Thermoplastic polyurethane matt film as well as preparation method and application thereof

Abstract

The invention relates to the technical field of thermoplastic polyurethane, in particular to a thermoplastic polyurethane matt film as well as a preparation method and application thereof. The thermoplastic polyurethane matt film is prepared from the following raw materials in parts by mass: 500 to 550 parts of polyester crystalline thermoplastic polyurethane, 400 to 660 parts of polyether amorphous thermoplastic polyurethane, 60 to 100 parts of graphene oxide / silicon dioxide compound, 10 to 30 parts of nucleating agent, 15 to 25 parts of compatilizer and 8 to 12 parts of organic silicon rheological additive. The matting TPU film can be used for a vamp decoration material, is high in haze (gt, 70%) and low in glossiness (lt, 15%), has the matting characteristic, is soft in texture and washable, and can keep a good matting effect for a long time.

Description

Technical Field

[0001] The invention relates to the technical field of thermoplastic polyurethane, in particular to a thermoplastic polyurethane matte film and a preparation method and application thereof. Background Art

[0002] Thermoplastic polyurethane (TPU) materials are widely used in the field of sports shoe upper decoration materials due to their excellent elasticity, wear resistance and processing properties. The current mainstream TPU shoe upper decoration film has three major technical problems: 1) The surface glossiness of conventional polyester TPU films is generally higher than 30%, which cannot meet the matte texture requirements of high-end sports shoes; 2) Existing matte films mostly use polyolefin systems, which have a low glass transition temperature and are prone to microcrack propagation during repeated bending and washing, resulting in reduced durability of the decorative layer; Currently, polyester TPU and polyether TPU blends face significant phase separation challenges. When the two are combined through simple physical blending, the difference between the rigid benzene ring structure of the polyester segments and the flexible ether bonds of the polyether segments easily leads to the formation of a macroscopic phase separation structure, resulting in insufficient surface roughness and high gloss in the film. This urgently needs to be addressed. For example, while inorganic matting agents can reduce gloss, they also result in low tensile strength and the nanoparticles tend to agglomerate, forming stress concentration points. These issues have severely restricted the application and expansion of TPU materials in the high-end footwear and apparel market. Summary of the Invention

[0003] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a thermoplastic polyurethane matte film and a preparation method and application thereof.

[0004] A thermoplastic polyurethane matte film comprises the following raw materials in parts by mass: 500-550 parts of polyester crystalline thermoplastic polyurethane, 400-660 parts of polyether non-crystalline thermoplastic polyurethane, 60-100 parts of graphene oxide / silicon dioxide composite, 10-30 parts of nucleating agent, 15-25 parts of compatibilizer, and 8-12 parts of organosilicon rheological additive.

[0005] Preferably, the crystallinity of the polyester crystalline thermoplastic polyurethane is ≥60%, and the crystallinity of the polyether non-crystalline thermoplastic polyurethane is ≤20%.

[0006] Preferably, the mass ratio of the polyester crystalline thermoplastic polyurethane to the polyether non-crystalline thermoplastic polyurethane is 1:0.8-1.2.

[0007] Preferably, the nucleating agent is talc.

[0008] Preferably, the compatibilizer is ethylene-methacrylic acid copolymer and / or ethylene-acrylic acid copolymer.

[0009] Preferably, the graphene oxide / silicon dioxide composite is prepared by the following steps: adding graphene oxide to an ethanol aqueous solution and ultrasonically treating it for 10-20 minutes, adjusting the pH value of the system to 4-5, adding ethyl orthosilicate thereto and continuing ultrasonically treating it for 2-5 hours, adjusting the system to be neutral, adding a silane coupling agent thereto and continuing ultrasonically treating it for 1-2 hours, refluxing at 70-80°C for 1-5 hours, centrifuging, washing, vacuum drying, and crushing.

[0010] More preferably, the mass ratio of graphene oxide, tetraethyl orthosilicate, and silane coupling agent is 5-15:1-5:0.5-1.

[0011] The preparation method of the above-mentioned thermoplastic polyurethane matte film includes the following steps: premixing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane, melt blending at 180-200°C for 5-8 minutes, adding graphene oxide / silicon dioxide composite and continuing stirring for 3-5 minutes, adding nucleating agent, compatibilizer and silicone rheological additive and stirring for 30-90 seconds, and extruding.

[0012] Preferably, a T-die is used for extrusion, with a die temperature of 170-190°C, a pulling speed of 5-8 m / min, and a cooling water tank temperature of 20-30°C.

[0013] The thermoplastic polyurethane matte film is used as a decorative material for clothing or sports shoe uppers.

[0014] Beneficial effects: The present invention adopts polyester crystalline TPU and polyether non-crystalline TPU as the matrix materials and reasonably controls the ratio of the two. It induces microphase separation through the difference in molecular chain segments, thereby forming an irregular sea island structure on the surface. It is further combined with the effect of graphene oxide / silicon dioxide composite to effectively reduce gloss and increase haze. In combination with rheological additives and compatibilizers, it effectively improves processing fluidity.

[0015] In the graphene oxide / silicon dioxide composite used in the present invention, nano-silicon dioxide is deposited and combined with the graphene oxide sheets, and the product can be effectively combined with the matrix material. On the one hand, due to the unique two-dimensional sheet structure of graphene oxide, its large-area declustering and relative slip deformation can generate energy dissipation, thereby reducing the impact of external forces, effectively preventing crack propagation, and imparting good tensile strength. On the other hand, the nanoparticles deposited on the surface of the stacked functionalized graphene oxide cooperate with the irregular sea-island structure to exhibit excellent extinction performance, achieving high haze and low gloss.

[0016] The present invention uses polyester TPU and polyether TPU with significantly different crystallinity as matrix materials. By precisely controlling the blending process, an island structure is induced in the molten state, in which the polyester phase forms a continuous phase and the polyether phase forms a dispersed phase. This microstructure makes the surface roughness of the film high. Combined with the effect of the graphene oxide / silicon dioxide composite, it can maintain excellent mechanical properties, solve the dispersion problem of graphene oxide in the TPU matrix, and construct a multi-level extinction method to meet the requirements of the matte effect.

[0017] The present invention can be used for shoe upper decorative materials to achieve a TPU film with high haze (>70%) and low gloss (<15%), and has matte properties. It is not only soft and washable, but also can maintain a good matte effect for a long time. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a comparison chart of the surface gloss and haze of the thermoplastic polyurethane matte films obtained in Example 5 and Comparative Examples 1-2.

[0019] Figure 2 1-2 is a comparison chart of the longitudinal / transverse tensile strength of the thermoplastic polyurethane matte films obtained in Example 5 and Comparative Examples 1-2.

[0020] Figure 3 1-2 is a comparison chart of longitudinal / transverse tear strength of the thermoplastic polyurethane matte films obtained in Example 5 and Comparative Examples 1-2. DETAILED DESCRIPTION

[0021] The present invention will be further explained below with reference to specific embodiments.

[0022] The polyester crystalline thermoplastic polyurethane used below was purchased from XX Company, with a brand name of YY and a crystallinity of ≥60%. The polyether amorphous thermoplastic polyurethane used below was purchased from XX Company, with a brand name of YY and a crystallinity of ≤20%. [Shell Mask 1] Example 1: A thermoplastic polyurethane matte film, the raw materials of which include: 500g of polyester crystalline thermoplastic polyurethane, 400g of polyether non-crystalline thermoplastic polyurethane, 60g of graphene oxide / silicon dioxide composite, 10g of talc, 15g of ethylene-acrylic acid copolymer, and 8g of BYK-333 rheological agent.

[0023] The graphene oxide / silicon dioxide composite was prepared by the following steps: 5 g of graphene oxide was added to 40 g of 40% ethanol aqueous solution and ultrasonically treated for 10 minutes at an ultrasonic frequency of 40 kHz. The pH value of the system was adjusted to 4-5 using a 1 mol / L acetic acid solution. 1 g of ethyl orthosilicate was added thereto and ultrasonic treatment was continued for 2 hours to adjust the system to neutrality. 0.5 g of KH560 coupling agent was added thereto and ultrasonic treatment was continued for 1 hour. The product was refluxed at 70°C for 1 hour, centrifuged, washed, vacuum dried, and crushed.

[0024] The method for preparing the thermoplastic polyurethane matte film comprises the following steps: placing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane into a twin-screw extruder and melt blending for 5 minutes, wherein the processing temperature is 180°C, the screw speed is 100 r / min, and the vacuum exhaust section pressure is -0.08 MPa (gauge pressure); adding a graphene oxide / silicon dioxide composite from a side feed port and continuing stirring for 3 minutes; adding talc powder, ethylene-acrylic acid copolymer, and BYK-333 rheological agent and stirring for 30 seconds to obtain a premix; and extruding the premix through a T-die with a die temperature of 170°C, a pulling speed of 5 m / min, and a cooling water tank temperature of 20°C.

[0025] Example 2: A thermoplastic polyurethane matte film, the raw materials of which include: 550g of polyester crystalline thermoplastic polyurethane, 660g of polyether non-crystalline thermoplastic polyurethane, 100g of graphene oxide / silicon dioxide composite, 30g of talc, 15g of ethylene-methacrylic acid copolymer, 10g of ethylene-acrylic acid copolymer, and 12g of BYK-333 rheological agent.

[0026] The graphene oxide / silicon dioxide composite was prepared by the following steps: 15 g of graphene oxide was added to 60 g of 60% ethanol aqueous solution and ultrasonically treated for 20 minutes at an ultrasonic frequency of 60 kHz. The pH value of the system was adjusted to 4-5 using a 2 mol / L acetic acid solution. 5 g of ethyl orthosilicate was added thereto and ultrasonic treatment was continued for 5 hours to adjust the system to neutrality. 1 g of KH560 coupling agent was added thereto and ultrasonic treatment was continued for 2 hours. The product was refluxed at 80°C for 5 hours, centrifuged, washed, vacuum dried, and crushed.

[0027] The method for preparing the thermoplastic polyurethane matte film comprises the following steps: placing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane into a twin-screw extruder for melt blending for 8 minutes, wherein the processing temperature is 200°C, the screw speed is 120 r / min, and the vacuum exhaust section pressure is -0.09 MPa (gauge pressure); adding a graphene oxide / silicon dioxide composite from a side feed port and continuing stirring for 5 minutes; adding talc, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, and BYK-333 rheological agent and stirring for 90 seconds to obtain a premix; and extruding the premix through a T-die with a die temperature of 190°C, a pulling speed of 8 m / min, and a cooling water tank temperature of 30°C.

[0028] Example 3: A thermoplastic polyurethane matte film, the raw materials of which include: 510g of polyester crystalline thermoplastic polyurethane, 510g of polyether non-crystalline thermoplastic polyurethane, 90g of graphene oxide / silicon dioxide composite, 15g of talc, 22g of ethylene-methacrylic acid copolymer, and 9g of BYK-333 rheological agent.

[0029] The graphene oxide / silicon dioxide composite was prepared by the following steps: 12 g of graphene oxide was added to 45 g of 55% ethanol aqueous solution and ultrasonically treated for 12 minutes at an ultrasonic frequency of 55 kHz. The pH value of the system was adjusted to 4-5 using a 1.5 mol / L acetic acid solution. 2 g of ethyl orthosilicate was added and ultrasonically treated for 4 hours to adjust the system to neutral. 0.6 g of KH560 coupling agent was added and ultrasonically treated for 100 minutes. The mixture was refluxed at 73°C for 4 hours, centrifuged, washed, vacuum dried, and crushed.

[0030] The method for preparing the thermoplastic polyurethane matte film comprises the following steps: placing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane into a twin-screw extruder and melt blending for 6 minutes, wherein the processing temperature is 195°C, the screw speed is 105 r / min, and the vacuum exhaust section pressure is -0.1 MPa (gauge pressure); adding a graphene oxide / silicon dioxide composite from a side feed port and continuing stirring for 4 minutes; adding talc powder, ethylene-methacrylic acid copolymer, and BYK-333 rheological agent and stirring for 80 seconds to obtain a premix; and extruding the premix through a T-die with a die temperature of 175°C, a pulling speed of 7 m / min, and a cooling water tank temperature of 22°C.

[0031] Example 4: A thermoplastic polyurethane matte film, the raw materials of which include: 530g of polyester crystalline thermoplastic polyurethane, 530g of polyether non-crystalline thermoplastic polyurethane, 70g of graphene oxide / silicon dioxide composite, 25g of talc, 18g of ethylene-acrylic acid copolymer, and 11g of BYK-333 rheological agent.

[0032] The graphene oxide / silicon dioxide composite was prepared by the following steps: 8 g of graphene oxide was added to 55 g of 45% ethanol aqueous solution and ultrasonically treated for 18 minutes at an ultrasonic frequency of 45 kHz. The pH value of the system was adjusted to 4-5 using a 1.5 mol / L acetic acid solution. 4 g of ethyl orthosilicate was added and ultrasonically treated for 3 hours to adjust the system to neutral. 0.8 g of KH560 coupling agent was added and ultrasonically treated for 80 minutes. The product was refluxed at 77°C for 2 hours, centrifuged, washed, vacuum dried, and crushed.

[0033] The method for preparing the thermoplastic polyurethane matte film comprises the following steps: placing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane into a twin-screw extruder and melt blending for 7 minutes, wherein the processing temperature is 185°C, the screw speed is 115 r / min, and the vacuum exhaust section pressure is -0.1 MPa (gauge pressure); adding a graphene oxide / silicon dioxide composite from a side feed port and continuing stirring for 4 minutes; adding talc powder, ethylene-acrylic acid copolymer, and BYK-333 rheological agent and stirring for 40 seconds to obtain a premix; and extruding the premix through a T-die with a die temperature of 185°C, a pulling speed of 6 m / min, and a cooling water tank temperature of 28°C.

[0034] Example 5: A thermoplastic polyurethane matte film, the raw materials of which include: 520g of polyester crystalline thermoplastic polyurethane, 520g of polyether non-crystalline thermoplastic polyurethane, 80g of graphene oxide / silicon dioxide composite, 20g of talc powder, 20g of ethylene-methacrylic acid copolymer, and 10g of BYK-333 rheological agent.

[0035] The graphene oxide / silicon dioxide composite was prepared by the following steps: 10 g of graphene oxide was added to 50 g of 50% ethanol aqueous solution and ultrasonically treated for 15 minutes at an ultrasonic frequency of 50 kHz. The pH value of the system was adjusted to 4-5 using a 1.5 mol / L acetic acid solution. 3 g of ethyl orthosilicate was added thereto and ultrasonic treatment was continued for 3.5 hours to adjust the system to neutrality. 0.7 g of KH560 coupling agent was added thereto and ultrasonic treatment was continued for 90 minutes. The product was refluxed at 75°C for 3 hours, centrifuged, washed, vacuum dried, and crushed.

[0036] The method for preparing the thermoplastic polyurethane matte film comprises the following steps: placing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane into a twin-screw extruder and melt blending them for 6.5 minutes, wherein the processing temperature is 190°C, the screw speed is 110 r / min, and the vacuum exhaust section pressure is -0.1 MPa (gauge pressure); adding a graphene oxide / silicon dioxide composite from a side feed port and continuing stirring for 4 minutes; adding talc powder, ethylene-methacrylic acid copolymer, and BYK-333 rheological agent and stirring for 60 seconds to obtain a premix; and extruding the premix through a T-die with a die temperature of 180°C, a pulling speed of 6.5 m / min, and a cooling water tank temperature of 25°C.

[0037] Comparative Example 1: A thermoplastic polyurethane matte film, the raw materials of which include: 780g of polyester crystalline thermoplastic polyurethane, 260g of polyether non-crystalline thermoplastic polyurethane, 80g of graphene oxide / silicon dioxide composite, 20g of talc, 20g of ethylene-methacrylic acid copolymer, and 10g of BYK-333 rheological agent.

[0038] The graphene oxide / silicon dioxide composite was prepared by the following steps: 10 g of graphene oxide was added to 50 g of 50% ethanol aqueous solution and ultrasonically treated for 15 minutes at an ultrasonic frequency of 50 kHz. The pH value of the system was adjusted to 4-5 using a 1.5 mol / L acetic acid solution. 3 g of ethyl orthosilicate was added thereto and ultrasonic treatment was continued for 3.5 hours to adjust the system to neutrality. 0.7 g of KH560 coupling agent was added thereto and ultrasonic treatment was continued for 90 minutes. The product was refluxed at 75°C for 3 hours, centrifuged, washed, vacuum dried, and crushed.

[0039] The method for preparing the thermoplastic polyurethane matte film comprises the following steps: placing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane into a twin-screw extruder and melt blending them for 6.5 minutes, wherein the processing temperature is 190°C, the screw speed is 110 r / min, and the vacuum exhaust section pressure is -0.1 MPa (gauge pressure); adding a graphene oxide / silicon dioxide composite from a side feed port and continuing stirring for 4 minutes; adding talc powder, ethylene-methacrylic acid copolymer, and BYK-333 rheological agent and stirring for 60 seconds to obtain a premix; and extruding the premix through a T-die with a die temperature of 180°C, a pulling speed of 6.5 m / min, and a cooling water tank temperature of 25°C.

[0040] Comparative Example 2: A thermoplastic polyurethane matte film, the raw materials of which include: 520g of polyester crystalline thermoplastic polyurethane, 520g of polyether non-crystalline thermoplastic polyurethane, 80g of graphene oxide / silicon dioxide composite, 20g of talc, 20g of ethylene-methacrylic acid copolymer, and 10g of BYK-333 rheological agent.

[0041] The graphene oxide / silica composite was prepared by the following steps: taking 50 g of a 50% ethanol aqueous solution, adjusting the pH value of the system to 4-5 with a 1.5 mol / L acetic acid solution, adding 3 g of ethyl orthosilicate and ultrasonically treating for 3.5 hours at an ultrasonic frequency of 50 kHz to adjust the system to neutrality, adding 0.7 g of KH560 coupling agent and continuing ultrasonic treatment for 90 minutes, reflux at a temperature of 75°C for 3 hours, centrifuging, washing, vacuum drying, crushing, and then adding 10 g of graphene oxide and mixing evenly.

[0042] The method for preparing the thermoplastic polyurethane matte film comprises the following steps: placing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane into a twin-screw extruder and melt blending them for 6.5 minutes, wherein the processing temperature is 190°C, the screw speed is 110 r / min, and the vacuum exhaust section pressure is -0.1 MPa (gauge pressure); adding a graphene oxide / silicon dioxide composite from a side feed port and continuing stirring for 4 minutes; adding talc powder, ethylene-methacrylic acid copolymer, and BYK-333 rheological agent and stirring for 60 seconds to obtain a premix; and extruding the premix through a T-die with a die temperature of 180°C, a pulling speed of 6.5 m / min, and a cooling water tank temperature of 25°C.

[0043] The surface gloss of the thermoplastic polyurethane matte films obtained in Example 5 and Comparative Examples 1-2 was measured at a 60° angle with reference to GB / T 8807-1988, "Test Method for Specular Gloss of Plastics." The haze of the thermoplastic polyurethane matte films obtained in Example 5 and Comparative Examples 1-2 was also measured with reference to GB / T 2410-2008, "Transparent Plastics - Determination of Light Transmittance and Haze."

[0044] like Figure 1 As shown, the surface glossiness of the thermoplastic polyurethane matte film obtained in Example 5 is the smallest, while the haze is the highest, which is better than that of Comparative Examples 1-2 (P < 0.05).

[0045] The longitudinal / transverse tensile strength and longitudinal / transverse tear strength of the thermoplastic polyurethane matte films obtained in Example 5 and Comparative Examples 1-2 were measured with reference to HG / T 5070-2016 “Thermoplastic Polyurethane (TPU) Films”.

[0046] like Figure 2 and Figure 3 As shown, the tensile strength and tear strength of the thermoplastic polyurethane matte film obtained in Example 5 are the highest, which are better than those of Comparative Examples 1-2 (P < 0.05).

[0047] The applicant believes that the present invention uses polyester crystalline TPU and polyether amorphous TPU as the matrix material and reasonably controls the ratio of the two. Through the difference in molecular segments, microphase separation is induced, and an irregular island structure is formed on the surface. The graphene oxide / silica composite further cooperates to effectively reduce gloss and increase haze. In combination with rheological additives and compatibilizers, the processing fluidity is effectively improved. At the same time, in the graphene oxide / silica composite used in the present invention, nano-silica is deposited on the graphene oxide sheet, and the product can be effectively combined with the matrix material. On the one hand, due to the unique two-dimensional sheet structure of graphene oxide, its large-area declustering and relative slip deformation can generate energy dissipation, thereby reducing the impact of external forces, effectively preventing crack propagation, and imparting good tensile strength. On the other hand, the nanoparticles deposited on the surface of the stacked functionalized graphene oxide cooperate with the irregular island structure to exhibit excellent extinction performance, achieving high haze and low gloss. The present invention uses polyester TPU and polyether TPU with significantly different crystallinity as matrix materials. By precisely controlling the blending process, an island structure is induced in the molten state, in which the polyester phase forms a continuous phase and the polyether phase forms a dispersed phase. This microstructure makes the surface roughness of the film high. Combined with the effect of the graphene oxide / silicon dioxide composite, it can maintain excellent mechanical properties, solve the dispersion problem of graphene oxide in the TPU matrix, and construct a multi-level extinction method to meet the requirements of the matte effect.

[0048] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A thermoplastic polyurethane matte film, characterized in that: The raw materials include, by mass, 500-550 parts of polyester crystalline thermoplastic polyurethane, 400-660 parts of polyether non-crystalline thermoplastic polyurethane, 60-100 parts of graphene oxide / silicon dioxide composite, 10-30 parts of nucleating agent, 15-25 parts of compatibilizer, and 8-12 parts of organic silicon rheological additive.

2. The thermoplastic polyurethane matte film according to claim 1, characterized in that: The crystallinity of polyester crystalline thermoplastic polyurethane is ≥60%, and the crystallinity of polyether non-crystalline thermoplastic polyurethane is ≤20%.

3. The thermoplastic polyurethane matte film according to claim 1, characterized in that: The mass ratio of polyester crystalline thermoplastic polyurethane to polyether non-crystalline thermoplastic polyurethane is 1:0.8-1.

2.

4. The thermoplastic polyurethane matte film according to claim 1, characterized in that: The nucleating agent is talc.

5. The thermoplastic polyurethane matte film according to claim 1, characterized in that: The compatibilizer is ethylene-methacrylic acid copolymer and / or ethylene-acrylic acid copolymer.

6. The thermoplastic polyurethane matte film according to claim 1, characterized in that: The silicone rheological additive is BYK-333 rheological agent.

7. The thermoplastic polyurethane matte film according to claim 1, characterized in that: The graphene oxide / silicon dioxide composite is prepared by the following steps: adding graphene oxide to an ethanol aqueous solution and ultrasonically treating the composite for 10-20 minutes, adjusting the pH value of the system to 4-5, adding ethyl orthosilicate thereto and continuing ultrasonically treating the composite for 2-5 hours, adjusting the system to be neutral, adding a silane coupling agent thereto and continuing ultrasonically treating the composite for 1-2 hours, refluxing at 70-80° C. for 1-5 hours, centrifuging, washing, vacuum drying, and crushing.

8. The thermoplastic polyurethane matte film according to claim 7, characterized in that: The mass ratio of graphene oxide, tetraethyl orthosilicate and silane coupling agent is 5-15:1-5:0.5-1.

9. A method for preparing the thermoplastic polyurethane matte film according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: premixing polyester crystalline thermoplastic polyurethane and polyether non-crystalline thermoplastic polyurethane, melt-blending at 180-200° C. for 5-8 minutes, adding graphene oxide / silicon dioxide composite and continuing stirring for 3-5 minutes, adding nucleating agent, compatibilizer and organosilicon rheological additive and stirring for 30-90 seconds, and extruding.

10. Use of the thermoplastic polyurethane matte film according to any one of claims 1 to 8 as a decorative material for clothing or sports shoe uppers.

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