Fluoroplastic film, and method of making and using same

Abstract

This invention discloses a fluoroplastic film, the raw material composition of which includes the following components in parts by weight: 100 parts fluoroplastic, 0.25-2.3 parts infrared absorber, 0.09-1.5 parts dispersant, and 0.09-1.5 parts other additives; wherein the other additives include mineral oil and / or organosiloxanes. This invention uses fluoroplastic as a substrate, nano-cesium tungsten bronze powder, ITO, and ATO as infrared absorbers, and combines them with stearic acid or synthetic wax, supplemented with mineral oil or silicone oil, to successfully produce a fluoroplastic film material with good mechanical properties, high visibility, and significant heat insulation performance through a casting process. The fluoroplastic film prepared by this invention has a tensile strength of up to 51 MPa and a breaking productivity of 420%; visible light transmittance up to 58% and haze as low as 34%; IR (760-2500nm) transmittance as low as 10% and UV (200-380nm) transmittance as low as 4%; and a temperature rise of 18°C ​​after 30 minutes. It can be used as a fluoroplastic film material with high comprehensive requirements for mechanical, visibility and thermal insulation performance.

Description

Technical Field

[0001] This invention belongs to the field of plastic processing technology, and particularly relates to a fluoroplastic film, its preparation method and application. Background Technology

[0002] In the construction and automotive industries, the high solar transmittance of installed glass causes indoor temperatures to rise rapidly. To improve the heat insulation of the glass, sunshades are typically installed for shading and heat insulation. However, during use, extending or pulling the sunshades can easily cause them to loosen or fall off, creating safety hazards and incurring additional costs.

[0003] To reduce safety hazards, heat-insulating films can be applied to glass. However, existing heat-insulating films are all based on PET, and their outdoor service life is no more than 10 years, indicating low durability.

[0004] Fluoroplastic films are widely used in outdoor exhibition halls, stadiums, agricultural greenhouses, and other buildings due to their excellent weather resistance, mechanical properties, and pollution resistance. However, because fluoroplastics have very high light transmittance (visible light, UV band, and IR band), they are particularly ineffective at blocking heat-generating wavelengths of sunlight, allowing direct sunlight to enter the interior and causing a rapid temperature rise. This significantly reduces human comfort, especially in hot weather, particularly summer. Therefore, it is necessary to reduce the transmittance of heat-generating wavelengths of sunlight, especially the infrared band.

[0005] Therefore, there is an urgent need in this field to develop a thin film with low safety risks, excellent durability, and ideal mechanical properties and thermal insulation. Summary of the Invention

[0006] The technical problem to be solved by the present invention is to overcome the safety hazards of existing heat insulation methods such as sunshade curtains, the low durability and short service life of existing film materials, the low transmittance of UV and IR bands and the low heat insulation performance, and the reduction of human comfort in high temperature seasons. The present invention provides a fluoroplastic film, its preparation method and application.

[0007] The fluoroplastic film prepared by this invention has ideal mechanical properties, with a tensile strength greater than or equal to 51 MPa, a breaking productivity of 420% or more, a haze as low as 34%, and excellent thermal insulation performance, with a UV band transmittance as low as 10% and an IR band transmittance as low as 4%. The temperature rise after 30 minutes is significantly reduced. This fluoroplastic film can be used as a thermal insulation film plastic material with high requirements for mechanical and thermal insulation performance.

[0008] The present invention solves the above-mentioned technical problems by adopting the following technical solutions:

[0009] This invention provides a raw material composition for a fluoroplastic film, comprising the following components in parts by weight: 100 parts fluoroplastic, 0.25 to 2.3 parts infrared absorber, 0.09 to 1.5 parts dispersant, and 0.09 to 1.5 parts other additives;

[0010] The other additives include mineral oil and / or organosiloxanes.

[0011] In some embodiments, the raw material composition of the fluoroplastic film may include the following components in parts by weight: 100 parts fluoroplastic, 0.3 to 2.1 parts infrared absorber, 0.1 to 1.1 parts dispersant and 0.1 to 1.1 parts other additives.

[0012] Preferably, the raw material composition of the fluoroplastic film may include the following components in parts by weight: 100 parts fluoroplastic, 0.3 to 1.1 parts infrared absorber, 0.1 to 0.9 parts dispersant and 0.1 to 0.9 parts other additives.

[0013] More preferably, the raw material composition of the fluoroplastic film may include the following components in parts by weight: 100 parts fluoroplastic, 0.3 to 0.6 parts infrared absorber, 0.1 to 0.5 parts dispersant and 0.1 to 0.5 parts other additives.

[0014] In some embodiments, the fluoroplastic may include a fluoropolymer, preferably one of ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride polymer, and perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer.

[0015] In some embodiments, the infrared absorber may include at least one of cesium tungsten bronze powder, indium tin oxide (ITO), and antimony tin oxide (ATO).

[0016] Wherein, when the infrared absorber includes the cesium tungsten bronze powder, the particle size of the cesium tungsten bronze powder is at the nanometer level. It can be nano-sized cesium tungsten bronze powder.

[0017] Wherein, when the infrared absorber includes indium tin oxide (ITO), the particle size of the indium tin oxide (ITO) is at the nanometer level.

[0018] Wherein, when the infrared absorber includes antimony tin oxide (ATO), the particle size of the antimony tin oxide (ATO) is at the nanometer level.

[0019] In some embodiments, the dispersant may include stearic acid homologues and / or synthetic waxes.

[0020] The stearic acid homologues may include ethylene bis-stearamide (EBS), zinc stearate, and calcium stearate.

[0021] The synthetic wax may include polyethylene wax.

[0022] In some embodiments, the mineral oil may include white mineral oil.

[0023] The organosiloxane may include silicone oil.

[0024] In some embodiments, when the other additives include the mineral oil and the organosilane, the weight ratio of the mineral oil to the organosilane is 1:(1-5).

[0025] This invention also provides a method for preparing a fluoroplastic film, wherein the raw materials include the raw material composition of the fluoroplastic film as described above, and the preparation method specifically includes the following steps:

[0026] (1) The fluoroplastic, the infrared absorber, the dispersant and the other additives are premixed to obtain a particle mixture;

[0027] (2) The particle mixture obtained in step (1) is melt-granulated to obtain modified particles;

[0028] (3) The modified particles obtained in step (2) are dried and cast into a film to obtain a fluoroplastic film.

[0029] In some embodiments, the premixing in step (1) can be a conventional premixing operation in the art, and the premixing operation can generally be performed in a high-speed mixer.

[0030] In some embodiments, the premixing time in step (1) can be 4 to 8 minutes, preferably 5 minutes.

[0031] In some embodiments, in step (1), the rotational speed of the premixing can be 300 to 600 rpm.

[0032] In some embodiments, the melting in step (2) can be a conventional melting operation in the art, and the melting operation can generally be carried out in a twin-screw extruder.

[0033] In some embodiments, the melting temperature in step (2) can be 250–400°C, preferably 300–380°C.

[0034] In some embodiments, the drying temperature in step (3) can be 120-150°C.

[0035] In some embodiments, the drying time in step (3) can be 2 to 4 hours.

[0036] In some embodiments, step (3) may include casting, extrusion, and shaping.

[0037] In some embodiments, the film casting can be conventional in the art, and the film casting operation can generally be performed in a film casting extruder.

[0038] The present invention also provides a fluoroplastic film, which is prepared by the fluoroplastic film preparation method described above.

[0039] The present invention also provides an application of the fluoroplastic film described above as a heat insulation film in the construction or automotive fields.

[0040] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0041] The reagents and raw materials used in this invention are all commercially available.

[0042] The positive and progressive effects of this invention are as follows: This invention uses fluoroplastics as the base material, nano-cesium tungsten bronze powder, ITO, and ATO as infrared absorbers, and combines them with stearic acid or synthetic wax, supplemented with mineral oil or silicone oil, to successfully produce fluoroplastic film materials with good mechanical properties, high visibility, and significant heat insulation performance through a casting film forming process.

[0043] The fluoroplastic film prepared by this invention has a tensile strength of up to 51 MPa and a breaking productivity of 420%; visible light transmittance up to 58% and haze as low as 34%; IR (760-2500nm) transmittance as low as 10% and UV (200-380nm) transmittance as low as 4%; and a temperature rise of 18°C ​​after 30 minutes. It can be used as a fluoroplastic film material with high comprehensive requirements for mechanical, visibility and thermal insulation performance. Attached Figure Description

[0044] This disclosure can be better understood by referring to the description given below in conjunction with the accompanying drawings. These drawings, together with the detailed description below, are incorporated in and form part of this specification, and are used to further illustrate preferred embodiments of the disclosure and explain the principles and advantages of the disclosure.

[0045] Figure 1 Flowchart of fluoroplastic film preparation process;

[0046] Figure 2 This is a comparison of the heating curves of the fluoroplastic film prepared in Example 1 of the present invention and the transparent fluoroplastic film.

[0047] Figure 3 This is a schematic diagram illustrating the reflection principle of a heat-insulating film. Detailed Implementation

[0048] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0049] The transparent fluoroplastic film is made of ETFE raw material without any additives, and is sourced from Shanghai Fujia New Material Technology Co., Ltd.

[0050] Example 1

[0051] (1) 100 parts of ethylene-tetrafluoroethylene copolymer (ETFE), 0.5 parts of nano cesium tungsten bronze powder, 0.4 parts of synthetic wax, 0.2 parts of mineral oil and 0.2 parts of organosiloxane were added to a high-speed mixer for premixing. The premixing time was 5 min and the premixing speed was 500 rpm. After the premixing was completed, a particle mixture was obtained.

[0052] (2) The particle mixture is added to a twin screw extruder and melt-extruded to obtain modified particles, wherein the melting temperature is 350℃;

[0053] (3) Place the modified particles into a dryer at a drying temperature of 150℃ and dry for 120 min. After drying, add them to a casting extruder for casting, extrusion and shaping.

[0054] Example 2

[0055] The difference from Example 1 is that the nano-cesium tungsten bronze powder is replaced with ITO, while all other conditions are the same as in Example 1.

[0056] (1) 100 parts of ethylene-tetrafluoroethylene copolymer (ETFE), 0.5 parts of indium tin oxide (ITO), 0.4 parts of synthetic wax, 0.2 parts of mineral oil and 0.2 parts of organosiloxane were added to a high-speed mixer for premixing. The premixing time was 5 min and the premixing speed was 500 rpm. After the premixing was completed, a particle mixture was obtained.

[0057] (2) The particle mixture is added to a twin screw extruder and melt-extruded to obtain modified particles, wherein the melting temperature is 350℃;

[0058] (3) Place the modified particles into a dryer at a drying temperature of 150℃ and dry for 120 min. After drying, add them to a casting extruder for casting, extrusion and shaping.

[0059] Example 3

[0060] The difference from Example 1 is that the synthetic wax in the dispersant is replaced with zinc stearate, while all other conditions are the same as in Example 1.

[0061] (1) 100 parts of ethylene-tetrafluoroethylene copolymer (ETFE), 0.5 parts of nano cesium tungsten bronze powder, 0.4 parts of zinc stearate, 0.2 parts of mineral oil and 0.2 parts of organosiloxane were added to a high-speed mixer for premixing. The premixing time was 5 min and the premixing speed was 500 rpm. After the premixing was completed, a particle mixture was obtained.

[0062] (2) The particle mixture is added to a twin screw extruder and melt-extruded to obtain modified particles, wherein the melting temperature is 350℃;

[0063] (3) Place the modified particles into a dryer at a drying temperature of 150℃ and dry for 120 min. After drying, add them to a casting extruder for casting, extrusion and shaping.

[0064] Comparative Example 1

[0065] The difference from Example 1 is that no dispersant, mineral oil and organosiloxane were added, while all other conditions were the same.

[0066] (1) 100 parts of ethylene-tetrafluoroethylene copolymer (ETFE), 0.5 parts of nano cesium tungsten bronze powder and 0.4 parts of synthetic wax were premixed in a high-speed mixer for 5 minutes and 500 rpm. After premixing, a particle mixture was obtained.

[0067] (2) The particle mixture is added to a twin screw extruder and melt-extruded to obtain modified particles, wherein the melting temperature is 350℃;

[0068] (3) Place the modified particles into a dryer at a drying temperature of 150℃ and dry for 120 min. After drying, add them to a casting extruder for casting, extrusion and shaping.

[0069] Comparative Example 2

[0070] The difference from Example 1 is that no dispersant or other additives were added, and the weight of nano-cesium tungsten bronze powder was 0.75 parts, while all other conditions were the same.

[0071] (1) 100 parts of ethylene-tetrafluoroethylene copolymer (ETFE), 0.75 parts of nano cesium tungsten bronze powder and 0.4 parts of synthetic wax were premixed in a high-speed mixer for 5 minutes and 500 rpm. After premixing, a particle mixture was obtained.

[0072] (2) The particle mixture is added to a twin screw extruder and melt-extruded to obtain modified particles, wherein the melting temperature is 350℃;

[0073] (3) Place the modified particles into a dryer at a drying temperature of 150℃ and dry for 120 min. After drying, add them to a casting extruder for casting, extrusion and shaping.

[0074] Comparative Example 3

[0075] The difference from Example 1 is that no dispersant or other additives were added, and the weight of nano-cesium tungsten bronze powder was 1, while all other conditions were the same.

[0076] (1) 100 parts of ethylene-tetrafluoroethylene copolymer (ETFE), 0.5 parts of nano cesium tungsten bronze powder, 0.4 parts of synthetic wax, 0.2 parts of mineral oil and 0.2 parts of organosiloxane other additives were added to a high-speed mixer for premixing. The premixing time was 5 min and the premixing speed was 500 rpm. After the premixing was completed, a particle mixture was obtained.

[0077] (2) The particle mixture is added to a twin screw extruder and melt-extruded to obtain modified particles, wherein the melting temperature is 350℃;

[0078] (3) Place the modified particles into a dryer at a drying temperature of 150℃ and dry for 120 min. After drying, add them to a casting extruder for casting, extrusion and shaping.

[0079] The preparation process flow charts for the embodiments and comparative examples of this invention are shown below. Figure 1 .

[0080] Example 1

[0081] The thermal insulation effects of the transparent fluoroplastic film and the fluoroplastic film prepared in Example 1 of this invention are shown in Table 1 and [other tables]. Figure 2 .

[0082] Table 1

[0083]

[0084] From Table 1 and Figure 2 It can be seen that the fluoroplastic film prepared in Example 1 of the present invention has a significantly reduced temperature rise rate compared with the transparent fluoroplastic film, which shows that the fluoroplastic film prepared in Example 1 of the present invention has ideal heat insulation performance.

[0085] Example 2

[0086] (1) Test the mechanical properties of the fluoroplastic films prepared in the above embodiments and comparative examples.

[0087] Mechanical property testing: The film was cut into dumbbell-shaped test strips according to the ISO527-3 test standard and placed in a universal tensile testing machine for tensile strength testing. The tensile speed was 200 mm / min. The test results are shown in Table 1.

[0088] (2) Test the optical properties and thermal insulation properties of the fluoroplastic films prepared in the above embodiments and comparative examples.

[0089] Thermal insulation performance test: The film was cut into 10*20cm samples, placed in a thermal insulation film tester, and the thermal insulation performance of each embodiment was tested after 30 minutes of light exposure. The test results are shown in Table 1.

[0090] Table 2

[0091]

[0092] As shown in Table 2, Example 1 exhibits the best overall performance, reaching 51 MPa and a breakage productivity of 420%. Visible light transmittance reaches 58%, haze is as low as 34%, IR (760–2500 nm) transmittance is as low as 10%, UV (200–380 nm) transmittance is as low as 4%, and the temperature rise after 30 minutes is 18°C. Comparative Example 1, without the addition of a dispersant, has higher haze, higher IR and UV transmittance, and poorer barrier properties. Comparative Examples 2 and 3, due to the excessive addition of infrared absorbers, have excessively low visible light transmittance and excessively high haze, and cannot be used as heat-insulating films without the addition of dispersants and other additives.

[0093] Depend on Figure 3 It is known that the thin film prepared by the present invention blocks the transmittance of IR and UV and promotes the transmittance of visible light.

[0094] Finally, it should be noted that in this invention, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus.

[0095] Although this disclosure has been described above through specific embodiments, it should be understood that those skilled in the art can devise various modifications, improvements, or equivalents to this disclosure within the spirit and scope of the appended solutions. Such modifications, improvements, or equivalents should also be considered to be included within the scope of protection claimed in this disclosure.

Claims

1. A fluoroplastic film, characterized in that, The raw material composition comprises the following components in parts by weight: 100 parts fluoroplastic, 0.25 to 2.3 parts infrared absorber, 0.09 to 1.5 parts dispersant, and 0.09 to 1.5 parts other additives; The other additives include mineral oil and organosiloxanes; the dispersant is a synthetic wax.

2. The fluoroplastic film as described in claim 1, characterized in that, The raw material composition comprises the following components in parts by weight: 100 parts fluoroplastic, 0.3 to 2.1 parts infrared absorber, 0.1 to 1.1 parts dispersant and 0.1 to 1.1 parts other additives.

3. The fluoroplastic film as described in claim 2, characterized in that, The raw material composition of the fluoroplastic film comprises the following components in parts by weight: 100 parts fluoroplastic, 0.3 to 1.1 parts infrared absorber, 0.1 to 0.9 parts dispersant and 0.1 to 0.9 parts other additives.

4. The fluoroplastic film as described in claim 2, characterized in that, The raw material composition of the fluoroplastic film includes the following components in parts by weight: 100 parts fluoroplastic, 0.3 to 0.6 parts infrared absorber, 0.1 to 0.5 parts dispersant and 0.1 to 0.5 parts other additives.

5. The fluoroplastic film as described in claim 2, characterized in that, The fluoroplastic film raw material composition satisfies at least one of the following conditions: The fluoroplastics include fluoropolymers; The infrared absorber includes cesium tungsten bronze powder, indium tin oxide, or tin antimony oxide.

6. The fluoroplastic film as described in claim 5, characterized in that, The fluoroplastic film raw material composition satisfies at least one of the following conditions: The fluoropolymer includes one of ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride polymer, and perfluoroalkyl vinyl ether-tetrafluoroethylene copolymer; The cesium tungsten bronze powder has a particle size in the nanometer range. When the infrared absorber includes indium tin oxide (ITO), the particle size of indium tin oxide (ITO) is in the nanometer range. When the infrared absorber includes antimony tin oxide (ATO), the particle size of antimony tin oxide (ATO) is in the nanometer range. The synthetic wax includes polyethylene wax.

7. The fluoroplastic film as described in claim 6, characterized in that, The cesium tungsten bronze powder is nano-cesium tungsten bronze powder.

8. The fluoroplastic film as described in claim 6, characterized in that, When the other additives include the mineral oil and the organosilane, the weight ratio of the mineral oil to the organosilane is 1:(1~5).

9. A method for preparing a fluoroplastic film as described in any one of claims 1 to 8, characterized in that, The preparation method specifically includes the following steps: (1) The fluoroplastic, the infrared absorber, the dispersant and the other additives are premixed to obtain a particle mixture; (2) The particle mixture obtained in step (1) is melt-granulated to obtain modified particles; (3) The modified particles obtained in step (2) are dried and cast into a film to obtain a fluoroplastic film.

10. The method for preparing the fluoroplastic film according to claim 9, characterized in that, The preparation method satisfies at least one of the following conditions: In step (1), the premixing is performed in a high-speed mixer; In step (1), the premixing time is 4~8 min; In step (1), the rotation speed of the premixing is 300~600 rpm.

11. The method for preparing fluoroplastic film according to claim 10, characterized in that, In step (1), the premixing time is 5 minutes; In step (1), the rotation speed of the premixing is 300~600 rpm.

12. The method for preparing fluoroplastic film as described in claim 9, characterized in that, The preparation method satisfies at least one of the following conditions: In step (2), the melting is performed in a twin-screw extruder. In step (2), the melting temperature is 250~400℃; In step (3), the drying temperature is 120~150℃; In step (3), the drying time is 2-4 hours; In step (3), the film casting process includes casting, extrusion, and shaping.

13. The method for preparing fluoroplastic film according to claim 12, characterized in that, In step (2), the melting temperature is 300~380℃.

14. A fluoroplastic film, which is prepared by the method for preparing the fluoroplastic film according to any one of claims 9-13.

15. The fluoroplastic film as described in claim 14, used as a heat insulation film in the construction or automotive sectors.

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