A matte low-temperature toughness polyolefin film, a preparation method and application thereof

Abstract

The application relates to the field of film materials, and more particularly to a low-temperature-resistant tough polyolefin film with a matte surface and a preparation method and application thereof. The low-temperature-resistant tough polyolefin film with a matte surface comprises, in mass parts, at least 50-70 parts of a main resin, 20-30 parts of a crystallization regulator, 5-15 parts of a compatilizer, 1-10 parts of a toughening agent and 5-15 parts of a modified reinforcing resin. The finally-prepared polyolefin film not only can maintain excellent matte and low-temperature-resistant tough properties, but also can simultaneously maintain good weather resistance, aging resistance, waterproofness and mechanical properties, and can meet the performance requirements of the polyolefin film in the related fields.

Description

Technical Field

[0001] This application relates to the field of membrane materials, and more specifically mentions a matte, low-temperature resistant, tough polyolefin film, its preparation method, and its application. Background Technology

[0002] Polypropylene (PP) film is widely used in food packaging, daily necessities packaging, electronic component insulation, medical device encapsulation, and cold chain logistics due to its excellent mechanical properties (such as high tensile strength and chemical resistance), good processing adaptability (can be blown, cast, or biaxially stretched) and low production cost. However, with the development of market demand, the requirements for film materials are also constantly increasing, especially for applications in special environments.

[0003] To meet market demands for aesthetics and anti-glare properties, a matte finish has become a key characteristic of polypropylene films. Through special surface treatments or the addition of specific additives, a uniform and delicate matte effect can be achieved on the film surface. This not only enhances the product's appearance and texture but also effectively reduces light reflection, improving visual comfort. Therefore, this type of film has broad application prospects in various fields.

[0004] In practical applications, especially in cold regions or during cold chain transportation, film materials are required to have excellent low-temperature resistance. Traditional polypropylene films become brittle at low temperatures, exhibiting significantly reduced impact resistance and a tendency to crack, which greatly limits their application range. Therefore, developing a polypropylene film that possesses both excellent matte finish and good toughness under low-temperature conditions is particularly urgent. Summary of the Invention

[0005] In summary, how to simultaneously satisfy the aforementioned multiple properties of polypropylene films has become an important issue that needs to be addressed by those skilled in the art. Through in-depth research on this type of film material, the applicant has ultimately proposed a matte, low-temperature resistant, and tough polyolefin film and its preparation method in this application. The polyolefin film ultimately obtained in this application not only maintains excellent matte finish and low-temperature toughness, but also simultaneously maintains good weather resistance, aging resistance, waterproofing, and mechanical properties, thus meeting the performance requirements of existing related fields for polyolefin films.

[0006] A matte, low-temperature resistant, tough polyolefin film, comprising, by weight, at least: 50-70 parts of main resin, 20-30 parts of crystallization regulator, 5-15 parts of compatibilizer, 1-10 parts of toughening agent, and 5-15 parts of modified reinforcing resin.

[0007] In a preferred embodiment, the main resin is polypropylene resin.

[0008] In a preferred embodiment, the melt flow rate of the main resin is 1.5–7.5 g / 10 min, 230 °C, and 2.16 kg.

[0009] In a preferred embodiment, the mass ratio of the main resin, crystallization regulator and modified reinforcing resin is (55-65):(20-25):(6-12).

[0010] In a preferred embodiment, the mass ratio of the main resin, the crystallization regulator and the modified reinforcing resin is (58-62):(23-25):(8-11).

[0011] In a preferred embodiment, the mass ratio of the main resin to the toughening agent is (55-65):(3-8).

[0012] In a preferred embodiment, the crystallization regulator is a copolymer polypropylene regulator.

[0013] In a preferred embodiment, the compatibilizer is low-density polyethylene.

[0014] In a preferred embodiment, the toughening agent is EVA or SEBS.

[0015] In a preferred embodiment, the toughening agent is EVA.

[0016] In a preferred embodiment, the preparation method of the modified reinforced resin specifically includes the following steps: S1: EVA, PP-g-MAH, glycidyl methacrylate and epoxy-terminated hyperbranched polyester are mixed in a high-speed mixer; S2: The mixture is extruded in a twin-screw extruder, and azobisisobutyronitrile is injected into the reaction zone to ensure a residence reaction, followed by vacuum degassing; S3: The extruded strip is cooled in a water bath, granulated by a pelletizer, and then dried with hot air to obtain the final product.

[0017] In a preferred embodiment, the preparation method of the modified reinforced resin specifically includes the following steps: S1: EVA, PP-g-MAH, glycidyl methacrylate and epoxy-terminated hyperbranched polyester are mixed in a high-speed mixer at 600-800 rpm for 10-20 min; S2: The mixture is extruded in a twin-screw extruder with the following temperatures: feeding zone 160-165℃, melting zone 170-175℃, reaction zone 180-190℃, homogenization zone 170-180℃, die 165-170℃, and rotation speed 120-150 rpm. Azobisisobutyronitrile is injected into the reaction zone and held for 1-2 min, followed by vacuum degassing; S3: The extruded strip is cooled in a water bath, granulated by a pelletizer, and then dried with hot air at 75-80℃ for 4-5 h to obtain the final product.

[0018] In a preferred embodiment, the mass ratio of EVA, PP-g-MAH, glycidyl methacrylate, and epoxy-terminated hyperbranched polyester is (5-8):(1-2.2):(0.8-1.6):(0.3-0.8).

[0019] In a preferred embodiment, the mass ratio of EVA, PP-g-MAH, glycidyl methacrylate, and epoxy-terminated hyperbranched polyester is (6-7):(1.5-2):(1-1.3):(0.4-0.6).

[0020] In a preferred embodiment, the VA content of the EVA is 20-30%.

[0021] In a preferred embodiment, the grafting rate of the PP-g-MAH is 0.8% to 1.5%.

[0022] In a preferred embodiment, the matte low-temperature resistant tough polyolefin film, by weight, further comprises: 0.3-0.8 parts antioxidant, 0.6-1.5 parts lubricant, 0.3-0.5 parts nucleating agent, 0.2-0.4 parts antistatic agent, and 5-12 parts toughening and matte composition.

[0023] In a preferred embodiment, the mass ratio of the main resin to the toughening matte composition is (55-65):(6-10).

[0024] In a preferred embodiment, the mass ratio of the main resin to the toughening matte composition is (58-62):(7.5-9).

[0025] In a preferred embodiment, the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 245, and antioxidant 1098.

[0026] In a preferred embodiment, the antioxidant is antioxidant 168 or antioxidant 1076.

[0027] In a preferred embodiment, the lubricant is at least one selected from ethylene bis-stearamide, polyethylene wax, sodium stearate, and erucamide.

[0028] In a preferred embodiment, the lubricant is ethylene bis-stearamide or polyethylene wax.

[0029] In a preferred embodiment, the lubricant is ethylene bis-stearamide.

[0030] In a preferred embodiment, the nucleating agent is at least one of sorbitol diacetal, sodium phosphate salt, and talc.

[0031] In a preferred embodiment, the nucleating agent is sorbitol diacetal.

[0032] In a preferred embodiment, the antistatic agent is glyceryl monostearate or ethoxylated alkylamine.

[0033] In a preferred embodiment, the antistatic agent is glyceryl monostearate.

[0034] In a preferred embodiment, the toughening and matting composition is a combination of POE, SBS and nanoporous silica.

[0035] In a preferred embodiment, the mass ratio of POE, SBS and nanoporous silica is (5-6):(2-3):(1-2).

[0036] In a preferred embodiment, the mass ratio of POE, SBS and nanoporous silica is (5-5.5):(2.3-2.6):(1.4-1.6).

[0037] In a preferred embodiment, the average particle size of the nanoporous silica is 50–100 nm.

[0038] A method for preparing the above-mentioned matte, low-temperature resistant, tough polyolefin film includes the following steps: S1: Activate all the required raw materials, mix, stir, disperse, and heat them while stirring at high speed; S2: Add the raw materials to a twin-screw extruder for melt extrusion, then cut them into pellets and cast them into a film using a three-roll casting machine; S3: After film formation, perform corona treatment, ensure the haze is within acceptable limits, and then rewind the film to obtain the final product.

[0039] The preferred embodiment of the above-mentioned method for preparing a matte, low-temperature resistant, tough polyolefin film specifically includes the following steps: S1: After activating all the required raw materials, mix and disperse them at 300-400 rpm for 0.5-2 min, then heat to 100-120℃ and stir at 800-1000 rpm for 0.5 min; S2: Add to a twin-screw extruder, melt extrude at 190-200℃, granulate, and then cast into a film using a three-roll casting machine, with the upper roll at 85-90℃, the middle roll at 60-65℃, and the lower roll at 20-25℃, and a traction speed of 10-15 m / min; S3: After film formation, perform corona treatment to achieve a film density of 40-48 dynes / cm. 2 If the haze test is 80-85% qualified, the product can be rolled up.

[0040] This application further defines the application of the aforementioned matte, low-temperature resistant, tough polyolefin film in packaging materials, cold chain logistics, and protective film materials.

[0041] This application has practical significance and beneficial effects:

[0042] 1. The polyolefin film finally obtained in this application not only maintains excellent matte finish and low-temperature toughness, but also maintains good weather resistance, aging resistance, waterproofing and mechanical properties, which can meet the performance requirements of the existing related fields for the polyolefin film.

[0043] 2. The polyolefin film prepared in this application contains active groups on its molecular chain that can react with the matrix resin, such as epoxy groups, carboxyl groups, and hydroxyl groups, through the addition of modified reinforcing resin. These active groups can react chemically with the matrix resin to form a network structure, increase a portion of flexible chains, thereby improving the mechanical properties, matte and gloss-reducing effects, and low-temperature resistance of the composite material.

[0044] 3. Furthermore, by adding a toughening and matte composition, which has excellent compatibility with the main resin, it mixes with the matrix material through physical action to form a micro-phase separation structure, such as an "island structure," thereby improving the toughness and impact resistance of the material, changing the light path, forming scattering and refraction effects, resulting in matte and glossy phenomena, and helping to enhance the overall comprehensive performance. Attached Figure Description

[0045] Figure 1 This is a photograph of the matte, low-temperature resistant, tough polyolefin film prepared in Example 1 of this application.

[0046] Figure 2 A diagram illustrating the production and winding process of the matte, low-temperature resistant, tough polyolefin film prepared in Example 1 of this application.

[0047] Figure 3 This is an overview diagram of the production workshop for the matte, low-temperature resistant, tough polyolefin film of this application.

[0048] Figure 4 This is an overview diagram of the performance testing instrument for the matte, low-temperature resistant, tough polyolefin film of this application. Detailed Implementation

[0049] Example 1

[0050] The matte, low-temperature resistant, tough polyolefin film, by weight, comprises the following raw materials: 61.5 parts of main resin, 24 parts of crystallization regulator, 8.6 parts of compatibilizer, 6.5 parts of toughening agent, 10.2 parts of modified reinforcing resin, 0.4 parts of antioxidant, 0.9 parts of lubricant, 0.3 parts of nucleating agent, 0.3 parts of antistatic agent, and 8.8 parts of toughening and matte composition.

[0051] The main resin is polypropylene resin PP-1126NK, with a melt flow rate of 4.5 g / 10 min, a temperature of 230°C, and a yield of 2.16 kg. It is sourced from Thai petrochemicals.

[0052] The crystallization regulator is copolymer polypropylene regulator PP-V30G, sourced from Sinopec Maoming.

[0053] The compatibilizer is low-density polyethylene NA205-15, sourced from Shanghai Ouqinghong Chemical Co., Ltd., China.

[0054] The toughening agent is EVA-360, which is from DuPont, USA.

[0055] The preparation method of the modified reinforced resin, by weight, specifically includes the following steps: S1: Mix 7 parts EVA, 1.8 parts PP-g-MAH, 1.1 parts glycidyl methacrylate and 0.5 parts epoxy-terminated hyperbranched polyester in a high-speed mixer at 800 rpm for 15 min; S2: Extrude the mixture in a twin-screw extruder with the following temperatures: feeding zone 160℃, melting zone 170℃, reaction zone 185℃, homogenization zone 175℃, die 170℃, and rotation speed 150 rpm. Inject 0.03 parts azobisisobutyronitrile into the reaction zone and ensure a residence time of 2 min, followed by vacuum degassing; S3: Cool the extruded strip in a water bath, granulate it using a pelletizer, and then dry it with hot air at 80℃ for 4 h to obtain the final product.

[0056] The EVA content is 28%, Elvax-3165, from DuPont, USA.

[0057] The grafting rate of PP-g-MAH is 1%, Polybond-3200, from Kraton Pharmaceuticals, USA.

[0058] Oxygen-terminated hyperbranched polyester H2004 is from Evonik Industries, Germany.

[0059] The antioxidant is antioxidant 168; the lubricant is ethylene bis-stearamide; the nucleating agent is sorbitol bisacetal; and the antistatic agent is glyceryl monostearate.

[0060] The toughening and matting composition is a combination of POE, SBS and nanoporous silica in a mass ratio of 5.5:2.5:1.5.

[0061] The nanoporous silica has an average particle size of 60 nm and comes from Beijing Zhongke Keyou, China.

[0062] SBS is YH-792, sourced from Yueyang Petrochemical in China; POE is Engage-8180, sourced from Dow Chemical Company in the United States.

[0063] The preparation method of the above-mentioned matte low-temperature resistant tough polyolefin film specifically includes the following steps: S1: After activating all the required raw materials, mix and stir at 400 rpm for 1 min, then heat to 110℃ and stir at 1000 rpm for 0.5 min; S2: Add to a twin-screw extruder, melt extrude at 200℃, granulate, and then cast into a film using a three-roll casting machine with the upper roll at 90℃, the middle roll at 60℃, and the lower roll at 25℃, and a traction speed of 15 m / min; S3: After film formation, perform corona treatment, 48 dynes / cm 2 If the haze test is 80-85% qualified, the product can be rolled up.

[0064] The actual product of the matte, low-temperature resistant, tough polyolefin film prepared in this embodiment is shown below. Figure 1 As shown.

[0065] The production and winding process of the matte, low-temperature resistant, tough polyolefin film obtained in this embodiment is as follows: Figure 2 As shown.

[0066] The overview of the production workshop for the matte, low-temperature resistant, tough polyolefin film of this application is as follows: Figure 3 As shown.

[0067] The performance testing instrument for the matte, low-temperature resistant, tough polyolefin film of this application is described below. Figure 4 As shown.

[0068] Example 2

[0069] The only difference between this embodiment and Example 1 is as follows: The matte, low-temperature resistant, tough polyolefin film, by weight, comprises: 57.5 parts of main resin, 20 parts of crystallization regulator, 8.6 parts of compatibilizer, 6.5 parts of toughening agent, 7.5 parts of modified reinforcing resin, 0.4 parts of antioxidant, 0.9 parts of lubricant, 0.3 parts of nucleating agent, 0.3 parts of antistatic agent, and 8.8 parts of toughening and matte composition.

[0070] All other implementation schemes are the same.

[0071] Example 3

[0072] The only difference between this embodiment and Example 1 is as follows: The matte, low-temperature resistant, tough polyolefin film, by weight, comprises the following raw materials: 65 parts of main resin, 24 parts of crystallization regulator, 8.6 parts of compatibilizer, 6.5 parts of toughening agent, 11 parts of modified reinforcing resin, 0.4 parts of antioxidant, 0.9 parts of lubricant, 0.3 parts of nucleating agent, 0.3 parts of antistatic agent, and 6.2 parts of toughening and matte composition.

[0073] All other implementation schemes are the same.

[0074] Comparative Example 1

[0075] The only difference between this comparative example and Example 1 is as follows: The matte, low-temperature resistant, tough polyolefin film, by weight, comprises: 60 parts of main resin, 24 parts of crystallization regulator, 8.6 parts of compatibilizer, 6.5 parts of toughening agent, 3.5 parts of modified reinforcing resin, 0.4 parts of antioxidant, 0.9 parts of lubricant, 0.3 parts of nucleating agent, 0.3 parts of antistatic agent, and 12.5 parts of toughening matte composition.

[0076] All other implementation schemes are the same.

[0077] Comparative Example 2

[0078] The only difference between this comparative example and Example 1 is as follows: The matte, low-temperature resistant, tough polyolefin film, by weight, comprises: 70 parts of main resin, 24 parts of crystallization regulator, 8.6 parts of compatibilizer, 6.5 parts of toughening agent, 12.5 parts of modified reinforcing resin, 0.4 parts of antioxidant, 0.9 parts of lubricant, 0.3 parts of nucleating agent, 0.3 parts of antistatic agent, and 2.2 parts of toughening matte composition.

[0079] All other implementation schemes are the same.

[0080] Comparative Example 3

[0081] The only difference between this comparative example and Example 1 is as follows: The preparation method of the modified reinforced resin, by mass, specifically includes the following steps: S1: Mix 7 parts of EVA and 2.5 parts of glycidyl methacrylate in a high-speed mixer at 800 rpm for 15 min; S2: Extrude the mixture in a twin-screw extruder with the following temperatures: feeding zone 160°C, melting zone 170°C, reaction zone 185°C, homogenization zone 175°C, die 170°C, and rotation speed 150 rpm. Inject 0.03 parts of azobisisobutyronitrile into the reaction zone and ensure a residence time of 2 min, followed by vacuum degassing; S3: Cool the extruded strip in a water bath, granulate it using a pelletizer, and then dry it with hot air at 80°C for 4 h to obtain the final product.

[0082] All other implementation schemes are the same.

[0083] Comparative Example 4

[0084] The only difference between this comparative example and Example 1 is the following: The preparation method of the modified reinforced resin, by weight, specifically includes the following steps: S1: 10 parts of EVA, 0.6 parts of PP-g-MAH, 0.8 parts of glycidyl methacrylate and 0.2 parts of epoxy-terminated hyperbranched polyester are mixed in a high-speed mixer at 800 rpm for 15 min; S2: The mixture is extruded in a twin-screw extruder with the following temperatures: feeding zone 160°C, melting zone 170°C, reaction zone 185°C, homogenization zone 175°C, die 170°C, and rotation speed 150 rpm. 0.03 parts of azobisisobutyronitrile are injected into the reaction zone and held for 2 min, followed by vacuum degassing; S3: The extruded strip is cooled in a water bath, granulated by a pelletizer, and then dried with hot air at 80°C for 4 h to obtain the final product.

[0085] All other implementation schemes are the same.

[0086] Comparative Example 5

[0087] The only difference between this comparative example and Example 1 is that the toughening and matting composition is a combination of POE, SBS and nanoporous silica in a mass ratio of 8:1:0.5.

[0088] All other implementation schemes are the same.

[0089] Comparative Example 6

[0090] The only difference between this comparative example and Example 1 is that the toughening and matting composition is a combination of POE, SBS and nanoporous silica in a mass ratio of 1:2:3.

[0091] All other implementation schemes are the same.

[0092] Performance testing

[0093] 1. Low temperature toughness: Refer to standard ISO 179-1:2010, test temperature -25℃, impact velocity 3.8~4m / s, and the result is the average of 10 interpretations and is included in Table 1.

[0094] 2. Water resistance: Refer to standard ISO 15106-3:2003, 38℃±0.5℃ / 90%±2%RH, test area 100cm². 2 The test lasted for 24 hours, and the average of 10 interpretations was recorded in Table 1.

[0095] 3. Salt spray resistance: Refer to standard ISO 9227:2017, 5% NaCl, cycle: spray 2h-dry 1h-wet 4h-freeze-25℃ 1h, cumulative 720h, test the change rate of fog before and after, and the result is the average of 10 interpretations and is included in Table 1.

[0096] 4. Tensile strength: Referencing standard ISO 527-3:2018, the results are the average of 10 interpretations and are included in Table 1.

[0097] Table 1 Performance Test Results

[0098]

[0099] Based on the final performance test results of the examples and comparative examples, comparative examples 1 to 2 all adopted different formulation schemes for the main resin, modified reinforcing resin and toughening matting composition than those specified in this application. This directly led to the actual application effect of these two raw materials in the film system. In particular, when their content was significantly reduced, the overall performance of the film material was significantly reduced compared to examples 1 to 3.

[0100] Comparative Examples 3 to 6, however, did not adopt the preparation method of the modified reinforcing resin and the composition scheme of the toughening and matting composition specified in this application, which directly led to a significant reduction in their effect on the main resin, and thus directly affected the overall performance of the film, resulting in a decline in performance.

Claims

1. A matte, low-temperature resistant, tough polyolefin film, characterized in that: By weight, the raw materials include at least: 50-70 parts of main resin, 20-30 parts of crystallization regulator, 5-15 parts of compatibilizer, 1-10 parts of toughening agent, 5-15 parts of modified and reinforced resin, 0.3-0.8 parts of antioxidant, 0.6-1.5 parts of lubricant, 0.3-0.5 parts of nucleating agent, 0.2-0.4 parts of antistatic agent, and 5-12 parts of toughening and matting composition; The main resin is polypropylene resin, with a melt flow rate of 1.5~7.5 g / 10min, 230℃, and 2.16 kg. The crystallization regulator is homopolymer polypropylene regulator PP-V30G; The preparation method of the modified reinforced resin includes: S1: mixing EVA, PP-g-MAH, glycidyl methacrylate and epoxy-terminated hyperbranched polyester in a high-speed mixer; S2: mixing and extruding in a twin-screw extruder, and injecting azobisisobutyronitrile into the reaction zone therein, ensuring that the reaction is carried out under vacuum after the reaction is completed; S3: cooling the extruded strip in a water bath, granulating it in a pelletizer and then drying it to obtain the product; The mass ratio of EVA, PP-g-MAH, glycidyl methacrylate, and epoxy-terminated hyperbranched polyester is (5~8):(1~2.2):(0.8~1.6):(0.3~0.8). The toughening and matting composition is a combination of POE, SBS and nanoporous silica in a mass ratio of (5~6):(2~3):(1~2).

2. The matte, low-temperature resistant, tough polyolefin film according to claim 1, characterized in that: The mass ratio of the main resin, crystallization regulator and modified reinforcing resin is (55~65):(20~25):(6~12).

3. The matte, low-temperature resistant, tough polyolefin film according to claim 2, characterized in that: The toughening agent is EVA or SEBS.

4. The matte, low-temperature resistant, tough polyolefin film according to claim 3, characterized in that: The modified reinforced resin has an EVA content of 20-30%; the grafting rate of the PP-g-MAH is 0.8-1.5%.

5. The matte, low-temperature resistant, tough polyolefin film according to claim 4, characterized in that: The mass ratio of the main resin to the toughening matting composition is (55~65):(6~10).

6. A method for preparing a matte, low-temperature resistant, tough polyolefin film according to any one of claims 1 to 5, characterized in that: S1: Activate all required raw materials, mix, stir, disperse, and heat, stirring at high speed; S2: Add to a twin-screw extruder for melt extrusion, then cut into pellets, and cast into a film using a three-roll casting machine; S3: After film formation, perform corona treatment, ensure the haze test is qualified, and then rewind to obtain the final product.

7. The application of a matte, low-temperature resistant, tough polyolefin film according to any one of claims 1 to 5 in packaging materials and protective film materials.

Images