High-strength angle conversion pattern film and method for manufacturing the same

Abstract

The application relates to the technical field of color-changing film, and discloses a high-strength angle conversion pattern film and a preparation method thereof. In the application, color-changing dragon pearl pigments and carboxyl hyperbranched polymers are mixed in a high-speed mixer, then polyvinyl chloride resins, plasticizers, stabilizers and lubricants are added, the mixed materials are extruded into cast pieces through a screw extruder, and then bidirectional stretching, heat setting, cooling and winding are carried out through a bidirectional stretching machine to obtain the high-strength angle conversion pattern film. The hyperbranched polymer contains a large number of carboxyl groups, can form interaction with the surface of the color-changing dragon pearl pigments on the mica sheet base, can play the role of a dispersant, can improve the dispersibility of the pigments in the polyvinyl chloride, can reduce the influence of the pigments on the mechanical properties of the film, can make the film material have higher tensile strength and elongation at break, and the better the dispersibility of the color-changing dragon pearl pigments in the film matrix, the better the angle conversion effect of the color pattern of the film.

Description

Technical Field

[0001] This invention relates to the field of color-changing film technology, specifically to a high-intensity angle-changing patterned thin film and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) possesses high mechanical strength, excellent chemical resistance, and low cost, making it suitable for manufacturing films, pipes, and sheets. It has significant applications in daily necessities, building materials, and medical supplies. The preparation of high-performance PVC typically requires the addition of additives such as pigments, dispersants, and flame retardants. Chameleon pearlescent pigments are a unique type of pigment; when added to materials like films, they display different colors and patterns depending on the viewing angle or lighting, resulting in excellent aesthetics. The substrates for chameleon pearlescent pigments are usually mica flakes, glass flakes, or silica. These pigments exhibit poor dispersibility in PVC and other matrices, which can affect the material's mechanical properties.

[0003] Hyperbranched polymers are polymers with three-dimensional dendritic molecular chains. They can be used as processing aids, dispersants, flame retardants, etc., and are widely used in materials such as plastics, films, and coatings. This invention aims to use hyperbranched polymers and chameleon pearl pigments to endow polyvinyl chloride films with excellent mechanical properties and unique effects of changing color and pattern at different angles. Summary of the Invention

[0004] (a) Technical problems to be solved:

[0005] To address the shortcomings of existing technologies, this invention provides a high-strength angle-changing patterned film and its preparation method, thereby improving the mechanical properties of polyvinyl chloride patterned color-changing films.

[0006] (II) Technical solution: A high-strength angle-changing patterned film and its preparation method, wherein the high-strength angle-changing patterned film comprises 100 parts by weight of polyvinyl chloride resin, 1-3 parts by weight of chameleon pearl pigment, 2-6 parts by weight of carboxyl hyperbranched polymer, 20-30 parts by weight of plasticizer, 3-5 parts by weight of stabilizer, and 0.5-0.7 parts by weight of lubricant.

[0007] The preparation method of high-intensity angle-change patterned thin films is as follows:

[0008] (1) Add 2,4,6-tris(serine)triazine and triethylamine to N,N-dimethylformamide, stir, and then add diacyl chloride in an ice-water bath. After the reaction, dilute the solution with water, add hydrochloric acid solution dropwise, filter, wash with saturated sodium carbonate solution and ethanol, and dry to obtain a carboxyl hyperbranched polymer. The reaction formula is:

[0009] .

[0010] (2) Add chameleon pearl pigment and carboxylated hyperbranched polymer to a high-speed mixer for one mixing, then add polyvinyl chloride resin, plasticizer, stabilizer and lubricant for a second mixing, extrude the material through a screw extruder to form a cast sheet, and then perform biaxial stretching, heat setting, cooling and winding through a biaxial stretching machine to obtain a high-strength angle-changing pattern film.

[0011] Preferably, the reaction temperature in (1) is 20-40℃ and the reaction time is 18-24h.

[0012] Preferably, the ratio of 2,4,6-tris(serine)triazine, triethylamine, and diacyl chloride in (1) is 1 mol: (6-6.6) mol: (1.4-1.5) mol.

[0013] Preferably, the structural formula of the diacyl chloride in (1) is: , where a is 2-8.

[0014] Preferably, in (1), hydrochloric acid solution is added dropwise to adjust the pH to 3-4.

[0015] Preferably, the mass fraction of the hydrochloric acid solution in (1) is 10-37%.

[0016] Preferably, the plasticizer in (2) includes dioctyl phthalate and dibutyl phthalate.

[0017] Preferably, the lubricant in (2) includes calcium stearate, zinc stearate, polyethylene wax, and oleamide;

[0018] Preferably, the stabilizer in (2) includes a calcium-zinc stabilizer.

[0019] Preferably, the mixing time in (2) is 2-3 hours and the temperature is 30-50℃.

[0020] Preferably, the time for secondary mixing in (2) is 20-40 min and the temperature is 60-70℃.

[0021] Preferably, in (2), the temperature of each section of the screw extruder is 100-185℃ and the screw speed is 40-80r / min.

[0022] Preferably, in (2), the transverse stretching ratio is 3-4 times and the longitudinal stretching ratio is 3-4 times.

[0023] Preferably, (2) the temperature during heat setting is 90-110℃.

[0024] (III) Beneficial Technical Effects: This invention polymerizes 2,4,6-tris(serine)triazine and diacyl chloride to obtain a carboxyl hyperbranched polymer, which is then blended with chameleon pearl pigment, polyvinyl chloride resin, lubricant, etc. to form a film, resulting in a high-strength angle-changing patterned film. The carboxyl hyperbranched polymer contains a large number of imino groups, which can form hydrogen bonds with the chlorine atoms of polyvinyl chloride, giving the hyperbranched polymer good compatibility with polyvinyl chloride. The three-dimensional network molecular chains of the hyperbranched polymer form a physical cross-linking effect with the polyvinyl chloride molecular chains, which has a certain toughening effect and is beneficial to improving the tensile properties of polyvinyl chloride film.

[0025] The hyperbranched polymer of this invention contains a large number of carboxyl groups, which interact with the surface of the mica-based chameleon aurora pigment. This interaction enhances the dispersant effect, improves the pigment dispersion in polyvinyl chloride, reduces the influence of the pigment on the mechanical properties of the membrane, and gives the membrane material higher tensile strength and elongation at break. Furthermore, the better the dispersion of the chameleon aurora pigment in the membrane matrix, the better the color and pattern angle transformation effect of the membrane.

[0026] The hyperbranched polymer of this invention contains a large number of triazine char-forming and flame-retardant structures, which is beneficial to improving the char-forming and flame-retardant properties of polyvinyl chloride film materials and increasing the limiting oxygen index. Detailed Implementation

[0027] To enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention, and to make the above-mentioned objectives, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be further described below.

[0028] The following are product specifications: Polyvinyl chloride resin: Formosa Plastics S-70, Dongguan Tongchuangyuan Plastics Technology Co., Ltd.; Chameleon pearlescent pigment: DK9224BO, mica flake base, Xinxiang Deke Effect Pigment Co., Ltd.; Calcium-zinc stabilizer: Ruiying R-600, Qingyang Ruiying Plastic & Chemical Sales Co., Ltd.

[0029] Add 155 mmol of serine (CAS No. 302-84-1) and 310 mmol of sodium carbonate to 200 mL of water, stir in an ice bath, then add 100 mL of a solution containing 50 mmol of cyanuric chloride in 1,4-dioxane. Heat to 100 °C, stir, reflux for 10 h, and filter after cooling. Wash with ice water and dry to obtain 2,4,6-tris(serine)triazine, with the structural formula [insert structural formula here]. .

[0030] Example 1

[0031] (1) Add 0.1 mol of 2,4,6-tris(serine)triazine and 0.6 mol of triethylamine to 800 mL of N,N-dimethylformamide. After stirring, add 0.15 mol of succinyl chloride in an ice-water bath and stir at 25 °C for 24 h. Dilute the solution with water and adjust the pH to 3 by adding 15% hydrochloric acid solution. After filtration, wash with saturated sodium carbonate solution and ethanol, and dry to obtain carboxyl hyperbranched polymer.

[0032] (2) Add 60g of chameleon aluminous pigment and 40g of carboxylated hyperbranched polymer to a high-speed mixer and mix at 30°C for 3 hours. Then add 2kg of polyvinyl chloride resin, 600g of dioctyl phthalate, 80g of calcium zinc stabilizer, 10g of calcium stearate, and 4g of oleamide. Mix at 60°C for 40 minutes. Pass the material through a screw extruder with temperatures of 100°C, 150°C, 160°C, 175°C, 185°C, and 185°C in each section and a screw speed of 40r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 3 times and a longitudinal stretching ratio of 3 times. Heat set at 110°C, cool, and rewind to obtain a high-strength angle-changing patterned film.

[0033] Example 2

[0034] (1) Add 0.1 mol of 2,4,6-tris(serine)triazine and 0.6 mol of triethylamine to 700 mL of N,N-dimethylformamide. After stirring, add 0.14 mol of adipic acid chloride in an ice-water bath and stir at 40 °C for 18 h. Dilute the solution with water and adjust the pH to 4 by adding 10% hydrochloric acid solution. After filtration, wash with saturated sodium carbonate solution and ethanol, and dry to obtain carboxyl hyperbranched polymer.

[0035] (2) Add 20g of chameleon pearl pigment and 80g of carboxylated hyperbranched polymer to a high-speed mixer and mix at 30°C for 3 hours. Then add 2kg of polyvinyl chloride resin, 400g of dioctyl phthalate, 100g of calcium zinc stabilizer, 10g of calcium stearate and 3g of polyethylene wax and mix at 60°C for 30 minutes. Pass the material through a screw extruder with temperatures of 100°C, 150°C, 160°C, 175°C, 185°C and 185°C in each section and a screw speed of 80r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 4 times and a longitudinal stretching ratio of 4 times. Heat set at 90°C, cool and rewind to obtain a high-strength angle-changing patterned film.

[0036] Example 3

[0037] (1) Add 0.1 mol of 2,4,6-tris(serine)triazine and 0.66 mol of triethylamine to 800 mL of N,N-dimethylformamide. After stirring, add 0.15 mol of malonyl chloride in an ice-water bath and stir at 20 °C for 24 h. Dilute the solution with water and adjust the pH to 3 by adding 37% hydrochloric acid solution. After filtration, wash with saturated sodium carbonate solution and ethanol, and dry to obtain carboxyl hyperbranched polymer.

[0038] (2) Add 40g of chameleon pearl pigment and 120g of carboxylated hyperbranched polymer to a high-speed mixer and mix at 50°C for 2 hours. Then add 2kg of polyvinyl chloride resin, 600g of dioctyl phthalate, 60g of calcium zinc stabilizer, 7g of zinc stearate, and 3g of polyethylene wax. Mix at 70°C for 20 minutes. Pass the material through a screw extruder with temperatures of 100°C, 150°C, 160°C, 175°C, 185°C, and 185°C in each section and a screw speed of 50r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 3 times and a longitudinal stretching ratio of 3 times. Heat set at 110°C, cool, and rewind to obtain a high-strength angle-changing patterned film.

[0039] Comparative Example 1 differs from Example 1 in that it does not contain a carboxyl hyperbranched polymer.

[0040] (1) Add 60g of chameleon aluminous pigment to a high-speed mixer and mix at 30℃ for 3h. Then add 2kg of polyvinyl chloride resin, 600g of dioctyl phthalate, 80g of calcium zinc stabilizer, 10g of calcium stearate, and 4g of oleamide. Mix at 60℃ for 40min. Pass the material through a screw extruder with temperatures of 100℃, 150℃, 160℃, 175℃, 185℃, and 185℃ in each section and a screw speed of 40r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 3 times and a longitudinal stretching ratio of 3 times. Heat set at 110℃, cool, and rewind to obtain an angle-changing patterned film.

[0041] Comparative Example 2 differs from Example 1 in that sodium polyacrylate (Dow Acusol 445N) is used instead of the carboxyl hyperbranched polymer.

[0042] (1) Add 60g of chameleon pearl pigment and 40g of sodium polyacrylate to a high-speed mixer and mix at 30℃ for 3h. Then add 2kg of polyvinyl chloride resin, 600g of dioctyl phthalate, 80g of calcium zinc stabilizer, 10g of calcium stearate and 4g of oleamide and mix at 60℃ for 40min. Pass the material through a screw extruder with temperatures of 100℃, 150℃, 160℃, 175℃, 185℃ and 185℃ in each section and a screw speed of 40r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 3 times and a longitudinal stretching ratio of 3 times. Heat set at 110℃, cool and rewind to obtain an angle-changing patterned film.

[0043] Comparative Example 3 differs from Example 1 in that it uses trimethylolpropane instead of 2,4,6-tris(serine)triazine.

[0044] (1) Add 0.1 mol of trimethylolpropane and 0.6 mol of triethylamine to 800 mL of N,N-dimethylformamide, stir, add 0.15 mol of succinyl chloride in an ice-water bath, stir and react at 25 °C for 24 h, add water to dilute the solution, add 15% hydrochloric acid solution to adjust the pH to 3, filter, wash with saturated sodium carbonate solution and ethanol, dry, and obtain hyperbranched polymer.

[0045] (2) Add 60g of chameleon aluminous pigment and 40g of hyperbranched polymer to a high-speed mixer and mix at 30℃ for 3h. Then add 2kg of polyvinyl chloride resin, 600g of dioctyl phthalate, 80g of calcium zinc stabilizer, 10g of calcium stearate and 4g of oleamide and mix at 60℃ for 40min. Pass the material through a screw extruder with temperatures of 100℃, 150℃, 160℃, 175℃, 185℃ and 185℃ in each section and a screw speed of 40r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 3 times and a longitudinal stretching ratio of 3 times. Heat set at 110℃, cool and rewind to obtain an angle-changing patterned film.

[0046] Comparative Example 4: The main difference between this comparative example and Example 1 is that 2,2-dimethylolpropionic acid is used instead of 2,4,6-tris(serine)triazine.

[0047] (1) Add 0.15 mol of 2,2-dihydroxymethylpropionic acid and 0.6 mol of triethylamine to 800 mL of N,N-dimethylformamide, stir, and then add 0.15 mol of succinyl chloride in an ice-water bath. Stir the reaction at 25 °C for 24 h. Add water to dilute the solution, add 15% hydrochloric acid solution to adjust the pH to 3, filter, wash with saturated sodium carbonate solution and ethanol, and dry to obtain carboxyl polymer.

[0048] (2) Add 60g of chameleon pearl pigment and 40g of carboxyl polymer to a high-speed mixer and mix at 30°C for 3 hours. Then add 2kg of polyvinyl chloride resin, 600g of dioctyl phthalate, 80g of calcium zinc stabilizer, 10g of calcium stearate, and 4g of oleamide. Mix at 60°C for 40 minutes. Pass the material through a screw extruder with temperatures of 100°C, 150°C, 160°C, 175°C, 185°C, and 185°C in each section and a screw speed of 40r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 3 times and a longitudinal stretching ratio of 3 times. Heat set at 110°C, cool, and rewind to obtain an angle-changing patterned film.

[0049] Comparative Example 5, 2,4,6-tris(ethanolamine)triazine was used instead of 2,4,6-tris(serine)triazine.

[0050] (1) Add 150 mL of water, 76 mmol of cyanuric chloride, and 239.2 mmol of sodium hydroxide to 450 mL of 1,4-dioxane. After stirring, add 79.7 mmol of ethanolamine dropwise. After stirring, heat to 50 °C, then add another 159.5 mmol of ethanolamine and heat to 80 °C. Reflux for 7 h, cool, and filter. Recrystallize the product in ethanol to obtain 2,4,6-tris(ethanolamine)triazine, with the structural formula: .

[0051] (2) Add 0.1 mol of 2,4,6-tris(ethanolamine)triazine and 0.6 mol of triethylamine to 800 mL of N,N-dimethylformamide. After stirring, add 0.15 mol of succinyl chloride in an ice-water bath and stir at 25 °C for 24 h. Dilute the solution with water and adjust the pH to 3 by adding 15% hydrochloric acid solution. After filtration, wash with saturated sodium carbonate solution and ethanol, and dry to obtain hyperbranched polymer.

[0052] (3) Add 60g of chameleon aluminous pigment and 40g of hyperbranched polymer to a high-speed mixer and mix at 30℃ for 3h. Then add 2kg of polyvinyl chloride resin, 600g of dioctyl phthalate, 80g of calcium zinc stabilizer, 10g of calcium stearate and 4g of oleamide and mix at 60℃ for 40min. Pass the material through a screw extruder with temperatures of 100℃, 150℃, 160℃, 175℃, 185℃ and 185℃ in each section and a screw speed of 40r / min to extrude a cast sheet. Then, perform biaxial stretching through a biaxial stretching machine with a transverse stretching ratio of 3 times and a longitudinal stretching ratio of 3 times. Heat set at 110℃, cool and rewind to obtain an angle-changing patterned film.

[0053] The tensile properties of the film were tested according to GB / T 1040.3-2006. The flame retardancy was tested according to GB / T 2406.1-2008.

[0054] Table 1 Properties of the thin film

[0055] Transverse tensile strength (MPa) Transverse elongation at break (%) Limiting oxygen index (%) Example 1 26.2 338.4 25.0 Example 2 32.3 285.8 25.9 Example 3 28.0 423.5 26.7 Comparative Example 1 22.5 275.3 23.8 Comparative Example 2 23.6 287.1 23.4 Comparative Example 3 22.8 308.4 23.6 Comparative Example 4 23.9 285.1 23.5 Comparative Example 5 24.7 315.9 25.1

[0056] The polyvinyl chloride membrane in Comparative Example 1 has low tensile strength and elongation at break, mainly because the added mica-based chameleon atomizing pigment has poor compatibility with polyvinyl chloride and tends to agglomerate in the membrane matrix, which affects the mechanical properties of the membrane material.

[0057] Examples 1-3 incorporated a carboxyl-based hyperbranched polymer containing a large number of imino groups. These imino groups can form hydrogen bonds with the chlorine atoms of polyvinyl chloride (PVC), resulting in good compatibility between the hyperbranched polymer and PVC. The three-dimensional network molecular chains of the hyperbranched polymer physically cross-link with the PVC molecular chains, providing a toughening effect and improving the tensile properties of the PVC membrane. Simultaneously, the high carboxyl group content of the hyperbranched polymer interacts with the surface of the mica-based chameleon aluminosilicate pigment, enhancing the dispersibility of the pigment within the PVC membrane and reducing its impact on the membrane's mechanical properties. This results in higher tensile strength and elongation at break in the membrane material. Furthermore, better dispersibility of the chameleon aluminosilicate pigment leads to better angular changes in the membrane's color pattern. The hyperbranched polymer also contains a triazine-based char-forming flame-retardant structure, which improves the char-forming and flame-retardant properties of the PVC membrane material, increasing the limiting oxygen index.

[0058] Comparative Example 2's sodium polyacrylate does not have a hyperbranched structure or a triazine structure, resulting in poor toughening and flame retardant effects on polyvinyl chloride, and a low limiting oxygen index in the tensile properties of the polyvinyl chloride film.

[0059] Comparative Example 3: Trimethylolpropane and its prepared hyperbranched polymer do not contain imino, carboxyl, or triazine groups, resulting in poor compatibility with polyvinyl chloride and an inability to disperse mica-based chameleon aurora pigments. This leads to low tensile properties and a low limiting oxygen index in the membrane material.

[0060] The carboxyl polymer in Comparative Example 4 lacks hyperbranched structure and triazine groups, resulting in poor toughening and flame retardant effects on polyvinyl chloride.

[0061] The 2,4,6-tris(ethanolamine)triazine and hyperbranched polymer in Comparative Example 5 do not contain carboxyl groups and cannot disperse the mica-based chameleon atomizing pigments, resulting in low tensile properties of the film material.

[0062] The above description describes specific embodiments of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be covered within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims.

Claims

1. A high-strength angle-changing patterned thin film, characterized in that, The high-strength angle-changing patterned film comprises 100 parts by weight of polyvinyl chloride resin, 1-3 parts by weight of chameleon aluminous pigment, 2-6 parts by weight of carboxyl hyperbranched polymer, 20-30 parts by weight of plasticizer, 3-5 parts by weight of stabilizer, and 0.5-0.7 parts by weight of lubricant. The preparation method of the carboxyl hyperbranched polymer is as follows: 2,4,6-tris(serine)triazine and triethylamine are added to N,N-dimethylformamide, and after stirring, diacyl chloride is added in an ice-water bath. The mixture is stirred and reacted at 20-40℃ for 18-24 hours. Water is added to dilute the solution, and hydrochloric acid solution is added dropwise to adjust the pH to 3-4. The mixture is filtered, washed, and dried to obtain the carboxyl hyperbranched polymer. The ratio of the 2,4,6-tris(serine)triazine, triethylamine, and diacyl chloride is 1 mol: (6-6.6) mol: (1.4-1.5) mol; The structural formula of the diacyl chloride is: , where a is 2-8.

2. The high-strength angle-changing patterned thin film according to claim 1, characterized in that, The plasticizers include dioctyl phthalate and dibutyl phthalate.

3. The high-strength angle-changing patterned thin film according to claim 1, characterized in that, The lubricant includes calcium stearate, zinc stearate, polyethylene wax, and oleamide.

4. The high-intensity angle-changing patterned thin film according to claim 1, characterized in that, The stabilizer includes a calcium-zinc stabilizer.

5. A method for preparing a high-intensity angle-changing patterned thin film as described in any one of claims 1-4, characterized in that, The preparation method is as follows: Chameleon aluminous pigment and carboxylated hyperbranched polymer are added to a high-speed mixer for primary mixing, followed by the addition of polyvinyl chloride resin, plasticizer, stabilizer, and lubricant for secondary mixing. The material is then extruded into a cast sheet using a screw extruder, followed by biaxial stretching, heat setting, cooling, and winding using a biaxial stretching machine to obtain a high-strength angle-changing patterned film.

6. The method for preparing a high-intensity angle-changing patterned thin film according to claim 5, characterized in that, The first mixing time is 2-3 hours, and the temperature is 30-50℃; the second mixing time is 20-40 minutes, and the temperature is 60-70℃; the temperature of each section of the screw extruder is 100-185℃, and the screw speed is 40-80 r / min.

7. The method for preparing a high-intensity angle-changing patterned thin film according to claim 5, characterized in that, The transverse stretching ratio during biaxial stretching is 3-4 times, and the longitudinal stretching ratio is 3-4 times; the heat setting temperature is 90-110℃.

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