hours;

[0133] In the boiling resistance test, the boiling treatment condition is 80℃ boiling for 8 hours;

[0134] The aging resistance test was conducted using QUV340nm for 1000 hours with a light intensity of 0.8W / cm 2 .

[0135] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the scope of protection of the present invention.

Claims

1. A TPU high and low temperature film with optical color effects, characterized in that: It comprises an optical coating layer, a UV texture layer and a TPU carrier layer which are arranged in sequence from top to bottom, and the texture layer is made of polyurethane UV glue coating.

2. The TPU high and low temperature film with optical color effect according to claim 1, characterized in that: The texture layer is a grating structure layer, and the grating structure layer includes a plurality of continuously arranged cylindrical lenses, the upper ends of the cylindrical lenses are connected to the optical coating layer, and the lower ends of the cylindrical lenses are connected to the TPU carrier layer.

3. The TPU high and low temperature film with optical color effect according to claim 2, characterized in that: It also includes a hot melt adhesive layer and a pattern layer arranged on the upper end of the hot melt adhesive layer, the pattern layer is located at the lower end of the UV texture layer, the pattern layer includes a first pattern layer, a high-transparency material layer and a second pattern layer arranged in sequence from top to bottom, the first pattern layer is divided into a plurality of first pattern units arranged at intervals, a first gap is arranged between adjacent first pattern units, adjacent first pattern units and the first gap are located at the lower end of a single cylindrical lens, the second pattern layer is divided into a plurality of second pattern units arranged at intervals, a second gap is arranged between adjacent second pattern units, each second pattern unit is located at the lower end of the corresponding first gap, and each second gap is located at the lower end of the corresponding first pattern layer.

4. The TPU high and low temperature film with optical color effect according to claim 1, characterized in that: The polyurethane UV adhesive coating comprises the following raw materials in parts by weight: 30-36 parts of polyurethane prepolymer, 22-28 parts of bismaleimide resin, 45-55 parts of active diluent, and 4-6 parts of photoinitiator.

5. The TPU high and low temperature film with optical color effect according to claim 4, characterized in that: The preparation method of the polyurethane UV adhesive coating comprises the following steps: adding a polyurethane prepolymer and a bismaleimide resin into a reaction container at room temperature, and then adding an active diluent and a photoinitiator and mixing them evenly to prepare the polyurethane UV adhesive coating.

6. The TPU high and low temperature film with optical color effect according to claim 5, characterized in that: The active diluent is prepared by compounding 1,6-hexanediol diacrylate and 4-acryloylmorpholine.

7. The TPU high and low temperature film with optical color effect according to claim 4, characterized in that: The preparation method of the polyurethane prepolymer comprises the following steps: (1) adding isophorone diisocyanate and catalyst A into a reaction vessel, heating to 60-80° C., adding poly(ethylene-co-1,2-butene) glycol dropwise, reacting for 2.5-3.5 hours, cooling to 20-30° C., adding dihydroxypropionic acid, heating to 85-95° C., reacting for 1-2 hours, cooling to room temperature, and slowly adding diethylamine dropwise for neutralization to obtain product A; (2) Under nitrogen protection, add modified epoxy resin to product A, raise the temperature to 85-95° C. and continue stirring for 2.5-3.5 hours, then cool down to obtain the polyurethane prepolymer.

8. The TPU high and low temperature film with optical color effect according to claim 7, characterized in that: The molar ratio of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate is 1:(1-2); the added amount of the modified epoxy resin is 20-30% of the total mass of the poly(ethylene-co-1,2-butene) glycol and isophorone diisocyanate.

9. The TPU high and low temperature film with optical color effect according to claim 7, characterized in that: The catalyst A is at least one of dibutyltin dilaurate and stannous octoate.

10. A method for preparing the TPU high and low temperature film with optical color effect according to claim 1, characterized in that: The steps include: (1) At room temperature, a polyurethane UV adhesive coating is applied to the upper surface of the TPU carrier layer to form a UV adhesive layer; (2) using an embossing roller to roll the UV adhesive layer at a pressure of 392-490 kPa, so that an uneven texture structure is formed on the upper surface of the UV adhesive layer to obtain a prefabricated texture layer; (3) curing the prefabricated texture layer by ultraviolet light using a UV machine to obtain a prefabricated TPU high and low temperature film; (4) Electron beam physical vapor deposition technology is used to deposit a nano-metal film on the surface of the texture layer to form an optical coating layer, thereby producing a TPU high and low temperature film with optical color effects.

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