Heat insulation film as well as preparation method and application thereof

Abstract

The invention provides a heat-insulating film and a preparation method and application thereof.The heat-insulating film comprises rare earth hexaboride, antimony tin oxide and / or indium tin oxide, polymer resin and assistant.The rare earth hexaboride is compounded with the antimony tin oxide and / or indium tin oxide, and the prepared heat-insulating film has the advantages of being wide in infrared light blocking wave band range, high in heat-insulating property, good in heat-insulating property and the like. And the heat insulation capability is high.

Description

Technical Field

[0001] The invention belongs to the technical field of membrane materials, and in particular relates to a thermal insulation film and a preparation method and application thereof. Background Art

[0002] Thermal insulation film is a film material that can absorb or reflect infrared light and has a thermal insulation effect.

[0003] CN113980318A discloses a window film, wherein a heat-insulating layer is provided on at least one surface of a base film, wherein the heat-insulating layer is formed by a composition comprising indium tin oxide and a thermosetting resin, wherein the contents of indium tin oxide and the thermosetting resin in the composition forming the heat-insulating layer are measured by weight, and the mass ratio of indium tin oxide to the thermosetting resin is 80:20 to 95:5, and the average particle size of indium tin oxide contained in the heat-insulating layer is less than 60 nm. The window film provided by this technical solution has high heat-insulating properties.

[0004] CN114131969A discloses a method for preparing a composite transparent film, which comprises first preparing a transparent gel film and then loading silica microspheres on the surface of the transparent gel film; wherein the components for preparing the transparent gel film include indium tin oxide. The composite transparent film prepared by compounding indium tin oxide and silica in this technical solution can respectively absorb and reflect ultraviolet light and near-infrared light bands, thereby improving the shielding properties of the transparent film for ultraviolet light and near-infrared light, and has a shielding rate of 91% in the 380nm ultraviolet band and a shielding rate of 74% in the 1500nm near-infrared band.

[0005] CN104861762A discloses a transparent glass heat-insulating material, which is composed of a tungsten complex and indium tin oxide and / or antimony tin oxide in a mass ratio of 100:0 to 30:0 to 32, and the indium tin oxide and antimony tin oxide are not 0 at the same time. The transparent glass heat-insulating material provided by the technical solution can effectively block the transmission of infrared and ultraviolet rays and has a better heat-insulating effect.

[0006] The films made of antimony tin oxide or indium tin oxide and polymer provided in the above scheme can block part of infrared light and have a certain heat insulation effect. However, the infrared light blocking band of antimony tin oxide and indium tin oxide is relatively narrow, accounting for about 40% of the total infrared light energy, and the heat insulation effect shown in practical applications is limited.

[0007] Therefore, it is necessary to develop a thermal insulation film with a wide infrared light blocking band and good heat insulation effect. Summary of the invention

[0008] In view of the deficiencies in the prior art, the object of the present invention is to provide a thermal insulation film and a preparation method and application thereof. The thermal insulation film prepared by compounding rare earth hexaboride with antimony tin oxide and / or indium tin oxide has the characteristics of a wide infrared light blocking band and strong thermal insulation ability.

[0009] To achieve this object, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a thermal insulation film, which includes rare earth hexaboride, antimony tin oxide and / or indium tin oxide, a polymer resin and an additive.

[0011] In the present invention, the thermal insulation film is compounded by adding rare earth hexaboride and antimony tin oxide and / or indium tin oxide, thereby broadening the absorption and reflection band range of infrared light by the thermal insulation film and improving the thermal insulation effect of the thermal insulation film.

[0012] Preferably, the thermal insulation film has a one-layer or at least two-layer structure.

[0013] Preferably, the rare earth hexaboride and antimony tin oxide and / or indium tin oxide are simultaneously located in any one layer of the thermal insulation film having at least two layers.

[0014] Preferably, the thickness of the thermal insulation film is 0.06-2 mm, for example, 0.06 mm, 0.07 mm, 0.08 mm, 0.09 mm, 0.10 mm, 0.11 mm, 0.12 mm, 0.13 mm, 0.14 mm, 0.15 mm, 0.2 mm, 0.5 mm, 0.7 mm, 0.9 mm, 1 mm, 1.5 mm, 1.8 mm or 2 mm.

[0015] Preferably, the rare earth hexaboride is a surface-modified rare earth hexaboride, the antimony tin oxide is a surface-modified antimony tin oxide, and the indium tin oxide is a surface-modified indium tin oxide.

[0016] In the present invention, the surface modification can reduce the surface energy of rare earth hexaboride, antimony tin oxide and indium tin oxide, reduce agglomeration in the polymer resin, increase the dispersion effect, and help improve the infrared light blocking effect.

[0017] Preferably, the surface modification method includes any one of electrochemical modification, physical modification or chemical modification, or a combination of at least two of them.

[0018] Preferably, the physical modification method includes any one of a magnetic stirring method, a ball milling method, and an ultrasonic dispersion method, or a combination of at least two of them.

[0019] Preferably, the surface modification is physical modification and chemical modification performed sequentially.

[0020] Preferably, the chemical modification method includes any one of coupling agent modification, surfactant modification, organic acid modification or organic oligomer modification, or a combination of at least two thereof.

[0021] Preferably, the coupling agent includes a silane coupling agent and / or a titanate coupling agent.

[0022] Exemplarily, the surfactant includes any one of zinc stearate, sodium stearate or calcium stearate, or a combination of at least two of them; the organic acid includes stearic acid; and the organic oligomer includes polyethylene wax and / or polypropylene.

[0023] Preferably, the mass of the coupling agent in the surface-modified rare earth hexaboride is 0.2% to 10% of the mass of the rare earth hexaboride, for example, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, etc.

[0024] Preferably, the mass of the coupling agent in the surface-modified antimony tin oxide is 0.2% to 10% of the mass of the antimony tin oxide, for example, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0025] Preferably, the mass of the coupling agent in the surface-modified indium tin oxide is 0.2% to 10% of the mass of indium tin oxide, for example, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.

[0026] Preferably, the rare earth hexaboride includes any one of neodymium hexaboride, gadolinium hexaboride, praseodymium hexaboride, lanthanum hexaboride, cerium hexaboride or samarium hexaboride, or a combination of at least two thereof.

[0027] In the present invention, there are a large number of free electrons inside the rare earth hexaboride. When exposed to light, the free electrons are excited to produce surface plasma resonance, thereby absorbing and reflecting infrared light. The rare earth hexaboride has good reflection and absorption properties for light in the near-infrared band. Compared with adding antimony tin oxide and / or indium tin oxide for thermal insulation, the rare earth hexaboride has a better thermal insulation effect. When rare earth hexaboride and antimony tin oxide and / or indium tin oxide are added to the thermal insulation film at the same time for compounding, a synergistic effect is generated, which widens the infrared light blocking band of the thermal insulation film, and can still achieve a good thermal insulation effect when the amount added is small.

[0028] Preferably, the particle sizes of the rare earth hexaboride, antimony tin oxide and indium tin oxide are independently 0.01 to 200 μm, for example, 0.01 μm, 0.05 μm, 0.1 μm, 1 μm, 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 150 μm or 200 μm.

[0029] Preferably, based on the total mass of the thermal insulation film as 100%, the mass percentage of the rare earth hexaboride is 0.01% to 5% (for example, 0.01%, 0.05%, 0.08%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 2%, 3%, 4% or 5%, etc.), and more preferably 0.5% to 1%.

[0030] In the present invention, taking the total mass of the thermal insulation film as 100%, the mass percentage of the rare earth hexaboride is 0.01% to 5%. The reason is that if the mass percentage of the rare earth hexaboride is too large, it will greatly affect the transmittance of the thermal insulation film to visible light; if the mass percentage is too small, the thermal insulation effect will decrease.

[0031] Preferably, based on the total mass of the thermal insulation film as 100%, the mass percentage of antimony tin oxide is 0.1% to 10%, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 7%, 9% or 10%, etc., and more preferably 0.5% to 5%.

[0032] Preferably, based on the total mass of the thermal insulation film as 100%, the mass percentage of indium tin oxide is 0.1% to 10%, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 3%, 5%, 7%, 9% or 10%, etc., and more preferably 0.5% to 5%.

[0033] In the present invention, based on the total mass of the thermal insulation film as 100%, the mass percentage of the antimony tin oxide is 0.1% to 10%, and the mass percentage of the indium tin oxide is 0.1% to 10%. The reason is that if the mass percentage of the antimony tin oxide or the indium tin oxide is too large, the transmittance of the obtained thermal insulation film to visible light decreases, and when in contact with organisms, the toxicity of antimony, indium and tin will have a harmful effect on the growth and development of the organisms; if the mass percentage of the antimony tin oxide or the indium tin oxide is too small, the thermal insulation effect of the obtained thermal insulation film decreases.

[0034] Preferably, the polymer resin includes one or a combination of at least two of polyethylene, polypropylene, polyethylene terephthalate, polyethylene elastomer (POE), thermoplastic polyurethane (TPU), ethylene-vinyl alcohol copolymer (EVOH), nylon, polyvinyl chloride or ethylene-vinyl acetate copolymer.

[0035] Preferably, the mass percentage of the polymer resin in the thermal insulation film is 80% to 99% (for example, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96% or 99%, etc.), and more preferably 90% to 95%.

[0036] Preferably, the auxiliary agent includes any one or a combination of at least two of an antioxidant, a UV absorber, a nucleating agent, a plasticizer, a toughening agent, a heat stabilizer, a dispersant, a lubricant, a colorant, a light stabilizer or an antistatic agent.

[0037] Preferably, the mass percentage of the antioxidant, UV absorber, nucleating agent, plasticizer, toughening agent, heat stabilizer, dispersant, lubricant, colorant, light stabilizer or antistatic agent in the thermal insulation film is independently 0.1% to 1%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% or 1%, etc.

[0038] In a second aspect, the present invention provides a method for preparing the thermal insulation film according to the first aspect, the preparation method comprising the following steps:

[0039] (1) Rare earth hexaboride, antimony tin oxide and / or indium tin oxide, polymer resin and additives are prepared into thermal insulation masterbatch.

[0040] (2) Mixing the polymer resin and the thermal insulation masterbatch obtained in step (1), extruding, and molding to obtain the thermal insulation film.

[0041] Preferably, the step (1) specifically comprises mixing rare earth hexaboride, antimony tin oxide and / or indium tin oxide, polymer resin and additives, and extruding to prepare a thermal insulation masterbatch.

[0042] Preferably, the step (1) specifically comprises mixing rare earth hexaboride, a polymer resin and an additive, and extruding to prepare a thermal insulation masterbatch of rare earth hexaboride; mixing antimony tin oxide and / or indium tin oxide, a polymer resin and an additive, and extruding to prepare a thermal insulation masterbatch of antimony tin oxide and / or indium tin oxide.

[0043] Preferably, the step (1) specifically comprises mixing rare earth hexaboride, antimony tin oxide or indium tin oxide independently with a polymer resin and an additive, extruding, cooling, cutting and drying to obtain rare earth hexaboride thermal insulation masterbatch, antimony tin oxide thermal insulation masterbatch or indium tin oxide thermal insulation masterbatch respectively.

[0044] Preferably, in step (2), based on the total mass of the polymer resin and the thermal insulation masterbatch as 100%, the mass percentage of the thermal insulation masterbatch is 1% to 20%, for example, 1%, 2%, 5%, 8%, 10%, 11%, 12%, 15%, 18%, 19% or 20%, etc.

[0045] Preferably, in step (2), the molding comprises any one of extrusion molding, blow molding, calendering molding, cast molding or stretching molding.

[0046] Illustratively, the extrusion equipment in step (1) is a twin-screw extruder, and the extrusion equipment in step (2) is a single-screw extruder.

[0047] In a third aspect, the present invention provides a use of the thermal insulation film as described in the first aspect in a thermal insulation product.

[0048] Exemplarily, the thermal insulation product includes any one of a photobioreactor thermal insulation material, a thermal insulation functional photobioreactor, a thermal insulation agricultural film, a car thermal insulation film, a thermal insulation glass film, a laminated film for laminated glass, or a thermal insulation building material.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The present invention solves the problem of narrow infrared light blocking band of antimony tin oxide and / or indium tin oxide by compounding rare earth hexaboride with antimony tin oxide and / or indium tin oxide, and prepares a thermal insulation film with a wide infrared light blocking band and good heat insulation effect, and the thermal insulation film has a high visible light transmittance. The infrared light blocking band of the thermal insulation film is 700-2500nm, the visible light transmittance is 50.5%-84.5%, and the temperature difference of the natural light thermal insulation test is -8.5 to -1.7°C; preferably, the infrared light blocking band of the thermal insulation film is 700-2500nm, the visible light transmittance is 61.9%-71.7%, the temperature difference of the infrared light thermal insulation test is -9.2 to -6.4°C, and the temperature difference of the natural light thermal insulation test is -8.0 to -5.0°C. DETAILED DESCRIPTION

[0051] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0052] All "parts" mentioned below are "parts by mass".

[0053] Example 1

[0054] The present embodiment provides a thermal insulation film and a preparation method thereof, wherein the thermal insulation film includes the following components in percentage by mass: 0.99% rare earth hexaboride (surface-modified lanthanum hexaboride), 2.01% indium tin oxide (surface-modified indium tin oxide), 95.00% polymer resin (polyethylene) and 2.00% additives (antioxidant, lubricant and plasticizer in a mass ratio of 1:1:1), and the thermal insulation film is a one-layer structure with a thickness of 1 mm.

[0055] The preparation method of the above thermal insulation film is as follows:

[0056] Preparation of surface-modified lanthanum hexaboride: Weigh 100 parts of lanthanum hexaboride (particle size 0.05 μm) and 1000 parts of anhydrous ethanol, disperse them in an ultrasonic cell crusher for 30 minutes, adjust the pH to 3 with nitric acid (mass fraction 66%), add 2 parts of silane coupling agent (vinyl triethoxysilane) and stir at room temperature for 2 hours, centrifuge at 5000 r / min to remove particles with larger particle size, and dry in a vacuum oven at 80°C for 24 hours to obtain surface-modified lanthanum hexaboride.

[0057] Preparation of surface-modified indium tin oxide: Weigh 100 parts of indium tin oxide (particle size of 0.05 μm) and 1000 mL of anhydrous ethanol, disperse them in an ultrasonic cell crusher for 30 minutes, adjust the pH to 3 with nitric acid (mass fraction 66%), add 2 parts of silane coupling agent (vinyl triethoxysilane) and stir at room temperature for 2 hours, centrifuge at 5000 r / min to remove particles with larger particle size, and dry in a vacuum oven at 80°C for 24 hours to obtain surface-modified indium tin oxide.

[0058] (1) 52 parts of the surface-modified lanthanum hexaboride, 106 parts of the surface-modified indium tin oxide, 35 parts of an antioxidant (2,6-di-tert-butyl-4-methylphenol), 35 parts of a lubricant (liquid paraffin), 35 parts of a plasticizer (epoxidized soybean oil) and 1000 parts of polyethylene (Yanshan Petrochemical 3300F) were mixed uniformly in a high-speed mixer and added to a twin-screw extruder. The temperature of the heating zone of the extruder was 200°C, the temperature of the head heating extrusion zone was 180°C, and the speed of the barrel screw was controlled at 50 r / min. After extrusion, the mixture was cooled with cooling water, cut with a cutter, and dried in a vacuum oven at 80°C for 24 hours to obtain a thermal insulation masterbatch.

[0059] (2) 480 parts of the thermal insulation masterbatch obtained in step (1) and 1520 parts of polyethylene (Yanshan Petrochemical 3300F) were mixed evenly in a vacuum feeder and added to a single screw extruder. The temperature of the heating zone of the extruder was 190°C, the temperature of the head heating extrusion zone was 200°C, the speed of the barrel screw was controlled at 40r / min, and the melt was extruded and plasticized into a melt. The melt was passed through a flow channel to a die head and cast by a casting machine to obtain the thermal insulation film.

[0060] Example 2

[0061] The present embodiment provides a thermal insulation film and a preparation method thereof, wherein the thermal insulation film includes the following components in percentage by mass: 0.54% rare earth hexaboride (surface-modified neodymium hexaboride), 4.89% antimony tin oxide (surface-modified antimony tin oxide), 92.44% polymer resin (polyvinyl chloride) and 2.13% additives (antioxidant, lubricant and plasticizer in a mass ratio of 1:1:1), and the thermal insulation film is a one-layer structure with a thickness of 0.06 mm.

[0062] The preparation method of the above thermal insulation film is as follows:

[0063] Preparation of surface-modified neodymium hexaboride: Weigh 100 parts of neodymium hexaboride (particle size 0.2 μm) and 1000 parts of anhydrous ethanol, disperse them in an ultrasonic cell crusher for 30 minutes, adjust the pH to 3 with nitric acid (mass fraction 66%), add 4 parts of silane coupling agent (vinyl triethoxysilane) and stir at room temperature for 2 hours, centrifuge at 5000 r / min to remove particles with larger particle size, and dry in a vacuum oven at 80°C for 24 hours to obtain surface-modified neodymium hexaboride.

[0064] Preparation of surface-modified antimony tin oxide: Weigh 100 parts of antimony tin oxide (particle size of 0.2 μm) and 1000 parts of anhydrous ethanol, disperse them in an ultrasonic cell crusher for 30 minutes, adjust the pH to 3 with nitric acid (mass fraction 66%), add 2 parts of silane coupling agent (vinyl triethoxysilane) and stir at room temperature for 2 hours, centrifuge at 5000 r / min to remove particles with larger particle size, and dry in a vacuum oven at 80°C for 24 hours to obtain surface-modified antimony tin oxide.

[0065] (1) 28 parts of the surface-modified neodymium hexaboride, 18.3 parts of an antioxidant (2,6-di-tert-butyl-4-methylphenol), 18.3 parts of a lubricant (liquid paraffin), 18.3 parts of a plasticizer (epoxidized soybean oil) and 500 parts of polyvinyl chloride (S-1000 of Qilu Petrochemical) were mixed uniformly in a high-speed mixer and added to a twin-screw extruder. The temperature of the heating zone of the extruder was 200°C, the temperature of the head heating extrusion zone was 180°C, and the speed of the barrel screw was controlled at 50 r / min. After extrusion, the mixture was cooled with cooling water, cut with a cutter, and dried in a vacuum oven at 80°C for 24 hours to obtain a thermal insulation masterbatch of neodymium hexaboride.

[0066] 250 parts of the above-mentioned surface-modified antimony tin oxide, 18.3 parts of antioxidant (2,6-di-tert-butyl-4-methylphenol), 18.3 parts of lubricant (liquid paraffin), 18.3 parts of plasticizer (epoxidized soybean oil) and 500 parts of polyvinyl chloride (Qilu Petrochemical S-1000) were mixed evenly in a high-speed mixer, and added to a twin-screw extruder. The temperature of the heating zone of the extruder was 200°C, the temperature of the head heating extrusion zone was 180°C, and the speed of the barrel screw was controlled at 50r / min. After extrusion, it was cooled with cooling water, cut with a cutter, and placed in a vacuum oven at 80°C for 24 hours to obtain an insulating masterbatch of antimony tin oxide.

[0067] (2) 200 parts of the thermal insulation masterbatch of neodymium hexaboride obtained in step (1), 280 parts of the thermal insulation masterbatch of antimony tin oxide obtained in step (1) and 1300 parts of polyvinyl chloride (S-1000 of Qilu Petrochemical) are mixed evenly in a vacuum feeder and then added to a single screw extruder. The temperature of the heating zone of the extruder is 190°C, the temperature of the head heating extrusion zone is 200°C, the speed of the barrel screw is controlled to 40r / min, and the melt is extruded and plasticized into a melt, which is then transported through a flow channel to a die head and blown by a film blowing machine to obtain the thermal insulation film.

[0068] Example 3

[0069] The present embodiment provides a thermal insulation film and a preparation method thereof, wherein the thermal insulation film includes the following components in percentage by mass: 0.50% rare earth hexaboride (surface-modified cerium hexaboride), 3.12% indium tin oxide (surface-modified indium tin oxide), 3.12% antimony tin oxide (surface-modified antimony tin oxide), 91.62% polymer resin and 1.64% additives (thermal stabilizer and lubricant in a mass ratio of 1:1). The thermal insulation film has a three-layer structure and a thickness of 2 mm.

[0070] The preparation method of the above thermal insulation film is as follows:

[0071] Preparation of surface-modified cerium hexaboride: Weigh 100 parts of cerium hexaboride (particle size 0.01 μm) and 1000 parts of anhydrous ethanol, disperse them in an ultrasonic cell crusher for 30 minutes, adjust the pH to 3 with nitric acid (mass fraction 66%), add 10 parts of silane coupling agent (vinyl triethoxysilane) and stir at room temperature for 2 hours, centrifuge at 5000 r / min to remove particles with larger particle size, and dry in a vacuum oven at 80°C for 24 hours to obtain surface-modified cerium hexaboride.

[0072] Preparation of surface-modified indium tin oxide: Weigh 100 parts of indium tin oxide (particle size 0.01 μm) and 1000 parts of anhydrous ethanol, disperse them in an ultrasonic cell crusher for 30 minutes, adjust the pH to 3 with nitric acid (mass fraction 66%), add 2 parts of silane coupling agent (vinyl triethoxysilane) and stir at room temperature for 2 hours, centrifuge at 5000 r / min to remove particles with larger particle size, and dry in a vacuum oven at 80°C for 24 hours to obtain surface-modified indium tin oxide.

[0073] Preparation of surface-modified antimony tin oxide: Weigh 100 parts of antimony tin oxide (particle size 0.01 μm) and 1000 parts of anhydrous ethanol, disperse them in an ultrasonic cell crusher for 30 minutes, adjust the pH to 3 with nitric acid (mass fraction 66%), add 2 parts of silane coupling agent (vinyl triethoxysilane) and stir at room temperature for 2 hours, centrifuge at 5000 r / min to remove particles with larger particle size, and dry in a vacuum oven at 80°C for 24 hours to obtain surface-modified antimony tin oxide.

[0074] (1) 32 parts of the surface-modified cerium hexaboride, 200 parts of the surface-modified indium tin oxide, 200 parts of the surface-modified antimony tin oxide, 52.5 parts of a heat stabilizer (acetylacetone diphenylphenol), 52.5 parts of a lubricant (liquid paraffin) and 1000 parts of polypropylene (F5606 of Yanshan Petrochemical) were mixed uniformly in a high-speed mixer, and added to a twin-screw extruder. The temperature of the heating zone of the extruder was 180°C, the temperature of the head heating extrusion zone was 200°C, and the speed of the barrel screw was controlled at 50 r / min. After extrusion, the mixture was cooled with cooling water, cut with a cutter, and dried in a vacuum oven at 80°C for 24 hours to obtain a thermal insulation masterbatch.

[0075] (2) 480 parts of the thermal insulation masterbatch prepared in step (1) and 420 parts of polyethylene (3300F from Yanshan Petrochemical) were mixed uniformly in a vacuum feeder to obtain a blend;

[0076] 550 parts of polyethylene (Yanshan Petrochemical 3300F), the above-mentioned blend, and 550 parts of polyethylene (Yanshan Petrochemical 3300F) are respectively added into three single-screw extruders of a three-layer extrusion casting machine, so that the blend is located in the middle layer and extruded. The temperature of the heating zone of the extruder is 190°C, the temperature of the head heating extrusion zone is 200°C, the speed of the barrel screw is controlled at 40r / min, and the melt is extruded and plasticized into a melt, and then the melt is transported through the flow channel to the die head and cast to obtain the thermal insulation film.

[0077] Example 4

[0078] This embodiment provides a thermal insulation film and a preparation method thereof, which differs from Embodiment 1 in that the mass percentage of the surface-modified rare earth hexaboride is 0.01%, and the mass percentage of the polymer resin (polyethylene) is 95.98%. In the preparation method of the thermal insulation film, in step (1), the mass of the surface-modified lanthanum hexaboride is adjusted to 0.5 parts, and the mass of the polyethylene is adjusted to 1052.5 parts, and the rest is the same as Embodiment 1.

[0079] Example 5

[0080] This embodiment provides a thermal insulation film and a preparation method thereof, which differs from Embodiment 1 in that the mass percentage of the surface-modified rare earth hexaboride is 4.94%, and the mass percentage of the polymer resin (polyethylene) is 91.05%. In the preparation method of the thermal insulation film, in step (1), the mass of the surface-modified lanthanum hexaboride is adjusted to 260 parts, and the mass of the polyethylene is adjusted to 792 parts, and the rest is the same as Embodiment 1.

[0081] Example 6

[0082] This embodiment provides a thermal insulation film and a preparation method thereof, which differs from Embodiment 1 in that the mass percentage of the surface-modified indium tin oxide is 0.10%, and the mass percentage of the polymer resin (polyethylene) is 96.92%. In the preparation method of the thermal insulation film, in step (1), the mass of the surface-modified indium tin oxide is adjusted to 5 parts, and the mass of the polyethylene is adjusted to 1101 parts, and the rest is the same as Embodiment 1.

[0083] Example 7

[0084] This embodiment provides a thermal insulation film and a preparation method thereof, which differs from Embodiment 1 in that the mass percentage of the surface-modified indium tin oxide is 9.69%, and the mass percentage of the polymer resin (polyethylene) is 87.33%. In the preparation method of the thermal insulation film, in step (1), the mass of the surface-modified indium tin oxide is adjusted to 510 parts, and the mass of the polyethylene is adjusted to 596 parts, and the rest is the same as Embodiment 1.

[0085] Example 8

[0086] This embodiment provides a thermal insulation film and a preparation method thereof, which differs from Embodiment 1 in that the surface-modified lanthanum hexaboride is replaced with an equal mass of non-surface-modified lanthanum hexaboride (particle size of 0.05 μm), and the surface-modified indium tin oxide is replaced with an equal mass of non-surface-modified indium tin oxide (particle size of 0.05 μm), and the rest is the same as Embodiment 1.

[0087] Comparative Example 1

[0088] This comparative example provides a thermal insulation film and a preparation method thereof, which differs from Example 1 in that the thermal insulation film does not include surface-modified indium tin oxide, and the mass percentage of the surface-modified lanthanum hexaboride is 3%. In the preparation method of the thermal insulation film, step (1) does not add surface-modified indium tin oxide, and the mass of the surface-modified lanthanum hexaboride is adjusted to 158 parts, and the rest is the same as Example 1.

[0089] Comparative Example 2

[0090] This comparative example provides a thermal insulation film and a preparation method thereof, which differs from Example 1 in that the thermal insulation film does not include surface-modified lanthanum hexaboride, and the mass percentage of the surface-modified indium tin oxide is 3%. In the preparation method of the thermal insulation film, step (1) does not add surface-modified lanthanum hexaboride, and the mass of the surface-modified indium tin oxide is adjusted to 158 parts, and the rest is the same as Example 1.

[0091] The following performance tests were performed on the thermal insulation films provided in the above embodiments and comparative examples.

[0092] (1) Infrared light blocking band, infrared light transmittance and visible light transmittance: tested using UV-visible-near infrared absorption spectrometer.

[0093] (2) Infrared light insulation test: Cut the thermal insulation film into 12 cm × 12 cm sheets and stick them on the surface of a thermal insulation box of 25 cm × 10 cm × 10 cm. Use a 250 W infrared lamp with a distance of 30 cm between it and the infrared light blocking film to irradiate. After 30 minutes, record the temperature difference between the air temperature in the thermal insulation box with the thermal insulation film and the air temperature in the thermal insulation box without the thermal insulation film.

[0094] (3) Natural light insulation test: The thermal insulation film was used in an agricultural greenhouse. The agricultural greenhouse was made by cutting the thermal insulation film into 12 cm × 12 cm sheets and making a hollow greenhouse-like device. The length, width and height of the hollow greenhouse-like device were 4 cm × 4 cm and 4 cm respectively. The device was exposed to light at 36°C in summer from 10 am to 2 pm. The light intensity was 7500 lux. The temperature of the agricultural greenhouse with polyethylene film was used as a control sample. The temperature difference was obtained by subtracting the temperature of the hollow greenhouse-like plastic device with the thermal insulation film from the temperature of the hollow greenhouse-like plastic device with the polyethylene film at 2 pm.

[0095] The test results are shown in Table 1.

[0096] Table 1

[0097]

[0098]

[0099] In Table 1, “ / ” means that the test was not conducted.

[0100] According to the test results in Table 1, the infrared light blocking band of the thermal insulation film provided in Examples 1-8 is 700-2500nm, the visible light transmittance is 50.5%-84.5%, the temperature difference of the infrared light thermal insulation test is -9.8 to -2.2°C, and the temperature difference of the natural light thermal insulation test is -8.5 to -1.7°C. The infrared light blocking band of the thermal insulation film provided in Examples 1-3 is 700-2500nm, the visible light transmittance is 61.9%-71.7%, the temperature difference of the infrared light thermal insulation test is -9.2 to -6.4°C, and the temperature difference of the natural light thermal insulation test is -8.0 to -5.0°C.

[0101] Compared with Example 1, it can be seen that if the mass percentage of rare earth hexaboride is low (Example 4), the absolute values ​​of the temperature difference in the infrared light thermal insulation test and the absolute values ​​of the temperature difference in the natural light thermal insulation test both decrease, and the thermal insulation performance of the thermal insulation film decreases; if the mass percentage of rare earth hexaboride is high (Example 5), the infrared light transmittance and the visible light transmittance both decrease, and the visible light transmittance decreases significantly, proving that the thermal insulation film with a mass percentage of rare earth hexaboride of 0.5-1% has better performance.

[0102] Compared with Example 1, it can be seen that if the mass percentage of indium tin oxide is low (Example 6), the absolute values ​​of the temperature difference in the infrared light thermal insulation test and the absolute values ​​of the temperature difference in the natural light thermal insulation test both decrease, and the thermal insulation performance of the thermal insulation film decreases; if the mass percentage of indium tin oxide is high (Example 7), the absolute values ​​of the temperature difference in the infrared light thermal insulation test and the absolute values ​​of the temperature difference in the natural light thermal insulation test are similar to those in Example 1, but the visible light transmittance is greatly reduced, proving that the thermal insulation film with a mass percentage of antimony tin oxide or indium tin oxide of 0.5 to 5% has better performance.

[0103] Compared with Example 1, it can be seen that if the surface-modified lanthanum hexaboride is replaced by the same mass of non-surface-modified lanthanum hexaboride, and the surface-modified indium tin oxide is replaced by the same mass of non-surface-modified indium tin oxide (Example 8), the absolute values ​​of the temperature difference in the infrared light thermal insulation test and the absolute values ​​of the temperature difference in the natural light thermal insulation test both decrease, and the thermal insulation performance of the thermal insulation film decreases, which proves that the thermal insulation film prepared by adding surface-modified rare earth hexaboride, surface-modified antimony tin oxide and / or surface-modified indium tin oxide has better performance.

[0104] Compared with Example 1, it can be seen that if indium tin oxide is not added (Comparative Example 1), the infrared light blocking band of the thermal insulation film becomes narrower, the absolute value of the temperature difference in the infrared light thermal insulation test and the absolute value of the temperature difference in the natural light thermal insulation test both decrease, and the thermal insulation performance of the thermal insulation film decreases; if rare earth hexaboride is not added (Comparative Example 2), the infrared light blocking band of the thermal insulation film becomes narrower, the absolute value of the temperature difference in the infrared light thermal insulation test and the absolute value of the temperature difference in the natural light thermal insulation test both decrease, and the thermal insulation performance of the thermal insulation film decreases, which proves that the thermal insulation film obtained by compounding rare earth hexaboride with antimony tin oxide and / or indium tin oxide has a wide infrared light blocking band and strong thermal insulation ability.

[0105] The applicant declares that the present invention uses the above-mentioned embodiments to illustrate a thermal insulation film and its preparation method and application, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A thermal insulation film, characterized in that: The thermal insulation film comprises rare earth hexaboride, antimony tin oxide and / or indium tin oxide, polymer resin and additives.

2. The thermal insulation film according to claim 1, characterized in that: The thermal insulation film has a one-layer or at least two-layer structure; Preferably, the rare earth hexaboride and antimony tin oxide and / or indium tin oxide are simultaneously located in any one layer of the thermal insulation film of the at least two-layer structure; Preferably, the thickness of the thermal insulation film is 0.06-2 mm.

3. The thermal insulation film according to claim 1 or 2, characterized in that: The rare earth hexaboride is a surface-modified rare earth hexaboride, the antimony tin oxide is a surface-modified antimony tin oxide, and the indium tin oxide is a surface-modified indium tin oxide; Preferably, the surface modification method includes any one of electrochemical modification, physical modification or chemical modification, or a combination of at least two thereof; Preferably, the physical modification method includes any one of magnetic stirring method, ball milling method, ultrasonic dispersion method or a combination of at least two thereof; Preferably, the surface modification is physical modification and chemical modification performed sequentially; Preferably, the chemical modification method includes any one or a combination of at least two of coupling agent modification, surfactant modification, organic acid modification or organic oligomer modification; Preferably, the coupling agent includes a silane coupling agent and / or a titanate coupling agent.

4. The thermal insulation film according to claim 3, characterized in that: The mass of the coupling agent in the surface-modified rare earth hexaboride is 0.2% to 10% of the mass of the rare earth hexaboride; Preferably, the mass of the coupling agent in the surface-modified antimony tin oxide is 0.2% to 10% of the mass of the antimony tin oxide; Preferably, the mass of the coupling agent in the surface-modified indium tin oxide is 0.2% to 10% of the mass of the indium tin oxide.

5. The thermal insulation film according to any one of claims 1 to 4, characterized in that The rare earth hexaboride includes any one of neodymium hexaboride, gadolinium hexaboride, praseodymium hexaboride, lanthanum hexaboride, cerium hexaboride or samarium hexaboride, or a combination of at least two thereof; Preferably, the particle sizes of the rare earth hexaboride, antimony tin oxide and indium tin oxide are each independently 0.01 to 200 μm; Preferably, based on the total mass of the thermal insulation film being 100%, the mass percentage of the rare earth hexaboride is 0.01% to 5%, and more preferably 0.5% to 1%; Preferably, based on the total mass of the thermal insulation film being 100%, the mass percentage of the antimony tin oxide is 0.1% to 10%, and more preferably 0.5% to 5%; Preferably, based on the total mass of the thermal insulation film being 100%, the mass percentage of the indium tin oxide is 0.1% to 10%, and more preferably 0.5% to 5%.

6. The thermal insulation film according to any one of claims 1 to 5, characterized in that The polymer resin includes one or a combination of at least two of polyethylene, polypropylene, polyethylene terephthalate, polyethylene elastomer, thermoplastic polyurethane, ethylene-vinyl alcohol copolymer, nylon, polyvinyl chloride or ethylene-vinyl acetate copolymer; Preferably, the mass percentage of the polymer resin in the thermal insulation film is 80% to 99%, and more preferably 90% to 95%.

7. The thermal insulation film according to any one of claims 1 to 6, characterized in that The auxiliary agent includes any one or a combination of at least two of an antioxidant, an ultraviolet absorber, a nucleating agent, a plasticizer, a toughening agent, a heat stabilizer, a dispersant, a lubricant, a colorant, a light stabilizer or an antistatic agent; Preferably, the mass percentage of the antioxidant, ultraviolet absorber, nucleating agent, plasticizer, toughening agent, heat stabilizer, dispersant, lubricant, colorant, light stabilizer or antistatic agent in the thermal insulation film is independently 0.1% to 1%.

8. The method for preparing a thermal insulation film according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) preparing a thermal insulation masterbatch from rare earth hexaboride, antimony tin oxide and / or indium tin oxide, a polymer resin and an additive; (2) Mixing the polymer resin and the thermal insulation masterbatch obtained in step (1), extruding, and molding to obtain the thermal insulation film.

9. The preparation method according to claim 8, characterized in that: The step (1) specifically comprises mixing rare earth hexaboride, antimony tin oxide and / or indium tin oxide, polymer resin and additives, and extruding to prepare a thermal insulation masterbatch; Preferably, the step (1) specifically comprises mixing rare earth hexaboride, polymer resin and additives, and extruding to prepare thermal insulation masterbatch of rare earth hexaboride; mixing antimony tin oxide and / or indium tin oxide, polymer resin and additives, and extruding to prepare thermal insulation masterbatch of antimony tin oxide and / or indium tin oxide; Preferably, in step (2), based on the total mass of the polymer resin and the thermal insulation masterbatch as 100%, the mass percentage of the thermal insulation masterbatch is 1% to 20%; Preferably, in step (2), the molding comprises any one of extrusion molding, blow molding, calendering molding, cast molding or stretching molding.

10. Use of the thermal insulation film according to any one of claims 1 to 7 in thermal insulation products.

Images