A weather-resistant PVC decorative film

Abstract

The present invention relates to the technical field of decorative films, and relates to a weather-resistant PVC decorative film, comprising the following components in parts by weight: 1-5 parts by weight of a toughening agent, 10-20 parts by weight of a polyvinyl chloride resin, and Chimassorb 0.1-0.5 parts by weight of 944 hindered amine light stabilizer, 0.2-0.5 parts by weight of calcium zinc composite stabilizer, 0.3-0.7 parts by weight of 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.6-0.8 parts by weight of alizarin red cerium complex antioxidant, 0.1-0.3 parts by weight of talcum powder filler, and 0.2-0.4 parts by weight of carbon black pigment; wherein the toughening agent is obtained by mixing hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:1.5-2.0:0.5-1.0; the alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III), the toughening agent is used, the volume-increasing and toughening properties of ethoxyl are utilized to improve the compatibility of the vegetable oil toughening agent with the PVC material, the amino group and carboxyl group of L-serine can form hydrogen bonds and the ability to coordinate with metals, thereby providing an antioxidant effect and a bonding force between the components.

Description

Technical Field

[0001] The invention relates to the technical field of decorative films, in particular to a weather-resistant PVC decorative film. Background Art

[0002] PVC decorative film is a new type of decorative material made of polyvinyl chloride as the main raw material through a series of production processes (such as printing, lamination, embossing, etc.). It can be used for a long time under extreme weather conditions without obvious aging or performance degradation. This decorative film can be compounded with a variety of substrates to make multi-purpose decorative materials with rich textures and colors. It can simulate the effects of natural wood, stone and other materials, which not only increases the beauty of the items, but also provides more design freedom. In addition to beautifying the appearance, PVC decorative film also provides good protection. It is water-resistant and can effectively prevent moisture from penetrating into the interior of the substrate and causing deformation or corrosion of the substrate. Therefore, it is widely used in many fields.

[0003] Toughener is an additive used to increase the flexibility and plasticity of PVC, making the originally hard and brittle PVC soft and easy to process. Traditional phthalate tougheners are gradually replaced by natural plant oil tougheners due to their toxicity. However, the non-polar ratio in the plant oil-based toughener structure is too high, resulting in poor compatibility with PVC materials. In view of this, a weather-resistant PVC decorative film is provided. Summary of the invention

[0004] The object of the present invention is to provide a weather-resistant PVC decorative film to solve the problem of poor stability of active components in the preparation process of blueberry puree proposed in the above background technology.

[0005] To achieve the above object, the present invention provides a weather-resistant PVC decorative film, comprising the following components in parts by weight: 1-5 parts by weight of a toughening agent, 10-20 parts by weight of a polyvinyl chloride resin, 0.1-0.5 parts by weight of a Chimassorb 944 hindered amine light stabilizer, 0.2-0.5 parts by weight of a calcium zinc toughening agent, 0.3-0.7 parts by weight of a 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.6-0.8 parts by weight of an alizarin red cerium complex antioxidant, 0.1-0.3 parts by weight of a talc filler, and 0.2-0.4 parts by weight of a carbon black pigment;

[0006] The toughening agent is obtained by mixing hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:1.5-2.0:0.5-1.0;

[0007] Alizarin red cerium complex antioxidant is a complex formed by Alizarin Red S and cerium salt (III).

[0008] As a further improvement of the technical solution, the specific preparation method of the toughening agent is as follows:

[0009] Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer. Add hydrogenated dimer acid and tetraethylene glycol methyl ether in turn, continue stirring to fully mix, then add p-toluenesulfonic acid, adjust the heated magnetic stirrer to make the reaction mixture reach 110-120°C, react for 3-4 hours, add L-serine, continue to react for 4-5 hours, and when the reaction is complete, add Na 2 CO 3 The solution is adjusted to neutral with the remaining liquid, and then washed with distilled water, and unreacted substances are removed by reduced pressure distillation to obtain a toughening agent.

[0010] Hydrogenated dimer acid is derived from vegetable oil and has outstanding advantages such as non-toxicity, renewable, and biodegradable. However, the non-polar ratio in the structure of vegetable oil-based toughening agents is relatively high, resulting in poor compatibility with PVC materials. The ethoxy group on tetraethylene glycol monomethyl ether has the ability to increase capacity and toughness. Introducing it into hydrogenated dimer acid can effectively improve the compatibility of vegetable oil toughening agents with PVC materials, thereby improving the performance of PVC materials in terms of tensile strength, migration stability, solvent extraction stability, and thermal stability, thereby effectively improving the weather resistance of PVC materials. However, since toughening agents are usually oily liquids, they are more likely to move from the inside of PVC to the surface of the material under the action of water. This migration will cause the surface of the material to become greasy or sticky, and over time, the loss of toughening agents will cause the material to gradually harden and lose its original flexibility. Therefore, the move to hydrogenated dimer acid is more likely to cause the material to become greasy or sticky. L-serine containing amino and carboxyl groups is introduced into the polyacid. On the one hand, the amino and carboxyl groups can also form hydrogen bonds with other components in the PVC material, further enhancing the binding force between the toughening agent and the components, thereby alleviating the migration of the toughening agent. On the other hand, since some metal ions (such as copper and iron) can catalyze the generation of free radicals, thereby accelerating the oxidation reaction, the amino group on L-serine can form a stable complex with these metal ions, preventing their catalytic activity and passivating the metal ions, thereby achieving an antioxidant effect. At the same time, since antioxidants are usually small molecules, their diffusion coefficients in PVC are relatively large, and they are more likely to move between PVC chain segments, resulting in migration, while the carboxyl group on L-serine can coordinate with the cerium element, thereby improving the binding force of the antioxidant in the PVC material, thereby improving the overall performance of the PVC material.

[0011] The cerium ion in the Alizarin Red Cerium Complex Antioxidant can be used as a free radical scavenger because there is a conversion mechanism between trivalent cerium and tetravalent cerium in an acidic medium, and the presence of Alizarin Red S is to increase the molecular weight of the antioxidant, thereby effectively solving the migration problem of the antioxidant.

[0012] As a further improvement of the technical solution, the mass ratio of the hydrogenated dimer acid to N,N-dimethylformamide is 1:5-8.

[0013] As a further improvement of the technical solution, the mass fraction of p-toluenesulfonic acid is 0.5-1%.

[0014] As a further improvement of the technical solution, the mass ratio of p-toluenesulfonic acid to hydrogenated dimer acid is 0.12-0.17:1.

[0015] As a further improvement of the technical solution, when the reaction is finished, the acid value is less than or equal to 1 mgKOH / g.

[0016] As a further improvement of this technical solution, the Na 2 CO 3 The mass fraction of the solution is 5-10%.

[0017] As a further improvement of the technical solution, the specific preparation method of the weather-resistant PVC decorative film is as follows:

[0018] Add toughening agent, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment into a high-speed mixer, set the mixing time to 5-10 minutes and the rotation speed to 800-1200rpm to fully and evenly mix the raw materials, send the mixed materials into a twin-screw extruder for plasticization, set the temperature of each section of the extruder, extrude the plasticized material into a film through a shaped mold, pass the extruded film through a set of cooling rollers, and set the temperature to about room temperature to ensure that the film surface is smooth and the size is stable, and roll up the cooled and shaped film for acceptance to obtain a weather-resistant PVC decorative film.

[0019] As a further improvement of the technical solution, the temperature of the feeding zone of the extruder is 150-160°C, the temperature of the plasticizing zone is 170-180°C, and the temperature of the extrusion zone is 180-190°C.

[0020] As a further improvement of the technical solution, the screw speed of the extruder is 30-50rpm.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] In the weather-resistant PVC decorative film, tetraethylene glycol monomethyl ether and L-serine are introduced into hydrogenated dimer acid to prepare a toughening agent, and the compatibility of the plant oil toughening agent and the PVC material is improved by utilizing the volume-increasing and toughening properties of the ethoxy group, thereby improving the weather resistance of the PVC material. The amino group and carboxyl group of the L-serine can form hydrogen bonds and coordinate with metals, which, on the one hand, can passivate metals that can catalyze oxidation reactions and provide an antioxidant effect, and on the other hand, can form hydrogen bonds with other components and coordinate with the antioxidant, which not only improves the binding force between the components but also overcomes the problem that the antioxidant is prone to migration. DETAILED DESCRIPTION

[0023] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0024] Example 1: In this example, the specific preparation method of the weather-resistant PVC decorative film is as follows:

[0025] Prepare the following components: 5 parts by weight of toughening agent, 20 parts by weight of polyvinyl chloride resin, 0.5 parts by weight of Chimassorb 944 hindered amine light stabilizer, 0.5 parts by weight of calcium zinc composite stabilizer, 0.7 parts by weight of 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.8 parts by weight of alizarin red cerium complex antioxidant, 0.3 parts by weight of talc filler, and 0.4 parts by weight of carbon black pigment;

[0026] The toughening agent is a mixture of hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:1.5:0.5; the alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III); the mass ratio of hydrogenated dimer acid to N,N-dimethylformamide is 1:8; the mass ratio of p-toluenesulfonic acid to hydrogenated dimer acid is 0.17:1;

[0027] Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer, add hydrogenated dimer acid and tetraethylene glycol methyl ether in sequence, continue stirring to fully mix, then add 0.7% p-toluenesulfonic acid by mass, adjust the heated magnetic stirrer to make the reaction mixture reach 120° C., react for 4 hours, add L-serine, and continue to react for 5 hours. At the end of the reaction, the acid value is less than or equal to 1 mgKOH / g, adjust the remaining liquid to neutral with a Na2CO3 solution with a mass fraction of 8%, and then wash with distilled water, and remove the unreacted substances by reduced pressure distillation to obtain a toughening agent;

[0028] Toughener, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment are added to a high-speed mixer, and the mixing time is set to 10 minutes and the speed is 1000rpm to fully mix the raw materials. The mixed materials are sent to a twin-screw extruder for plasticization. The temperature of each section of the extruder is set to 150°C in the feeding zone, 170°C in the plasticizing zone, and 190°C in the extrusion zone. The plasticized material is extruded into a film through a shaped mold. The extruded film passes through a group of cooling rollers with a temperature set at about room temperature to ensure that the film surface is smooth and the size is stable. The film is rolled up and inspected after cooling and shaping to obtain a weather-resistant PVC decorative film.

[0029] Example 2: In this example, the specific preparation method of the weather-resistant PVC decorative film is as follows:

[0030] Prepare the following components: 5 parts by weight of toughening agent, 20 parts by weight of polyvinyl chloride resin, 0.5 parts by weight of Chimassorb 944 hindered amine light stabilizer, 0.5 parts by weight of calcium zinc composite stabilizer, 0.7 parts by weight of 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.8 parts by weight of alizarin red cerium complex antioxidant, 0.3 parts by weight of talc filler, and 0.4 parts by weight of carbon black pigment;

[0031] The toughening agent is a mixture of hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:1.7:0.8; the alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III); the mass ratio of hydrogenated dimer acid to N,N-dimethylformamide is 1:8; the mass ratio of p-toluenesulfonic acid to hydrogenated dimer acid is 0.17:1;

[0032] Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer, add hydrogenated dimer acid and tetraethylene glycol methyl ether in sequence, continue stirring to fully mix, then add 0.7% p-toluenesulfonic acid by mass, adjust the heated magnetic stirrer to make the reaction mixture reach 120° C., react for 4 hours, add L-serine, and continue to react for 5 hours. At the end of the reaction, the acid value is less than or equal to 1 mgKOH / g, adjust the remaining liquid to neutral with a Na2CO3 solution with a mass fraction of 8%, and then wash with distilled water, and remove the unreacted substances by reduced pressure distillation to obtain a toughening agent;

[0033] Toughener, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment are added to a high-speed mixer, and the mixing time is set to 10 minutes and the speed is 1000rpm to fully mix the raw materials. The mixed materials are sent to a twin-screw extruder for plasticization. The temperature of each section of the extruder is set to 150°C in the feeding zone, 170°C in the plasticizing zone, and 190°C in the extrusion zone. The plasticized material is extruded into a film through a shaped mold. The extruded film passes through a group of cooling rollers with a temperature set at about room temperature to ensure that the film surface is smooth and the size is stable. The film is rolled up and inspected after cooling and shaping to obtain a weather-resistant PVC decorative film.

[0034] Example 3: In this example, the specific preparation method of the weather-resistant PVC decorative film is as follows:

[0035] Prepare the following components: 5 parts by weight of toughening agent, 20 parts by weight of polyvinyl chloride resin, 0.5 parts by weight of Chimassorb 944 hindered amine light stabilizer, 0.5 parts by weight of calcium zinc composite stabilizer, 0.7 parts by weight of 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.8 parts by weight of alizarin red cerium complex antioxidant, 0.3 parts by weight of talc filler, and 0.4 parts by weight of carbon black pigment;

[0036] The toughening agent is a mixture of hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:2.0:1.0; the alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III); the mass ratio of hydrogenated dimer acid to N,N-dimethylformamide is 1:8; the mass ratio of p-toluenesulfonic acid to hydrogenated dimer acid is 0.17:1;

[0037] Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer, add hydrogenated dimer acid and tetraethylene glycol methyl ether in sequence, continue stirring to fully mix, then add 0.7% p-toluenesulfonic acid by mass, adjust the heated magnetic stirrer to make the reaction mixture reach 120° C., react for 4 hours, add L-serine, and continue to react for 5 hours. At the end of the reaction, the acid value is less than or equal to 1 mgKOH / g, adjust the remaining liquid to neutral with a Na2CO3 solution with a mass fraction of 8%, and then wash with distilled water, and remove the unreacted substances by reduced pressure distillation to obtain a toughening agent;

[0038] Toughener, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment are added to a high-speed mixer, and the mixing time is set to 10 minutes and the speed is 1000rpm to fully mix the raw materials. The mixed materials are sent to a twin-screw extruder for plasticization. The temperature of each section of the extruder is set to 150°C in the feeding zone, 170°C in the plasticizing zone, and 190°C in the extrusion zone. The plasticized material is extruded into a film through a shaped mold. The extruded film passes through a group of cooling rollers with a temperature set at about room temperature to ensure that the film surface is smooth and the size is stable. The film is rolled up and inspected after cooling and shaping to obtain a weather-resistant PVC decorative film.

[0039] Example 4: In this example, the specific preparation method of the weather-resistant PVC decorative film is as follows:

[0040] Prepare the following components: 5 parts by weight of toughening agent, 10 parts by weight of polyvinyl chloride resin, 0.1 parts by weight of Chimassorb 944 hindered amine light stabilizer, 0.2 parts by weight of calcium zinc composite stabilizer, 0.3 parts by weight of 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.6 parts by weight of alizarin red cerium complex antioxidant, 0.1 parts by weight of talc filler, and 0.2 parts by weight of carbon black pigment;

[0041] The toughening agent is a mixture of hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:2.0:1.0; the alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III); the mass ratio of hydrogenated dimer acid to N,N-dimethylformamide is 1:5; the mass ratio of p-toluenesulfonic acid to hydrogenated dimer acid is 0.12:1;

[0042] Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer, add hydrogenated dimer acid and tetraethylene glycol methyl ether in sequence, continue stirring to fully mix, then add 0.7% p-toluenesulfonic acid by mass, adjust the heated magnetic stirrer to make the reaction mixture reach 120° C., react for 4 hours, add L-serine, and continue to react for 5 hours. At the end of the reaction, the acid value is less than or equal to 1 mgKOH / g, adjust the remaining liquid to neutral with a Na2CO3 solution with a mass fraction of 8%, and then wash with distilled water, and remove the unreacted substances by reduced pressure distillation to obtain a toughening agent;

[0043] Toughener, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment are added to a high-speed mixer, and the mixing time is set to 10 minutes and the speed is 1000rpm to fully mix the raw materials. The mixed materials are sent to a twin-screw extruder for plasticization. The temperature of each section of the extruder is set to 150°C in the feeding zone, 170°C in the plasticizing zone, and 190°C in the extrusion zone. The plasticized material is extruded into a film through a shaped mold. The extruded film passes through a group of cooling rollers with a temperature set at about room temperature to ensure that the film surface is smooth and the size is stable. The film is rolled up and inspected after cooling and shaping to obtain a weather-resistant PVC decorative film.

[0044] Example 5: In this example, the specific preparation method of the weather-resistant PVC decorative film is as follows:

[0045] Prepare the following components: 3 parts by weight of toughening agent, 20 parts by weight of polyvinyl chloride resin, 0.5 parts by weight of Chimassorb 944 hindered amine light stabilizer, 0.5 parts by weight of calcium zinc composite stabilizer, 0.7 parts by weight of 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.8 parts by weight of alizarin red cerium complex antioxidant, 0.3 parts by weight of talc filler, and 0.4 parts by weight of carbon black pigment;

[0046] The toughening agent is a mixture of hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:2.0:1.0; the alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III); the mass ratio of hydrogenated dimer acid to N,N-dimethylformamide is 1:8; the mass ratio of p-toluenesulfonic acid to hydrogenated dimer acid is 0.17:1;

[0047] Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer, add hydrogenated dimer acid and tetraethylene glycol methyl ether in sequence, continue stirring to fully mix, then add 0.7% p-toluenesulfonic acid by mass, adjust the heated magnetic stirrer to make the reaction mixture reach 120° C., react for 4 hours, add L-serine, and continue to react for 5 hours. At the end of the reaction, the acid value is less than or equal to 1 mgKOH / g, adjust the remaining liquid to neutral with a Na2CO3 solution with a mass fraction of 8%, and then wash with distilled water, and remove the unreacted substances by reduced pressure distillation to obtain a toughening agent;

[0048] Toughener, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment are added to a high-speed mixer, and the mixing time is set to 10 minutes and the speed is 1000rpm to fully mix the raw materials. The mixed materials are sent to a twin-screw extruder for plasticization. The temperature of each section of the extruder is set to 150°C in the feeding zone, 170°C in the plasticizing zone, and 190°C in the extrusion zone. The plasticized material is extruded into a film through a shaped mold. The extruded film passes through a group of cooling rollers with a temperature set at about room temperature to ensure that the film surface is smooth and the size is stable. The film is rolled up and inspected after cooling and shaping to obtain a weather-resistant PVC decorative film.

[0049] Example 6: In this example, the specific preparation method of the weather-resistant PVC decorative film is as follows:

[0050] Prepare the following components: 1 part by weight of toughening agent, 20 parts by weight of polyvinyl chloride resin, 0.5 parts by weight of Chimassorb 944 hindered amine light stabilizer, 0.5 parts by weight of calcium zinc composite stabilizer, 0.7 parts by weight of 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.8 parts by weight of alizarin red cerium complex antioxidant, 0.3 parts by weight of talc filler, and 0.4 parts by weight of carbon black pigment;

[0051] The toughening agent is a mixture of hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine in a mass ratio of 1:2.0:1.0; the alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III); the mass ratio of hydrogenated dimer acid to N,N-dimethylformamide is 1:8; the mass ratio of p-toluenesulfonic acid to hydrogenated dimer acid is 0.17:1;

[0052] Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer, add hydrogenated dimer acid and tetraethylene glycol methyl ether in sequence, continue stirring to fully mix, then add 0.7% p-toluenesulfonic acid by mass, adjust the heated magnetic stirrer to make the reaction mixture reach 120° C., react for 4 hours, add L-serine, and continue to react for 5 hours. At the end of the reaction, the acid value is less than or equal to 1 mgKOH / g, adjust the remaining liquid to neutral with a Na2CO3 solution with a mass fraction of 8%, and then wash with distilled water, and remove the unreacted substances by reduced pressure distillation to obtain a toughening agent;

[0053] Toughener, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment are added to a high-speed mixer, and the mixing time is set to 10 minutes and the speed is 1000rpm to fully mix the raw materials. The mixed materials are sent to a twin-screw extruder for plasticization. The temperature of each section of the extruder is set to 150°C in the feeding zone, 170°C in the plasticizing zone, and 190°C in the extrusion zone. The plasticized material is extruded into a film through a shaped mold. The extruded film passes through a group of cooling rollers with a temperature set at about room temperature to ensure that the film surface is smooth and the size is stable. The film is rolled up and inspected after cooling and shaping to obtain a weather-resistant PVC decorative film.

[0054] Comparative Example 1: The method of Example 3 was adopted, and the amount of toughening agent added was 0.01 parts by weight.

[0055] Comparative Example 2: The method of Example 3 was adopted, and the toughening agent was prepared only from hydrogenated dimer acid, without modification by tetraethylene glycol methyl ether and L-serine.

[0056] Comparative Example 3: The method of Example 3 was adopted, and the toughening agent was prepared from hydrogenated dimer acid and tetraethylene glycol methyl ether, and L-serine was not used for modification.

[0057] The present invention prepares a weather-resistant PVC decorative film, which has good weather resistance, tensile strength and migration resistance in the application of the decorative film technology field. Specific tests are shown in the following table:

[0058] The tensile properties test was carried out using a universal testing machine (MTS E44.304, USA). The tensile specimens were cut into dumbbell-shaped specimens from PVC sheets according to GB / T 1040.3-2006 Determination of tensile properties of plastics Part 3: Test conditions for films and sheets. The tensile rate was set to 10 mm / min, and 5 specimens were tested for each sample.

[0059] The migration resistance test was carried out according to the standard of GB / T 3830-2008 Soft Polyvinyl Chloride Calendered Film and Sheet. The sample of 20mm (length) × 20mm (width) × 1mm (thickness) was immersed in n-hexane solution at a temperature of (23±2)℃ and a humidity of (50±10)%. After being placed for 24 hours, it was taken out and washed with a clean solvent. After being dried at 50℃ for 6 hours, the mass loss rate was obtained based on the mass change of the sample product before and after the measurement. Five specimens were tested for each sample. The mass loss rate (%) = (initial mass - mass after immersion) / initial mass × 100%.

[0060] The aging resistance test also uses samples with a size of 20mm (length) × 20mm (width) × 1mm (thickness). A xenon lamp aging box is used for UV irradiation. The light intensity is set to 0.69W / m²@340nm and the aging time is 24h to simulate natural aging conditions. After aging, the tensile strength is tested and the performance attenuation percentage before and after aging is calculated. Aging decay percentage (%) = (tensile strength before aging - tensile strength after aging) / tensile strength before aging × 100%.

[0061] The obtained data are shown in Table 1

[0062] Table 1 Performance data of Examples 1-6 and Comparative Examples 1-3

[0063]

[0064] By comparing Examples 1-6 with Comparative Examples 1-3, it can be seen that in a weather-resistant PVC decorative film, the toughening agent will have a significant effect on the weather resistance, tensile strength and migration resistance of the PVC decorative film.

[0065] According to Examples 1-3, as the proportion of components in the toughening agent continues to increase, the weather resistance, tensile strength and migration resistance of the PVC decorative film gradually improve. This is because the ethoxy group of tetraethylene glycol methyl ether provides a volume-enhancing and toughening effect, which improves the compatibility of the toughening agent with the PVC material. The amino and carboxyl groups of L-serine provide binding force and antioxidant properties for other components. The synergistic effect between them fully exerts the toughening effect of the toughening agent, so the overall performance is greatly improved.

[0066] According to Example 3 and Example 4, as the content of other components of the PVC decorative film continues to change, the weather resistance, tensile strength and migration resistance of the PVC decorative film do not change significantly. This is because the other components have a relatively small impact on the overall performance of the PVC decorative film, and their small changes within a certain range are not sufficient to cause significant performance changes, so the change range is not obvious.

[0067] According to Example 3, Example 5 and Example 6, it can be known that as the toughening agent content continues to decrease, the weather resistance, tensile strength and migration resistance of the PVC decorative film gradually decrease. This is because as the toughening agent content decreases, the active groups in the toughening agent decrease, the toughening effect of the toughening agent decreases, the binding force with the PVC material weakens, and it is easy to migrate and precipitate. The PVC decorative film becomes brittle and hard, and is more likely to be deformed or damaged when subjected to external forces or environmental factors, resulting in a decrease in weather resistance, tensile strength and migration resistance.

[0068] According to the above test experiments, Example 3 is used as the optimal example and compared with Comparative Examples 1-3 respectively.

[0069] By comparing Example 3 with Comparative Example 1, it can be seen that the weather resistance, tensile strength and migration resistance of the PVC decorative film are worse when the toughening agent is added in an amount of 0.01 parts by weight. This is because the toughening agent cannot provide sufficient flexibility for the PVC decorative film, resulting in a decrease in the toughness of the material, and the number of active groups amino and carboxyl groups in the toughening agent is insufficient, and it cannot be fully combined with other components, thereby resulting in a decrease in the overall performance of the PVC decorative film.

[0070] By comparing Example 3 with Comparative Example 2, it can be seen that the toughening agent is prepared only from hydrogenated dimer acid, and is not modified by tetraethylene glycol methyl ether and L-serine. The weather resistance, tensile strength and migration resistance of the PVC decorative film are worse. This is because the hydrogenated dimer acid has a high non-polar ratio and limited compatibility with the PVC decorative film, while the ethoxy group of tetraethylene glycol methyl ether can increase the mobility of the PVC chain segment and improve the toughness of the material, and the amino and carboxyl groups of L-serine can form hydrogen bonds and metal ion complexes with the PVC material. The toughening agent without these two modifiers cannot fully exert these effects, resulting in a decrease in the weather resistance, tensile strength and migration resistance of the PVC decorative film.

[0071] By comparing Example 3 with Comparative Example 3, it can be seen that the toughening agent is prepared from hydrogenated dimer acid and tetraethylene glycol methyl ether, and L-serine is not used for modification. The weather resistance, tensile strength and migration resistance of the PVC decorative film are worse. This is because although the ethoxy group of tetraethylene glycol methyl ether can improve the compatibility of the toughening agent with the PVC material and improve the toughness of the material, the hydrogen bond itself is weak, and the bonding force with other materials is weak, and the toughening agent is easy to precipitate. Therefore, L-serine modification is not used, and the bonding force between the toughening agent and the PVC material cannot be fully enhanced, so the toughening agent is easy to migrate out, and the performance of the PVC material is gradually deteriorated.

[0072] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments, and the above embodiments and descriptions are only preferred examples of the present invention, and are not intended to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A weather-resistant PVC decorative film, characterized in that: The invention comprises the following components in parts by weight: 1-5 parts by weight of a toughening agent, 10-20 parts by weight of a polyvinyl chloride resin, 0.1-0.5 parts by weight of a Chimassorb 944 hindered amine light stabilizer, 0.2-0.5 parts by weight of a calcium zinc composite stabilizer, 0.3-0.7 parts by weight of a 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, 0.6-0.8 parts by weight of an alizarin red cerium complex antioxidant, 0.1-0.3 parts by weight of a talc filler, and 0.2-0.4 parts by weight of a carbon black pigment; Wherein, the specific preparation method of the toughening agent is as follows: Add N,N-dimethylformamide to a four-necked flask with a water separator and a condenser, and place the four-necked flask on a heated magnetic stirrer, add hydrogenated dimer acid and tetraethylene glycol methyl ether in sequence, continue stirring to fully mix, then add p-toluenesulfonic acid, adjust the heated magnetic stirrer to make the reaction mixture reach 110-120° C., react for 3-4 hours, add L-serine, continue to react for 4-5 hours, and after the reaction is completed, adjust the remaining liquid to neutral with a Na2CO3 solution, wash with distilled water, and remove unreacted substances by reduced pressure distillation to obtain a toughening agent; The mass ratio of the hydrogenated dimer acid, tetraethylene glycol methyl ether and L-serine is 1:1.5-2.0:0.5-1.0; The alizarin red cerium complex antioxidant is a complex formed by alizarin red S and cerium salt (III).

2. The weather-resistant PVC decorative film according to claim 1, characterized in that: The mass ratio of the hydrogenated dimer acid to N,N-dimethylformamide is 1:5-8.

3. The weather-resistant PVC decorative film according to claim 1, characterized in that: The mass fraction of the p-toluenesulfonic acid is 0.5-1%.

4. The weather-resistant PVC decorative film according to claim 1, characterized in that: The mass ratio of the p-toluenesulfonic acid to the hydrogenated dimer acid is 0.12-0.17:

1.

5. The weather-resistant PVC decorative film according to claim 1, characterized in that: When the reaction is finished, the acid value is less than or equal to 1 mgKOH / g.

6. The weather-resistant PVC decorative film according to claim 1, characterized in that: The mass fraction of the Na2CO3 solution is 5-10%.

7. The weather-resistant PVC decorative film according to claim 1, characterized in that: The specific preparation method of the weather-resistant PVC decorative film is as follows: Add toughening agent, polyvinyl chloride resin, Chimassorb 944 hindered amine light stabilizer, calcium zinc composite stabilizer, 2-hydroxy-4-methoxybenzophenone anti-ultraviolet absorber, alizarin red cerium complex antioxidant, talcum powder filler and carbon black pigment into a high-speed mixer, set the mixing time to 5-10 minutes, and the rotation speed to 800-1200rpm to fully and evenly mix the raw materials, send the mixed materials into a twin-screw extruder for plasticization, set the temperature of each section of the extruder, extrude the plasticized material into a film through a shaped mold, pass the extruded film through a set of cooling rollers, and the temperature is set at room temperature to ensure that the film surface is smooth and the size is stable, and the film after cooling and shaping is rolled up for acceptance to obtain a weather-resistant PVC decorative film.

8. The weather-resistant PVC decorative film according to claim 7, characterized in that: The temperature of the feeding zone of the extruder is 150-160°C, the temperature of the plasticizing zone is 170-180°C, and the temperature of the extrusion zone is 180-190°C.

9. The weather-resistant PVC decorative film according to claim 7, characterized in that: The screw speed of the extruder is 30-50 rpm.

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