TPU high- and low-temperature film having optical color effects and method for manufacturing the same

Abstract

This invention relates to the technical field of TPU, and more specifically to a TPU high-temperature film having an optical color effect and a method for manufacturing the same. The TPU high-temperature film having an optical color effect comprises, from top to bottom, an optical coating layer, a texture layer, a TPU carrier layer, and a hot-melt adhesive layer, wherein the texture layer is manufactured with a polyurethane UV adhesive coating. The TPU high-temperature film has stable quality and excellent tensile strength, resistance to UV degradation, resistance to hydrolysis, and resistance to boiling water, while its optical coating layer also has good adhesion, resistance to hydrolysis, resistance to boiling water, and resistance to degradation, making it easy to use. The method for manufacturing the TPU high-temperature film is simple in process, easy to control, and useful for large-scale industrial production. Furthermore, since no waste, wastewater, or exhaust gases are generated during the production process, it does not pollute the environment and contributes to human environmental protection.

Description

Technical Field

[0001] The present invention relates to the technical field of TPU, and specifically to a TPU high and low temperature film having an optical color effect and a manufacturing method thereof.

Background Art

[0002] At present, TPU high and low temperature films have already been widely applied and have characteristics such as being soft, highly elastic, and excellent in mechanical properties, so they can be applied to various fabrics such as clothing, bags, tents, shoe materials, and other products. Both sides of the TPU high and low temperature film have different melting points, mainly including 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 adhesion with other materials, and the high temperature layer can be applied to the surface of the product as a carrier or surface layer, thereby improving the performance of the product. Existing TPU high and low temperature films have a dazzling optical film layer manufactured to meet the needs of consumers, but the existing optical film layer becomes weak in adhesion and prone to powder falling after long-term use, and waste gas and waste water are generated in the production process, which also has an adverse impact on the environment.

Summary of the Invention

Problems to be Solved by the Invention

[0003] In order to overcome the drawbacks and defects of the prior art, the object of the present invention is to provide a TPU high and low temperature film having an optical color effect and a TPU film having an optical color effect. The TPU high and low temperature film has excellent tensile properties, ultraviolet degradation resistance, hydrolysis resistance, and boiling water resistance, and at the same time, its optical coating layer also has good adhesion, hydrolysis resistance, boiling water resistance, durability, and degradation resistance, and is easy to use.

[0004] Another object of the present invention is to provide a method for manufacturing a TPU high-temperature film having an optical color effect, the method being simple in process and easy to control, useful for large-scale industrial production, and the manufactured TPU high-temperature film having excellent tensile strength, UV degradation resistance and boiling water resistance, as well as its optical coating layer having good adhesion, hydrolysis resistance, boiling water resistance, durability and degradation resistance, resulting in excellent overall performance. [Means for solving the problem]

[0005] The object of the present invention is achieved by the following technical solution: A TPU high-temperature film having an optical color effect, comprising an optical coating layer, a UV texture layer, and a TPU carrier layer arranged in order from top to bottom, wherein the texture layer is manufactured from a polyurethane UV adhesive coating.

[0006] The TPU high-temperature film and TPU film having optical color effects according to the present invention have a simple structure, stable connection between the TPU carrier layer and the texture layer, and the TPU high-temperature film has excellent tensile strength, resistance to UV degradation, resistance to hydrolysis and boiling water, while its optical coating layer also has good adhesion, resistance to hydrolysis, resistance to boiling water, durability and resistance to degradation.

[0007] Furthermore, the thickness of the optical coating layer is 1 to 2 μm, the thickness of the texture layer is 4 to 6 μm, and the thickness of the TPU high / low temperature film is 0.5 to 1.5 cm.

[0008] Furthermore, the texture layer is a lattice structure layer containing a plurality of cylindrical lenses arranged in a continuous pattern, the upper ends of the cylindrical lenses being connected to an optical coating layer, and the lower ends of the cylindrical lenses being connected to a TPU carrier layer.

[0009] Furthermore, the TPU high-temperature film having the optical color effect further includes a hot-melt adhesive layer and a pattern layer provided at the upper end of the hot-melt adhesive layer, the pattern layer being located at the lower end of the UV texture layer and comprising a first pattern layer, a high-transparency material layer and a second pattern layer arranged in order from top to bottom, the first pattern layer being divided into a plurality of spaced-apart first pattern units, with a first gap between adjacent first pattern units, the adjacent first pattern units and the first gaps being located at the lower end of a single cylindrical lens, the second pattern layer being divided into a plurality of spaced-apart second pattern units, with a second gap between adjacent second pattern units, each second pattern unit being located at the lower end of the corresponding first gap, and each second gap being located at the lower end of the corresponding first pattern layer.

[0010] Furthermore, the polyurethane UV adhesive coating comprises 30 to 36 parts polyurethane prepolymer, 22 to 28 parts bismaleimide resin, 45 to 55 parts reactive diluent, and 4 to 6 parts photoinitiator.

[0011] Furthermore, the method for manufacturing the polyurethane UV adhesive coating is as follows: The process includes adding a polyurethane prepolymer and a bismaleimide resin to a reaction vessel at room temperature, then adding a reactive diluent and a photoinitiator and mixing them uniformly to obtain a polyurethane UV adhesive coating.

[0012] The present invention, by employing the above manufacturing method to produce polyurethane UV adhesive coating, achieves a good blend of each raw material, resulting in a TPU high / low temperature film with excellent tensile strength, UV degradation resistance, hydrolysis resistance, and boiling water resistance. At the same time, its optical coating layer also possesses good adhesion, hydrolysis resistance, boiling water resistance, durability, and degradation resistance, and exhibits strong adhesion to the TPU carrier layer.

[0013] Furthermore, the photoinitiator is at least one of Irgacure2959, Irgacure1173, and Irgacure184, and the reactive diluent is a mixture of 1,6-hexanediol diacrylate and 4-acryloylmorpholine. The mass ratio of 1,6-hexanediol diacrylate to 4-acryloylmorpholine is 1:1 to 2.

[0014] Furthermore, the method for producing the polyurethane prepolymer is as follows: Step (1) involves adding isophorone diisocyanate and catalyst A to a reaction vessel, raising the temperature to 60-80°C, adding poly(ethylene-co-1,2-butylene)diol dropwise, reacting for 2.5-3.5 hours, then cooling to 20-30°C, adding dihydroxypropionic acid, raising the temperature to 85-95°C and reacting for 1-2 hours, then cooling to room temperature, and finally slowly adding diethylamine dropwise to neutralize and obtain product A. The process includes step (2), in which a modified epoxy resin is added to product A under nitrogen protection, the temperature is raised to 85-95°C, the mixture is continuously stirred for 2.5-3.5 hours, and then the temperature is lowered to obtain the polyurethane prepolymer. Preferably, the poly(ethylene-co-1,2-butylene)diol needs to be dehydrated for 5 to 10 hours before the reaction by high temperature (100 to 110°C) or by vacuum drying using a 4A molecular sieve, with a vacuum level of 0.01 to 0.05, and more preferably, the poly(ethylene-co-1,2-butylene)diol is dehydrated and dried for 5 hours under conditions of 110°C and a vacuum level of 0.01.

[0015] Furthermore, the molar ratio of poly(ethylene-co-1,2-butylene)diol to isophorone diisocyanate is 1:(1~2), and the amount of modified epoxy resin added is 20~30% of the total mass of poly(ethylene-co-1,2-butylene)diol and isophorone diisocyanate.

[0016] Furthermore, the amount of dihydroxypropionic acid added is 10-14% of the total mass of poly(ethylene-co-1,2-butylene)diol and isophorone diisocyanate.

[0017] Furthermore, the catalyst A is at least one of dibutyltin dilaurate and stannous octoate. The addition amount of the catalyst A is 3% of the total mass of poly(ethylene-co-1,2-butylene) diol and isophorone diisocyanate.

[0018] Furthermore, the method for producing the modified epoxy resin is as follows: Dissolve the epoxy resin in butyl acrylate, then add polytetramethylene ether glycol 250, a polymerization inhibitor, and catalyst B, raise the temperature to 80-100 °C, and react for 3-4 h to obtain product C in step (1); Lower the temperature of the system to 90-100 °C, slowly dropwise add α-methacrylic acid to product C and continue the reaction for 1-2 h, and then continue the reaction at the same temperature for 1-2 h to obtain the modified epoxy resin in step (2).

[0019] Furthermore, the catalyst B is one of tetrabutylammonium bromide and triethylamine. The addition amount of the catalyst B is 2% of the total mass of the epoxy resin and polytetramethylene ether glycol 250.

[0020] Furthermore, the molar ratio of polytetramethylene ether glycol 250 to the epoxy resin is 0.3-0.4:1.

[0021] Furthermore, the polymerization inhibitor uses p-hydroxyanisole, and the usage amount is 0.04-0.06% of the total mass of the epoxy resin and polytetramethylene ether glycol 250.

[0022] Furthermore, the molar ratio of the addition amount of α-methacrylic acid to the epoxy resin is 0.6-0.8:1.

[0023] Furthermore, the epoxy resin is bisphenol A type epoxy resin or hydrogenated bisphenol A type epoxy resin.

[0024] The present invention is a method for manufacturing a TPU high and low temperature film having the optical color effect, comprising: Step (1) of applying a polyurethane UV adhesive paint on the upper surface of a TPU carrier layer at room temperature to form a UV adhesive layer; Step (2) of rolling the UV adhesive layer with an embossing roller at a pressure of 392 to 490 kPa to form a concavo-convex texture structure on the upper surface of the UV adhesive layer and obtaining a pre-texture layer; Step (3) of irradiating the pre-texture layer with ultraviolet rays by a UV device to cure it and obtaining a pre-TPU high and low temperature film; Step (4) of adopting an electron beam physical vapor deposition technology (e-beam PVD) to deposit a nano metal thin film on the surface of the texture layer to form an optical coating layer and obtaining a TPU high and low temperature film having an optical color effect. Further provided is the method for manufacturing a TPU high and low temperature film having the optical color effect.

[0025] Furthermore, the TPU carrier layer uses a transparent TPU film with the model number ZD-135CM*85A manufactured by Guangdong Zhongding Technology Development Co., Ltd., and has a thickness of 0.5 to 1.2 mm.

[0026] Furthermore, the nano metal thin film includes a nano silicon dioxide particle layer, a nano titanium dioxide particle layer, and a nano zinc oxide-coated silicon dioxide particle layer provided in sequence from top to bottom. The nano silicon dioxide particle layer contains nano silicon dioxide particles, the nano titanium dioxide particle layer contains nano titanium dioxide particles, and the nano zinc oxide-coated silicon dioxide particle layer contains nano zinc oxide-coated silicon dioxide particles.

[0027] Furthermore, the thickness ratio of the nano silicon dioxide particle layer, the nano titanium dioxide particle layer, and the nano zinc oxide-coated silicon dioxide particle layer is 0.2 to 0.4: (0.2 to 0.4): (0.5 to 0.7). <opropyl acetate and 1,2-dichlorobenzene; Furthermore, the particle diameter of the nano silicon dioxide particles is 200 to 260 nm, the particle diameter of the nano titanium dioxide particles is 150 to 180 nm, and the particle diameter of the nano zinc oxide-coated silicon dioxide particles is 280 to 350 nm.

[0029] Furthermore, the method for manufacturing the metal film layer is as follows: Step (1) involves ultrasonically cleaning the above pre-TPU high-temperature film with clean water for 3-4 hours, dehydrating it with anhydrous ethanol, degreasing it with butyl acetate, drying it in a vacuum dryer for 5-6 hours, then mounting it on a substrate jig and loading it into the furnace. Nano zinc oxide-coated silicon dioxide particles are used as a metal target. The metal target is placed on a target holder, and the position and dimensions of the laser beam spot are adjusted using a low-power laser beam. The coating chamber is 6.6-6.8 × 10⁻⁶. -3 Vacuum is drawn down to a vacuum of Pa, then argon gas is introduced to increase the vacuum level to 2.5-2.9 × 10⁻⁶. -3 Step (2) involves controlling the temperature to Pa, heating the substrate to 160-190°C, starting the laser device, gradually increasing the laser beam output to 350-380W, and simultaneously rotating the metal target at a constant speed to stabilize evaporation, thereby depositing a nano zinc oxide coated silicon dioxide particle layer onto the upper surface of the pre-TPU high-temperature film. Step (3) involves using nanotitanium dioxide particles as a metal target, repeating step (2) above, and depositing a layer of nanotitanium dioxide particles onto the upper surface of the nanozinc oxide-coated silicon dioxide particle layer. The method includes step (4), in which nanosilicon dioxide particles are used as a metal target, and the above step (2) is repeated to deposit a nanosilicon dioxide particle layer onto the upper surface of the nanotitanium dioxide particle layer, ultimately obtaining a metal film layer.

[0030] Furthermore, the method for producing the nano zinc oxide coated silicon dioxide particles is as follows: Step (1) involves weighing 1-3 g of the above nano silicon dioxide particles, dispersing them in 1-2 L of ethanol, dispersing them uniformly using ultrasound, adding 20-30 mL of a 2-3% volume fraction APTES ethanol solution and 45-55 mL of deionized water, stirring slowly at room temperature for 2-3 hours, washing the resulting product twice with deionized water, and then washing it 3-4 times with ethanol to obtain pre-treated silicon dioxide particles. Step (2) involves dispersing pre-treated silicon dioxide particles in 20-30 mL of diluted glutaraldehyde solution, stirring for 3-4 hours, washing twice with deionized water and ethanol, and then dispersing them in 15-25 mL of ethanol to obtain solution A. The method includes step (3), which involves placing the system of solution A in a water bath at 75-85°C, adding 7-8 mL of zinc ammonia solution to solution A in three separate additions every 15-25 minutes, continuing the reaction for 18-22 minutes after the final addition is complete, and washing by centrifugation three times with ethanol to obtain nano zinc oxide coated silicon dioxide particles.

[0031] Furthermore, the method for producing the glutaraldehyde diluent includes the steps of dissolving 1.2 g of anhydrous sodium dihydrogen phosphate and 0.156 g of sodium hydroxide in water, stirring uniformly to obtain a 0.1 mol / L phosphate buffer, and then diluting the glutaraldehyde solution to a volume fraction of 5% with the 0.1 mol / L phosphate buffer to obtain the glutaraldehyde diluent.

[0032] Furthermore, the method for producing the zinc ammonia solution includes the steps of diluting ammonia water to a volume fraction of 2% with distilled water, preparing a 0.1 mol / L zinc chloride solution with deionized water using solid zinc chloride, placing an appropriate amount of the zinc chloride solution into a beaker, and slowly adding the diluted ammonia aqueous solution drop by drop while stirring until the precipitate disappears.

[0033] The method for manufacturing TPU high-temperature films according to the present invention is simple in process, easy to control, and useful for large-scale industrial production. The manufactured TPU high-temperature films have stable quality and excellent tensile strength, resistance to UV degradation, resistance to hydrolysis, and resistance to boiling water. At the same time, their optical coating layer also has good adhesion, resistance to hydrolysis, resistance to boiling water, durability, and resistance to degradation, resulting in excellent overall performance. [Effects of the Invention]

[0034] The beneficial effects of the present invention are as follows: The TPU high-temperature film having optical color effect according to the present invention has a simple structure, stable connection between the TPU carrier layer and the texture layer, and stable connection between the optical coating and the texture layer, making the TPU high-temperature film useful for large-scale industrial production. It has excellent tensile strength, resistance to UV degradation and boiling water, and at the same time, its optical coating layer also has good adhesion, hydrolysis resistance, boiling water resistance, durability and degradation resistance. The manufacturing method of the TPU high-temperature film is simple, easy to control, and furthermore, does not generate wastewater or exhaust gas during the production process, thus not polluting the environment and being very useful for protecting the environment for humans. [Brief explanation of the drawing]

[0035] [Figure 1] Figure 1 is a product diagram of the present invention. [Modes for carrying out the invention]

[0036] To facilitate understanding for those skilled in the art, the present invention will be further described below with reference to examples. The contents described in the examples are not intended to limit the present invention.

[0037] Example 1 In this embodiment, the TPU high-temperature film having an optical color effect includes an optical coating layer, a UV texture layer, and a TPU carrier layer arranged in order from top to bottom, wherein the texture layer is manufactured with a polyurethane UV adhesive paint, the connection between the TPU carrier layer and the texture layer is stable, and the connection between the optical coating and the texture layer is stable. The TPU high-temperature film has excellent tensile strength, resistance to UV degradation, resistance to hydrolysis and boiling water, and at the same time, its optical coating layer also has good adhesion, resistance to hydrolysis, resistance to boiling water, durability and resistance to degradation.

[0038] Furthermore, the texture layer is a lattice structure layer containing a plurality of cylindrical lenses arranged in a continuous pattern, the upper ends of the cylindrical lenses being connected to an optical coating layer, and the lower ends of the cylindrical lenses being connected to a TPU carrier layer.

[0039] The TPU high-temperature film having an optical color effect according to the present invention has a simple structure, stable connection between the TPU carrier layer and the texture layer, stable connection between the optical coating and the texture layer, and the TPU high-temperature film has excellent tensile strength, resistance to UV degradation, resistance to hydrolysis and boiling water, while its optical coating layer also has good adhesion, resistance to hydrolysis, resistance to boiling water, durability and resistance to degradation. As a result, the manufactured TPU high-temperature film having an optical color effect has stable quality.

[0040] Example 2 The TPU high-temperature film having the optical color effect further includes a hot-melt adhesive layer and a pattern layer provided at the upper end of the hot-melt adhesive layer, the pattern layer being located at the lower end of the UV texture layer and comprising a first pattern layer, a high-transparency material layer and a second pattern layer provided in order from top to bottom, the first pattern layer being divided into a plurality of spaced-apart first pattern units, with a first gap between adjacent first pattern units, the adjacent first pattern units and the first gaps being located at the lower end of a single cylindrical lens, the second pattern layer being divided into a plurality of spaced-apart second pattern units, with a second gap between adjacent second pattern units, each second pattern unit being located at the lower end of the corresponding first gap, and each second gap being located at the lower end of the corresponding first pattern layer.

[0041] Example 3 In this embodiment, the polyurethane UV adhesive coating comprises 30 parts polyurethane prepolymer, 22 parts bismaleimide resin, 48 parts reactive diluent, and 5 parts photoinitiator.

[0042] Furthermore, the method for producing the polyurethane UV adhesive coating includes the steps of adding a polyurethane prepolymer and a bismaleimide resin to a reaction vessel at room temperature, then adding a reactive diluent and a photoinitiator and mixing them uniformly to obtain the polyurethane UV adhesive coating.

[0043] Furthermore, the bismaleimide resin used is bismaleimide resin with CAS number 13676-54-5 manufactured by Huaxiang Kejie.

[0044] Furthermore, the photoinitiator was Irgacure 184, and the reactive diluent was a mixture of 1,6-hexanediol diacrylate and 4-acryloylmorpholine. The mass ratio of 1,6-hexanediol diacrylate to 4-acryloylmorpholine was 1:1.

[0045] Furthermore, the method for producing the polyurethane prepolymer is as follows: Step (1) involves adding isophorone diisocyanate and catalyst A to a reaction vessel, raising the temperature to 75°C, adding poly(ethylene-co-1,2-butylene)diol dropwise, reacting for 3 hours, cooling to 25°C, adding dihydroxypropionic acid, raising the temperature to 90°C and reacting for 1.5 hours, cooling to room temperature, and then slowly adding diethylamine dropwise to neutralize and obtain product A. The process includes step (2), in which a modified epoxy resin is added to product A under nitrogen protection, the temperature is raised to 90°C, the mixture is continuously stirred for 3 hours, and then the temperature is lowered to obtain the polyurethane prepolymer.

[0046] Furthermore, it should be explained that poly(ethylene-co-1,2-butylene)diol is dehydrated and dried for 5 hours at 110°C under a vacuum of 0.01.

[0047] Furthermore, the molar ratio of the poly(ethylene-co-1,2-butylene)diol to the isophorone diisocyanate is 1:1, and the amount of the modified epoxy resin added is 25% of the total mass of the poly(ethylene-co-1,2-butylene)diol and isophorone diisocyanate.

[0048] Furthermore, the amount of dihydroxypropionic acid added is 12% of the total mass of poly(ethylene-co-1,2-butylene)diol and isophorone diisocyanate.

[0049] Furthermore, the poly(ethylene-co-1,2-butylene)diol used is polytetramethylene glycol with CAS number 68954-10-9 manufactured by Shanghai Kaiyin Chemical.

[0050] Furthermore, catalyst A was dibutyltin dilaurate. The amount of catalyst A added was 3% of the total mass of poly(ethylene-co-1,2-butylene)diol and isophorone diisocyanate.

[0051] Furthermore, the method for producing the modified epoxy resin is as follows: Step (1) involves dissolving a hydrogenated bisphenol A type epoxy resin in butyl acrylate, then adding polytetramethylene ether glycol 250, a polymerization inhibitor, and catalyst B, raising the temperature to 90°C, and reacting for 3 hours to obtain product C. The method includes step (2) lowering the temperature of the system to 95°C, slowly adding α-methacrylic acid dropwise to product C and continuing the reaction for 1 hour, and then continuing the reaction at the same temperature for 1 hour to obtain a modified epoxy resin.

[0052] Furthermore, catalyst B was tetrabutylammonium bromide. The amount of catalyst B added was 2% of the total mass of hydrogenated bisphenol A epoxy resin and polytetramethylene ether glycol 250.

[0053] Furthermore, the molar ratio of the polytetramethylene ether glycol 250 to the hydrogenated bisphenol A type epoxy resin is 0.4:1.

[0054] Furthermore, the polymerization inhibitor used 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.

[0055] Furthermore, the molar ratio of the amount of α-methacrylic acid added to the hydrogenated bisphenol A type epoxy resin is 0.7:1.

[0056] Furthermore, the hydrogenated bisphenol A type epoxy resin used is a hydrogenated bisphenol A type epoxy resin with an epoxy value of 0.46 manufactured by Shanghai Luohe High-tech Materials Co., Ltd.

[0057] The present invention relates to a method for manufacturing a TPU high-temperature film having the optical color effect, Step (1) involves applying a polyurethane UV adhesive coating to the upper surface of a TPU carrier layer at room temperature to form a UV adhesive layer, Step (2) involves rolling the UV adhesive layer with an embossing roller at a pressure of 420 kPa to form an uneven textured structure on the upper surface of the UV adhesive layer, thereby obtaining a pre-textured layer. Step (3) involves curing the pretexture layer by irradiating it with ultraviolet light using a UV device to obtain a pre-TPU high-temperature film, The present invention further provides a method for manufacturing a TPU high-temperature film having an optical color effect, which includes step (4) depositing a nanometal thin film onto the surface of a texture layer using electron beam physical deposition (e-beam PVD) technology to form an optical coating layer and obtain a TPU high-temperature film having an optical color effect.

[0058] Furthermore, the TPU carrier layer uses a transparent TPU film with model number ZD-135CM*85A manufactured by Guangdong Zhongding Technology Development Co., Ltd., and has a thickness of 1.2 mm.

[0059] Furthermore, the nanometal thin film includes a layer of nanosilicon dioxide particles, a layer of nanotitanium dioxide particles, and a layer of nanozinc oxide-coated silicon dioxide particles, arranged in order from top to bottom. The nanosilicon dioxide particle layer contains nanosilicon dioxide particles, the nanotitanium dioxide particle layer contains nanotitanium dioxide particles, and the nanozinc oxide-coated silicon dioxide particle layer contains nanozinc oxide-coated silicon dioxide particles.

[0060] Furthermore, the particle size of the nano silicon dioxide particles is 230 nm, and the particle size of the nano titanium dioxide particles is 167 nm.

[0061] Furthermore, the thickness ratio of the nano silicon dioxide particle layer, the nano titanium dioxide particle layer, and the nano zinc oxide coated silicon dioxide particle layer is 0.3:0.3:0.6.

[0062] Furthermore, the method for manufacturing the metal film layer is as follows:

[0063] Step (1) involves ultrasonically cleaning the pre-TPU high-temperature film with clean water for 4 hours, dehydrating it with anhydrous ethanol, degreasing it with butyl acetate, drying it in a vacuum dryer for 6 hours, then mounting it on a substrate jig and loading it into the furnace. Nano zinc oxide-coated silicon dioxide particles are used as a metal target. The metal target is placed on a target holder, and the position and dimensions of the laser beam spot are adjusted using a low-power laser beam. The coating chamber is 6.7 × 10⁻⁶. -3 The vacuum was reduced to a pressure of Pa, and then argon gas was introduced to increase the vacuum to 2.7 × 10⁻⁶. -3 Step (2) involves controlling the temperature to Pa, heating the substrate to 180°C, starting the laser device, gradually increasing the laser beam output to 360W, and simultaneously rotating the metal target at a constant speed to stabilize evaporation, thereby depositing a nano zinc oxide coated silicon dioxide particle layer onto the upper surface of the pre-TPU high-temperature film. Step (3) involves using nanotitanium dioxide particles as a metal target, repeating step (2) above, and depositing a layer of nanotitanium dioxide particles onto the upper surface of the nanozinc oxide-coated silicon dioxide particle layer. The method includes step (4), in which nanosilicon dioxide particles are used as a metal target, and the above step (2) is repeated to deposit a nanosilicon dioxide particle layer onto the upper surface of the nanotitanium dioxide particle layer, ultimately obtaining a metal film layer.

[0064] Furthermore, the method for producing the nano zinc oxide coated silicon dioxide particles is as follows: Step (1) involves weighing 2 g of the above nano silicon dioxide particles, dispersing them in 2 L of ethanol, and uniformly dispersing them using ultrasound. Step (2) involves adding 25 mL of a 2% volume fraction APTES ethanol solution and 50 mL of deionized water, stirring slowly at room temperature for 2 hours, washing the resulting product twice with deionized water, and then washing it three times with ethanol to obtain pre-treated silicon dioxide particles. Step (3) involves dispersing pre-treated silicon dioxide particles in 25 mL of glutaraldehyde dilution, stirring for 3 hours, washing twice with deionized water and ethanol, and then dispersing them in 20 mL of ethanol to obtain solution A. The method includes step (4), which involves placing the system of solution A in an 80°C water bath, adding 6 mL of zinc ammonia solution to solution A in three separate additions every 20 minutes, continuing the reaction for 20 minutes after the final addition is complete, washing by centrifugation three times with ethanol to obtain nano zinc oxide coated silicon dioxide particles.

[0065] Furthermore, it should be explained that differential centrifugation is used to separate the precipitate from the supernatant, and by alternating between low-speed and high-speed centrifugation, various nano-zinc oxide coated silicon dioxide particles with different settling coefficients are precipitated, and nano-zinc oxide coated silicon dioxide particles that are too large or too small in size are removed from the product system.

[0066] Furthermore, the particle size of the obtained nano-zinc oxide coated silicon dioxide particles was measured to be 310 nm.

[0067] Furthermore, the method for producing the glutaraldehyde diluent includes the steps of dissolving 1.2 g of anhydrous sodium dihydrogen phosphate and 0.156 g of sodium hydroxide in water, stirring uniformly to obtain a 0.1 mol / L phosphate buffer, and then diluting the glutaraldehyde solution to a volume fraction of 5% with the 0.1 mol / L phosphate buffer to obtain the glutaraldehyde diluent.

[0068] Furthermore, the method for producing the zinc ammonia solution includes the steps of diluting ammonia water to a volume fraction of 2% with distilled water, preparing a 0.1 mol / L zinc chloride solution with deionized water using solid zinc chloride, placing an appropriate amount of the zinc chloride solution into a beaker, and slowly adding the diluted ammonia aqueous solution drop by drop while stirring until the precipitate disappears.

[0069] Furthermore, it should be explained that differential centrifugation is used to separate the precipitate from the supernatant, and by alternating between low-speed and high-speed centrifugation, various nanoparticles with different settling coefficients are precipitated separately, and fine particles that are too large or too small in size are removed from the product system.

[0070] The remaining details of this embodiment are the same as those of Embodiment 1.

[0071] Example 4 In this embodiment, the method for producing the modified epoxy resin is as follows: Step (1) involves dissolving a bisphenol A type epoxy resin in butyl acrylate, then adding polytetramethylene ether glycol 250, a polymerization inhibitor, and catalyst B, raising the temperature to 90°C, and reacting for 3 hours to obtain product C. The method includes step (2) lowering the temperature of the system to 95°C, slowly adding α-methacrylic acid dropwise to product C and continuing the reaction for 1 hour, and then continuing the reaction at the same temperature for 1 hour to obtain a modified epoxy resin.

[0072] Furthermore, the molar ratio of the polytetramethylene ether glycol 250 to the bisphenol A type epoxy resin is 0.4:1.

[0073] Furthermore, the molar ratio of the amount of α-methacrylic acid added to the bisphenol A type epoxy resin is 0.7:1.

[0074] Furthermore, the bisphenol A type epoxy resin used is a bisphenol A type epoxy resin with an epoxy value of 0.46 manufactured by Shanghai Luohe High-tech Materials Co., Ltd.

[0075] The remainder of this embodiment is the same as in Embodiment 3.

[0076] Example 5 In this embodiment, the polyurethane UV adhesive coating comprises 33 parts polyurethane prepolymer, 25 parts bismaleimide resin, 48 parts reactive diluent, and 5 parts photoinitiator.

[0077] Furthermore, the polyurethane prepolymer and bismaleimide resin are added to a reaction vessel at room temperature, followed by the addition of a reactive diluent and a photoinitiator, which are then mixed uniformly to obtain a polyurethane UV adhesive coating.

[0078] The remaining details of this embodiment are the same as those of Embodiment 4.

[0079] Example 6 In this embodiment, the polyurethane UV adhesive coating comprises 36 parts polyurethane prepolymer, 28 parts bismaleimide resin, 52 parts reactive diluent, and 5 parts photoinitiator.

[0080] Furthermore, the polyurethane prepolymer and bismaleimide resin are added to a reaction vessel at room temperature, followed by the addition of a reactive diluent and a photoinitiator, which are then mixed uniformly to obtain a polyurethane UV adhesive coating.

[0081] The remaining details of this embodiment are the same as those of Embodiment 4.

[0082] Comparative Example 1 The difference between this comparative example and Example 3 is that, in the method for producing the polyurethane prepolymer, a hydrogenated bisphenol A type epoxy resin is used instead of a modified epoxy resin.

[0083] Furthermore, the hydrogenated bisphenol A type epoxy resin used is a hydrogenated bisphenol A type epoxy resin with an epoxy value of 0.46 manufactured by Shanghai Luohe High-tech Materials Co., Ltd.

[0084] Comparative Example 2 The difference between this comparative example and Example 3 is that the nano-zinc oxide coated silicon dioxide particles are replaced with nano-silicon dioxide particles of the same particle size.

[0085] Performance testing The thickness of the textured layer produced in Examples 3 to 6 and Comparative Example 1 was controlled to 6 μm, and the thickness of the produced optical coating layer was controlled to 1.5 μm. Performance tests were then conducted on the produced TPU high-temperature films with optical color effects. The tensile strength of the TPU high-temperature films and the adhesion of the corresponding optical coating layers to the surface of the textured layer were tested under different conditions, and the test data are shown in Table 1 below.

[0086] JPEG2026521908000002.jpg58170

[0087] Of these, the tensile strength test will be conducted in accordance with GB / T 1040.3-2006, with a tensile speed of 100 mm / min.

[0088] The adhesion test was conducted in accordance with GB / T 9286-1998. The hydrolysis resistance test was conducted in accordance with QB / T 2888, by immersion in a 10% volume fraction sodium hydroxide solution at 30°C for 24 hours. In the boiling water resistance test, the treatment conditions for immersion in boiling water are 80°C for 8 hours. The degradation resistance test involved 1000 hours of treatment using QUV 340nm with a light intensity of 0.8 W / cm². 2 Let's assume that.

[0089] The above embodiments are preferred embodiments of the present invention, and the present invention can be realized in yet other forms. Any obvious substitutions, as long as they do not depart from the concept of the present invention, are all within the scope of protection of the present invention.

Claims

1. A TPU high-temperature film having an optical color effect, A TPU high-temperature film having an optical color effect, comprising an optical coating layer, a UV texture layer, and a TPU carrier layer arranged in order from top to bottom, wherein the texture layer is manufactured from a polyurethane UV adhesive coating.

2. The TPU high-temperature film having an optical color effect according to claim 1, characterized in that the texture layer is a lattice structure layer including a plurality of cylindrical lenses arranged in a continuous pattern, the upper ends of the cylindrical lenses are connected to an optical coating layer, and the lower ends of the cylindrical lenses are connected to a TPU carrier layer.

3. The TPU high-temperature film having an optical color effect according to claim 2, further comprising a hot-melt adhesive layer and a pattern layer provided at the upper end of the hot-melt adhesive layer, wherein the pattern layer is located at the lower end of the UV texture layer and comprises a first pattern layer, a highly transparent material layer and a second pattern layer provided in order from top to bottom, wherein the first pattern layer is divided into a plurality of spaced first pattern units, with a first gap provided between adjacent first pattern units, and adjacent first pattern units and the first gap are located at the lower end of a single cylindrical lens, and the second pattern layer is divided into a plurality of spaced second pattern units, with a second gap 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.

4. The TPU high-temperature film having an optical color effect according to claim 1, characterized in that the polyurethane UV adhesive coating comprises 30 to 36 parts polyurethane prepolymer, 22 to 28 parts bismaleimide resin, 45 to 55 parts reactive diluent, and 4 to 6 parts photoinitiator.

5. The method for manufacturing the polyurethane UV adhesive coating is as follows: The TPU high-temperature film having an optical color effect according to claim 4, characterized by comprising the steps of adding a polyurethane prepolymer and a bismaleimide resin to a reaction vessel at room temperature, then adding a reactive diluent and a photoinitiator and mixing them uniformly to obtain a polyurethane UV adhesive coating.

6. The TPU high-temperature film having an optical color effect according to claim 5, characterized in that the reactive diluent comprises a mixture of 1,6-hexanediol diacrylate and 4-acryloylmorpholine.

7. The method for producing the aforementioned polyurethane prepolymer is: Step (1) involves adding isophorone diisocyanate and catalyst A to a reaction vessel, raising the temperature to 60-80°C, adding poly(ethylene-co-1,2-butylene)diol dropwise, reacting for 2.5-3.5 hours, then cooling to 20-30°C, adding dihydroxypropionic acid, raising the temperature to 85-95°C and reacting for 1-2 hours, then cooling to room temperature, and finally slowly adding diethylamine dropwise to neutralize and obtain product A. The TPU high-temperature film having an optical color effect according to claim 4, comprising step (2), which involves adding a modified epoxy resin to product A under nitrogen protection, raising the temperature to 85-95°C, continuously stirring for 2.5-3.5 hours, and then lowering the temperature to obtain the polyurethane prepolymer.

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

9. The TPU high-temperature film having an optical color effect according to claim 7, characterized in that the catalyst A is at least one of dibutyltin dilaurate and stannous octanoate.

10. A method for manufacturing a TPU high-temperature film having the optical color effect described in any one of claims 1 to 9, Step (1) involves applying a polyurethane UV adhesive coating to the upper surface of the TPU carrier layer at room temperature to form a UV adhesive layer, Step (2) involves rolling the UV adhesive layer with an embossing roller at a pressure of 392 to 490 kPa to form an uneven textured structure on the upper surface of the UV adhesive layer, thereby obtaining a pre-textured layer. Step (3) involves curing the pretexture layer by irradiating it with ultraviolet light using a UV device to obtain a pre-TPU high-temperature film, A method for producing a TPU high-temperature film having an optical color effect, comprising the step (4) of depositing a nanometal thin film on the surface of a texture layer using electron beam physical deposition technology to form an optical coating layer and obtain a TPU high-temperature film having an optical color effect.

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