A high temperature resistant film

Abstract

The present invention provides a high temperature resistant film, the high temperature resistant film comprises a TPU layer and a dry PU coating which are stacked in sequence; or, the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer and a dry PU coating which are stacked in sequence; or, the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer, a TPU layer and a dry PU coating which are stacked in sequence; or, the high temperature resistant film comprises a TPU layer, a knitted sandwich cloth layer, an adhesive layer and a TPU layer which are stacked in sequence; or, the high temperature resistant film comprises a TPU layer, a knitted sandwich cloth layer, an adhesive layer, a high temperature resistant PU layer and a TPU layer which are stacked in sequence; the raw materials for preparing the TPU layer include thermoplastic polyester, polyaryletherketone, inorganic nanoparticles, a film-forming aid and an antioxidant. The high temperature resistant film of the present invention has excellent high temperature resistance, wear resistance and scratch resistance, and can be used for the back plate of a mobile phone case.

Description

Technical Field

[0001] The invention belongs to the field of polymer materials and relates to a high temperature resistant film. Background Art

[0002] In people's daily life, various film products are used. For example, with the improvement of people's living standards, more and more fast-moving consumer foods have appeared. These fast-moving consumer foods use food packaging films during storage and transportation. Food packaging films are used to prevent and prolong food spoilage. At present, many fast-moving consumer foods do not need to be removed from the packaging when heated, which puts high demands on the high temperature resistance of film materials.

[0003] In order to prevent the product surface from being damaged during product transportation and processing, a protective film is also used on the product surface. However, the protective film may be exposed to sunlight for a long time during transportation, and may be exposed to high temperature environment during processing, which requires the protective film to be resistant to high temperature.

[0004] When the film is used in agricultural fields such as plastic greenhouses, in addition to meeting the requirements of high mechanical strength and good anti-aging properties, the film also needs to be resistant to high temperatures to prevent the film from decomposing due to long-term outdoor use.

[0005] The molded product for the back panel of the mobile phone case needs to have excellent high temperature resistance. The back panel of the mobile phone case is generally formed by one-time stamping, and it needs to withstand 3s-10s at 180°C. This requires the molded product to withstand 180°C high temperature / 3s-10s. When some existing high temperature resistant films are used for the back panel of the mobile phone case, their high temperature resistance usually does not meet the requirements.

[0006] CN112060707A discloses a composite high temperature resistant film, which relates to the technical field of composite films, including an inner packaging layer, a heat insulation layer, a transition layer, a buffer layer and an outer packaging layer. The heat insulation layer is connected to the inner packaging layer and the transition layer, and the buffer layer is connected to the transition layer and the outer packaging layer through adhesives. The inner packaging layer adopts a cast polypropylene film with a thickness of 20-50μm, and the heat insulation layer includes an outer high-pressure low-density polyethylene film layer and hollow glass microbeads located between the high-pressure low-density polyethylene film layers. The transition layer adopts an aluminum foil with a thickness of 5-20μm, and the buffer layer adopts an ethylene-vinyl alcohol copolymer film bag filled with nitrogen. The outer packaging layer adopts a polyester film with a thickness of 2-25μm. The invention is aimed at a composite film used for covering or packaging protection of food. After rationally designing the inner packaging layer, the heat insulation layer, the transition layer, the buffer layer and the outer packaging layer and the materials used in the corresponding layers, the packaging composite film has the ability of heat insulation, light blocking, collision prevention and extrusion prevention. However, the high temperature resistance and mechanical properties of the composite high temperature resistant membrane of the invention need to be further improved, and the preparation process is relatively complicated.

[0007] CN104401087A discloses a high temperature resistant anti-blue light protective film, which includes, from top to bottom, a first separation membrane layer, a first base membrane layer, a high temperature resistant membrane layer, a second base membrane layer, an anti-blue light membrane layer and a second separation membrane layer, wherein the first separation membrane layer is connected to the upper surface of the first base membrane layer by an adhesive; the high temperature resistant membrane layer is arranged between the first base membrane layer and the second base membrane layer, and is composed of high temperature resistant glue; the anti-blue light membrane layer is arranged between the second base membrane layer and the second separation membrane layer, and is composed of anti-blue light glue; the anti-blue light membrane layer is connected to the second separation membrane layer by an adhesive. The invention blocks blue light by absorbing and converting blue light emitted by luminous light sources such as flat panel displays, LED neon lights, fluorescent lights, etc., greatly reducing the damage of blue light to the eyes and protecting human eyes; it also has high heat resistance, and is waterproof, oil-proof, corrosion-resistant, and scratch-resistant. However, the high temperature resistance of the high temperature resistant anti-blue light protective film of the invention needs to be further improved.

[0008] Therefore, in the art, it is desired to develop a high temperature resistant film which not only has good high temperature resistance but also has excellent mechanical properties, wear resistance and scratch resistance, and can be used for the back plate of a mobile phone case. Summary of the invention

[0009] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a high temperature resistant film. The high temperature resistant film of the present invention not only has good high temperature resistance, but also has excellent mechanical properties, wear resistance and scratch resistance, can be used in processes such as impact molding, and can withstand high temperatures of 180°C / 3s-10s, and can be used to prepare the back plate of a mobile phone case through a one-time stamping molding process.

[0010] To achieve this object, the present invention adopts the following technical solutions:

[0011] In a first aspect, the present invention provides a high temperature resistant film, the high temperature resistant film comprising a TPU layer and a dry PU coating layer stacked in sequence;

[0012] Alternatively, the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer and a dry PU coating layer stacked in sequence;

[0013] Alternatively, the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer, a TPU layer and a dry PU coating layer stacked in sequence;

[0014] Alternatively, the high temperature resistant film comprises a TPU layer, a knitted sandwich cloth layer, an adhesive layer and a TPU layer which are stacked in sequence;

[0015] Alternatively, the high temperature resistant film comprises a TPU layer, a knitted sandwich cloth layer, an adhesive layer, a high temperature resistant PU layer and a TPU layer which are stacked in sequence;

[0016] The raw materials for preparing the TPU layer include thermoplastic polyester, polyaryletherketone, inorganic nanoparticles, film-forming aid and antioxidant.

[0017] In the present invention, the structure of the high temperature resistant film can be any one of the five structures mentioned above. In each structure, a TPU layer is contained, and in the TPU layer, thermoplastic polyester and polyaryletherketone are used in synergy, so that the prepared TPU layer has both excellent high temperature resistance and excellent mechanical properties. Polyaryletherketone contains rigid benzene rings in its molecular structure, which has excellent high temperature resistance, and thermoplastic polyester has good mechanical properties. The two are used in combination, so that the prepared TPU layer has the advantages of both. At the same time, the addition of inorganic nanoparticles can further improve the high temperature resistance of the TPU layer. In addition, polyaryletherketone itself has flame retardancy, and the TPU layer can be made flame retardant without the need to add additional flame retardants, thereby making the high temperature resistant film have excellent high temperature resistance.

[0018] In addition, in the present invention, both the high temperature resistant PU layer and the adhesive layer are resistant to high temperatures, which can further improve the high temperature resistance of the high temperature resistant film.

[0019] It should be noted that the present invention does not impose any specific restrictions on the thickness of each layer of the high temperature resistant films of the above five structures, and it can be set according to the specific needs of customers.

[0020] In the present invention, the high temperature resistant film refers to a film that can withstand a high temperature of 180°C for 3s-10s.

[0021] Preferably, the raw materials for preparing the TPU layer include the following components in parts by weight:

[0022]

[0023] Preferably, in the preparation raw materials of the TPU layer, the amount of thermoplastic polyester used can be 60-80 parts, for example, 60 parts, 62 parts, 63 parts, 65 parts, 68 parts, 70 parts, 72 parts, 73 parts, 75 parts, 78 parts or 80 parts, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] Preferably, in the raw materials for preparing the TPU layer, the amount of polyaryletherketone can be 3-8 parts, for example 3 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] If the amount of polyaryletherketone is too small, the high temperature resistance of the high temperature resistant film will be reduced. If the amount of polyaryletherketone is too large, the elongation at break of the high temperature resistant film will be reduced.

[0026] Preferably, in the preparation raw materials of the TPU layer, the amount of inorganic nanoparticles used can be 0.5-5 parts, for example, 0.5 parts, 0.8 parts, 1 parts, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0027] If the amount of inorganic nanoparticles used is too small, the high temperature resistance of the high temperature resistant film will decrease. If the amount of inorganic nanoparticles used is too large, agglomeration will occur and the elongation at break of the high temperature resistant film will decrease.

[0028] Preferably, in the preparation raw materials of the TPU layer, the amount of the film-forming aid can be 5-10 parts, for example, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, 9.5 parts or 10 parts, etc., but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0029] Preferably, in the preparation raw materials of the TPU layer, the amount of antioxidant used can be 1-5 parts, for example, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts or 5 parts, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0030] Preferably, the thermoplastic polyester comprises polyethylene terephthalate and / or polybutylene terephthalate.

[0031] As a preferred technical solution of the present invention, the thermoplastic polyester is selected from polyethylene terephthalate and / or polybutylene terephthalate. The thermoplastic polyester has both a rigid structure and good mechanical properties. The thermoplastic polyester and polyaryletherketone are compounded so that the prepared film has excellent comprehensive properties.

[0032] Preferably, the polyaryletherketone comprises any one of polyetheretherketone (PEEK), polyetherketone (PEK), polyetherketoneketone (PEKK) or polyetherketoneetherketoneketone (PEKEKK) or a combination of at least two thereof, preferably polyetherketone. Compared with other polyaryletherketones, polyetherketone has both good high temperature resistance and suitable mechanical properties.

[0033] Preferably, the particle size of the inorganic nanoparticles is 10-200nm, for example 10nm, 20nm, 30nm, 50nm, 80nm, 100nm, 110nm, 120nm, 130nm, 150nm, 180nm or 200nm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] Preferably, the inorganic nanoparticles include any one of nano-silicon dioxide, nano-titanium dioxide, nano-aluminum oxide or nano-zinc oxide, or a combination of at least two thereof.

[0035] Preferably, the film-forming aid includes any one of ethylene glycol, propylene glycol, hexylene glycol, dodecyl alcohol ester, hexylene glycol butyl ether acetate or 3-ethoxyethyl propionate, or a combination of at least two thereof.

[0036] Preferably, the antioxidant includes any one of antioxidant 1010, antioxidant 1076, antioxidant 168 or antioxidant 164, or a combination of at least two thereof.

[0037] Preferably, the raw materials for preparing the TPU layer further include 0.1-1 parts (e.g., 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 parts, etc.) of thermal stabilizer in parts by weight.

[0038] Preferably, the heat stabilizer includes any one of trimethyl phosphate, barium stearate or magnesium stearate, or a combination of at least two thereof.

[0039] Preferably, the raw materials for preparing the dry PU coating include the following components in parts by weight:

[0040] 90-110 parts of polycarbonate polyurethane;

[0041] 3-5 parts of isocyanate curing agent;

[0042] 80-100 parts of solvent.

[0043] Preferably, in the raw materials for preparing the dry PU coating, the amount of polycarbonate polyurethane used can be 90 parts, 92 parts, 93 parts, 95 parts, 98 parts, 100 parts, 102 parts, 103 parts, 105 parts, 108 parts or 110 parts, etc.

[0044] Preferably, in the raw materials for preparing the dry PU coating, the amount of isocyanate curing agent used can be 3 parts, 4 parts or 5 parts, etc.

[0045] Preferably, in the raw materials for preparing the dry PU coating, the amount of solvent used can be 80 parts, 82 parts, 83 parts, 85 parts, 88 parts, 90 parts, 92 parts, 93 parts, 95 parts, 98 parts or 100 parts, etc.

[0046] Preferably, the polycarbonate polyurethane comprises a waterborne organosilicon-modified polycarbonate polyurethane resin.

[0047] Preferably, the isocyanate curing agent includes any one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate, or a combination of at least two thereof.

[0048] Preferably, the solvent includes any one of acetone, toluene or xylene.

[0049] Preferably, the raw materials for preparing the high temperature resistant PU layer include the following components in parts by weight:

[0050] Polyurethane resin 80-110 parts;

[0051] 5-10 parts of nano-alumina;

[0052] Solvent 90-110 parts.

[0053] In the present invention, the raw materials for preparing the high temperature resistant PU layer include nano-aluminum oxide, thereby improving the high temperature resistance of the high temperature resistant PU layer.

[0054] Preferably, in the raw materials for preparing the high temperature resistant PU layer, the amount of polyurethane resin used can be 80 parts, 82 parts, 83 parts, 85 parts, 88 parts, 90 parts, 92 parts, 93 parts, 95 parts, 98 parts, 100 parts, 102 parts, 103 parts, 105 parts, 108 parts or 110 parts, etc.

[0055] Preferably, in the raw materials for preparing the high temperature resistant PU layer, the amount of nano-aluminum oxide can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.

[0056] Preferably, in the raw materials for preparing the high temperature resistant PU layer, the amount of solvent used can be 90 parts, 92 parts, 93 parts, 95 parts, 98 parts, 100 parts, 102 parts, 103 parts, 105 parts, 108 parts or 110 parts, etc.

[0057] Preferably, the particle size of the nano-aluminum oxide is 30-60 nm, for example, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm or 60 nm.

[0058] Preferably, the solvent includes any one of acetone, toluene or xylene.

[0059] Preferably, the adhesive of the adhesive layer comprises a silicone rubber adhesive.

[0060] In the present invention, the adhesive of the adhesive layer is selected from silicone rubber adhesive, so that the adhesive layer also has excellent high temperature resistance.

[0061] The present invention does not limit the preparation method of the high temperature resistant film, and the high temperature resistant film can be prepared by a film preparation method commonly used in the prior art. For example, the TPU layer can be prepared by a casting process, and the high temperature resistant PU layer and the dry PU coating can both be prepared by a dry process. When the high temperature resistant film includes a knitted sandwich fabric layer, it can be integrally formed with the TPU layer by a casting process.

[0062] For example, when the high temperature resistant film includes a TPU layer and a dry PU coating layer stacked in sequence, the preparation method thereof includes:

[0063] (1) mixing the raw materials for preparing the TPU layer in a formula amount, plasticizing and melting at 120-160° C., extruding through a T-shaped structure forming die, and casting in a sheet shape onto the roller surface of a steadily rotating cooling roller, cooling and shaping the film on the cooling roller, and then pulling and trimming to obtain the TPU layer;

[0064] (2) Mixing the raw materials for preparing the dry PU coating in the formulated amount to obtain a mixture, coating the mixture on the surface of the TPU layer, and drying at 90-130° C. to obtain the high temperature resistant film.

[0065] When the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer and a dry PU coating layer stacked in sequence, the preparation method thereof comprises:

[0066] The TPU layer is prepared according to the above-mentioned casting process, the raw materials for preparing the high-temperature resistant PU layer are mixed to obtain a mixture, the mixture is coated on the surface of the TPU layer, dried, and then a dry PU coating is prepared on the high-temperature resistant PU layer according to the above-mentioned dry PU coating preparation method, thereby obtaining the high-temperature resistant film.

[0067] When the high temperature resistant film comprises a TPU layer, a knitted sandwich cloth layer, an adhesive layer and a TPU layer stacked in sequence, the preparation method thereof comprises:

[0068] The TPU layer and the knitted sandwich cloth layer are integrally formed by using a casting process, and then the TPU layer is prepared by using a casting process alone, and then the two are bonded by using an adhesive to obtain the high temperature resistant film.

[0069] For high temperature resistant membranes of other structures, they can be prepared by referring to the preparation methods given above.

[0070] Compared with the prior art, the present invention has at least the following beneficial effects:

[0071] The high temperature resistant film of the present invention may include five structures, each of which contains a TPU layer, and in the TPU layer, thermoplastic polyester and polyaryletherketone are used in coordination, so that the prepared TPU layer has both excellent high temperature resistance and excellent mechanical properties. The molecular structure of polyaryletherketone contains a rigid benzene ring, which has excellent high temperature resistance, and the thermoplastic polyester has good mechanical properties. The two are used in combination, so that the prepared TPU layer has the advantages of both. At the same time, the addition of inorganic nanoparticles can further improve the high temperature resistance of the TPU layer. In addition, polyaryletherketone itself has flame retardancy, and the TPU layer can be made flame retardant without the need to add additional flame retardants, thereby making the high temperature resistant film have excellent high temperature resistance.

[0072] In addition, in the present invention, both the high temperature resistant PU layer and the adhesive layer are resistant to high temperatures, which can further improve the high temperature resistance of the high temperature resistant film. DETAILED DESCRIPTION

[0073] 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.

[0074] The raw material information used in the examples and comparative examples of the present invention is as follows:

[0075] Polyethylene terephthalate: purchased from Dongguan Kaiwan Engineering Plastic Raw Materials Co., Ltd.;

[0076] Polybutylene terephthalate: BASF B6550, Germany;

[0077] Polyetherketone: purchased from Haozheng New Materials Technology (Dongguan) Co., Ltd.

[0078] Polyetherketoneketone: purchased from Hubei Nona Technology Co., Ltd.

[0079] Polyetheretherketone: purchased from Wenzhou Zetai Special Plastic Co., Ltd.

[0080] Waterborne silicone-modified polycarbonate polyurethane resin: purchased from Jining Tangyi Chemical Co., Ltd.;

[0081] Polyurethane resin: purchased from Shanghai Kaiyin Chemical Co., Ltd., NeoRez R 1010;

[0082] Silicone rubber adhesive: purchased from Shandong Xinrunjin Chemical Co., Ltd., 107 silicone rubber.

[0083] Example 1

[0084] In this embodiment, a high temperature resistant film is provided, wherein the high temperature resistant film comprises a TPU layer and a dry PU coating layer stacked in sequence;

[0085] The raw materials for preparing the TPU layer include the following components in parts by weight:

[0086]

[0087]

[0088] Wherein, the thermoplastic polyester is polyethylene terephthalate; the polyaryletherketone is polyetherketone; the inorganic nanoparticles are nanosilicon dioxide with a particle size of 100 nm; the film-forming aid is hexanediol; the antioxidant is antioxidant 1010; the heat stabilizer is trimethyl phosphate;

[0089] The raw materials for preparing the dry PU coating include the following components in parts by weight:

[0090] 100 parts of polycarbonate polyurethane;

[0091] 4 parts of isocyanate curing agent;

[0092] 90 parts of solvent;

[0093] The polycarbonate polyurethane is a water-based silicone-modified polycarbonate polyurethane resin, the isocyanate curing agent is toluene diisocyanate, and the solvent is acetone.

[0094] The preparation method comprises the following steps:

[0095] (1) Mixing the raw materials for preparing the TPU layer in a formula amount, plasticizing and melting at 150° C., extruding through a T-shaped structure forming die, and casting in a sheet shape onto the roller surface of a steadily rotating cooling roller, cooling and shaping the film on the cooling roller, and then pulling and trimming to obtain a TPU layer;

[0096] (2) Mixing the raw materials for preparing the dry PU coating in the formulated amount to obtain a mixture, coating the mixture on the surface of the TPU layer, and drying at 100° C. to obtain the high temperature resistant film.

[0097] Example 2

[0098] In this embodiment, a high temperature resistant film is provided, wherein the high temperature resistant film comprises a TPU layer and a dry PU coating layer stacked in sequence;

[0099] The raw materials for preparing the TPU layer include the following components in parts by weight:

[0100]

[0101] Wherein, the thermoplastic polyester is polyethylene terephthalate; the polyaryletherketone is polyetherketone; the inorganic nanoparticles are nano-titanium dioxide with a particle size of 10 nm; the film-forming aid is dodecyl alcohol ester; the antioxidant is antioxidant 1076;

[0102] The raw materials for preparing the dry PU coating include the following components in parts by weight:

[0103] 90 parts of polycarbonate polyurethane;

[0104] 3 parts of isocyanate curing agent;

[0105] 80 parts of solvent;

[0106] The polycarbonate polyurethane is a water-based silicone-modified polycarbonate polyurethane resin, the isocyanate curing agent is toluene diisocyanate, and the solvent is toluene.

[0107] The preparation method is as in Example 1.

[0108] Example 3

[0109] In this embodiment, a high temperature resistant film is provided, wherein the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer and a dry PU coating layer stacked in sequence;

[0110] The raw materials for preparing the TPU layer include the following components in parts by weight:

[0111]

[0112]

[0113] The thermoplastic polyester is polyethylene terephthalate; the polyaryletherketone is polyetherketone; the inorganic nanoparticles are nano zinc oxide with a particle size of 200 nm; the film-forming aid is ethylene glycol; the antioxidant is antioxidant 168; the heat stabilizer is trimethyl phosphate;

[0114] The raw materials for preparing the dry PU coating include the following components in parts by weight:

[0115] 110 parts of polycarbonate polyurethane;

[0116] 5 parts of isocyanate curing agent;

[0117] 100 parts of solvent;

[0118] Wherein, the polycarbonate polyurethane is a water-based silicone-modified polycarbonate polyurethane resin, the isocyanate curing agent is toluene diisocyanate, and the solvent is toluene;

[0119] The raw materials for preparing the high temperature resistant PU layer include the following components in parts by weight:

[0120] 100 parts of polyurethane resin;

[0121] 8 parts of nano-alumina;

[0122] 100 parts of solvent;

[0123] Wherein, the particle size of nano-alumina is 60nm, and the solvent is toluene.

[0124] The preparation method comprises the following steps:

[0125] The TPU layer is prepared by the casting process of Example 1, the raw materials for preparing the high-temperature resistant PU layer are mixed to obtain a mixture, the mixture is coated on the surface of the TPU layer, and dried at 100°C, and then a dry PU coating is prepared on the surface of the high-temperature resistant PU layer by referring to the preparation method of the dry PU coating in Example 1, thereby obtaining the high-temperature resistant film.

[0126] Example 4

[0127] In this embodiment, a high temperature resistant film is provided, wherein the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer, a TPU layer and a dry PU coating layer stacked in sequence;

[0128] The raw materials for preparing the two TPU layers include the following components in parts by weight:

[0129]

[0130] The thermoplastic polyester is polybutylene terephthalate; the polyaryletherketone is polyetherketone; the inorganic nanoparticles are nano zinc oxide with a particle size of 50 nm; the film-forming aid is hexanediol butyl ether acetate; the antioxidant is antioxidant 1076; the heat stabilizer is barium stearate;

[0131] The raw materials for preparing the dry PU coating include the following components in parts by weight:

[0132] 95 parts of polycarbonate polyurethane;

[0133] 4 parts of isocyanate curing agent;

[0134] 85 parts of solvent;

[0135] Wherein, the polycarbonate polyurethane is a water-based silicone-modified polycarbonate polyurethane resin, the isocyanate curing agent is toluene diisocyanate, and the solvent is acetone;

[0136] The raw materials for preparing the high temperature resistant PU layer include the following components in parts by weight:

[0137] 80 parts of polyurethane resin;

[0138] 5 parts of nano-alumina;

[0139] 90 parts of solvent;

[0140] Wherein, the particle size of nano-aluminum oxide is 40nm, and the solvent is acetone.

[0141] The preparation method comprises the following steps:

[0142] (1) obtaining a TPU layer + a dry PU coating according to the method of Example 1;

[0143] (2) Prepare a TPU layer according to the method of Example 1, then mix the raw materials for preparing the high-temperature resistant PU layer in the formulated amount to obtain a mixture, apply the mixture on the surface of the TPU layer, and then laminate the TPU layer + dry PU coating of step (1) (wherein, the TPU layer in the TPU layer + dry PU coating is laminated with the mixture), and dry at 120°C to obtain the high-temperature resistant film.

[0144] Example 5

[0145] In this embodiment, a high temperature resistant film is provided, wherein the high temperature resistant film comprises a TPU layer, a knitted sandwich cloth layer, an adhesive layer and a TPU layer which are stacked in sequence;

[0146] The raw materials for preparing the two TPU layers include the following components in parts by weight:

[0147]

[0148] The thermoplastic polyester is polybutylene terephthalate; the polyaryletherketone is polyetherketone; the inorganic nanoparticles are nanosilicon dioxide with a particle size of 80 nm; the film-forming aid is hexanediol; the antioxidant is antioxidant 168; the heat stabilizer is magnesium stearate;

[0149] The adhesive of the adhesive layer is a silicone rubber adhesive.

[0150] The preparation method comprises the following steps:

[0151] The TPU layer and the knitted clamping cloth are integrally formed by using a casting process, and then the TPU layer is prepared by using a casting process alone with reference to Example 1, and then the two are bonded by using an adhesive to obtain the high temperature resistant film.

[0152] Example 6

[0153] In this embodiment, a high temperature resistant film is provided, wherein the high temperature resistant film comprises a TPU layer, a knitted sandwich cloth layer, an adhesive layer, a high temperature resistant PU layer and a TPU layer which are stacked in sequence;

[0154] The raw materials for preparing the two TPU layers include the following components in parts by weight:

[0155]

[0156] The thermoplastic polyester is polybutylene terephthalate; the polyaryletherketone is polyetherketone; the inorganic nanoparticles are nano-titanium dioxide with a particle size of 150 nm; the film-forming aid is dodecyl alcohol ester; the antioxidant is antioxidant 1010; the heat stabilizer is barium stearate;

[0157] The raw materials for preparing the high temperature resistant PU layer include the following components in parts by weight:

[0158] 110 parts of polyurethane resin;

[0159] 10 parts of nano-alumina;

[0160] 110 parts of solvent;

[0161] Wherein, the particle size of nano-alumina is 40nm, and the solvent is toluene;

[0162] The adhesive of the adhesive layer is a silicone rubber adhesive.

[0163] The preparation method comprises the following steps:

[0164] (1) The TPU layer and the knitted sandwich cloth are integrally formed by a tape casting process to obtain a TPU layer and a knitted sandwich cloth layer;

[0165] (2) preparing a TPU layer by the casting process according to Example 1, mixing the raw materials for preparing the high temperature resistant PU layer in the formula amount to obtain a mixture, and coating the mixture on the surface of the TPU layer to obtain a TPU layer + a high temperature resistant PU layer;

[0166] (3) Adhesive is used to bond the products of step (1) and step (2) to obtain the high temperature resistant film.

[0167] Example 7

[0168] The only difference between this embodiment and embodiment 1 is that polyetherketone is replaced by an equal amount of polyetheretherketone.

[0169] Comparative Example 1

[0170] The only difference between this comparative example and Example 1 is that the raw materials for preparing the TPU layer do not include polyaryletherketone, and the weight proportion of the thermoplastic polyester is 75 parts.

[0171] Comparative Example 2

[0172] The only difference between this comparative example and Example 1 is that, in the raw material for preparing the TPU layer, polyethylene terephthalate is replaced by an equal amount of thermoplastic polyurethane elastomer (purchased from Wanhua Chemical, WHT-1490).

[0173] Comparative Example 3

[0174] The only difference between this comparative example and Example 1 is that, in the raw materials for preparing the TPU layer, the weight portion of polyaryletherketone is 1 part.

[0175] Comparative Example 4

[0176] The only difference between this comparative example and Example 1 is that the weight portion of the inorganic nanoparticles in the raw materials for preparing the TPU layer is 0.3 parts.

[0177] The performance of the high temperature resistant films provided in Examples 1-7 and Comparative Examples 1-4 was tested, and the testing method was as follows:

[0178] (1) High temperature resistance: Place the high temperature resistant film in an oven at 180°C for 10 seconds and observe the time it takes to deform. If it is less than 3 seconds, it is unqualified. If it still does not deform within 10 seconds, it is recorded as >10 seconds.

[0179] (2) Wear resistance: Tested according to the method of QB / 2726-2005;

[0180] (3) Scratch resistance: Use a one-yuan coin to repeatedly scratch the film surface 10 times with the same force, and compare the scratched area with the unscratched area. A: No change in the surface; B: No obvious change in the surface texture; C: The surface texture is blurred.

[0181] The performance test results are shown in Table 1.

[0182] Table 1

[0183] High temperature resistance Wear resistance Scratch resistance Example 1 5s Level 4 A Example 2 4s Level 4 A Example 3 8s Level 5 A Example 4 ＞10s Level 5 A Example 5 ＞10s Level 5 A Example 6 ＞10s Level 5 A Example 7 3s Level 4 A Comparative Example 1 Failure Level 4 A Comparative Example 2 Failure Level 4 A Comparative Example 3 Failure Level 4 A Comparative Example 4 Failure Level 2 B

[0184] It can be seen from Table 1 that the high temperature resistant films prepared in Examples 1-7 of the present invention all have excellent high temperature resistance (can withstand 180° C. high temperature for 3s-10s), wear resistance and scratch resistance.

[0185] Compared with Example 1, the high temperature resistance of the high temperature resistant films prepared in Comparative Examples 1-4 is significantly reduced.

[0186] The applicant declares that the present invention illustrates the high temperature resistant film of the present invention through the above-mentioned embodiments, 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 high temperature resistant film, characterized in that: The high temperature resistant film comprises a TPU layer and a dry PU coating layer stacked in sequence; Alternatively, the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer and a dry PU coating layer stacked in sequence; Alternatively, the high temperature resistant film comprises a TPU layer, a high temperature resistant PU layer, a TPU layer and a dry PU coating layer stacked in sequence; The raw materials for preparing the TPU layer are composed of the following components in parts by weight: The raw materials for preparing the dry PU coating include the following components in parts by weight: 90-110 parts of polycarbonate polyurethane; 3-5 parts of isocyanate curing agent; 80-100 parts of solvent; The raw materials for preparing the high temperature resistant PU layer include the following components in parts by weight: Polyurethane resin 80-110 parts; 5-10 parts of nano-alumina; Solvent 90-110 parts.

2. The high temperature resistant film according to claim 1, characterized in that: The thermoplastic polyester includes polyethylene terephthalate and / or polybutylene terephthalate.

3. The high temperature resistant film according to claim 1, characterized in that: The polyaryletherketone includes any one of polyetheretherketone, polyetherketone, polyetherketoneketone or polyetherketoneetherketoneketone or a combination of at least two thereof.

4. The high temperature resistant film according to claim 3, characterized in that: The polyaryletherketone is polyetherketone.

5. The high temperature resistant film according to claim 1, characterized in that: The particle size of the inorganic nanoparticles is 10-200 nm.

6. The high temperature resistant film according to claim 1, characterized in that: The inorganic nanoparticles include any one of nano silicon dioxide, nano titanium dioxide, nano aluminum oxide or nano zinc oxide, or a combination of at least two of them.

7. The high temperature resistant film according to claim 1, characterized in that: The film-forming aid includes any one of ethylene glycol, propylene glycol, hexylene glycol, dodecyl alcohol ester, hexylene glycol butyl ether acetate or 3-ethoxyethyl propionate, or a combination of at least two thereof.

8. The high temperature resistant film according to claim 1, characterized in that: The antioxidant includes any one of the antioxidant 1010 , the antioxidant 1076 , the antioxidant 168 , or the antioxidant 164 , or a combination of at least two of them.

9. The high temperature resistant film according to claim 1, characterized in that: The heat stabilizer includes any one of trimethyl phosphate, barium stearate or magnesium stearate, or a combination of at least two of them.

10. The high temperature resistant film according to claim 1, characterized in that: The polycarbonate polyurethane comprises water-based organosilicon-modified polycarbonate polyurethane resin.

11. The high temperature resistant film according to claim 1, characterized in that: The isocyanate curing agent includes any one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate or hexamethylene diisocyanate, or a combination of at least two thereof.

12. The high temperature resistant film according to claim 1, characterized in that: The solvent in the dry PU coating includes any one of acetone, toluene or xylene.

13. The high temperature resistant film according to claim 1, characterized in that: The particle size of the nano-alumina is 30-60nm.

14. The high temperature resistant film according to claim 1, characterized in that: The solvent in the high temperature resistant PU layer includes any one of acetone, toluene or xylene.

Images