Nano-abrasive agent and preparation method, composition and application in paper-like film

Abstract

The present invention belongs to the technical field of electronic materials, and relates to a nano-abrasive agent, a preparation method thereof, a composition, and an application in a paper-like film. The nano-abrasive agent is composed of hollow TPU fiber particles and a silicon dioxide layer deposited and grown in situ on its outer wall; the nano-abrasive agent composition is composed of nano-abrasive agents of different particle size ranges in a specific proportion; the method for preparing the nano-abrasive agent includes the steps of preparing hollow TPU fiber particles, preparing a solution A containing a silicon source, adding the hollow TPU fiber particles to the solution A for reaction, and then post-treating; the application is to prepare the nano-abrasive agent or the nano-abrasive agent composition into an extruded high-wear-resistant and high-rebound paper-like film. The present invention achieves a comprehensive improvement in the four aspects of damping, touch, wear resistance, and optical performance of the paper-like film.

Description

Technical Field

[0001] The present invention belongs to the technical field of electronic materials, and relates to a nano-abrasive agent and a preparation method and composition thereof, and application in paper-like films. Background Technology

[0002] In recent years, with the rapid development of electronic writing technology, paper-like films have received widespread attention as a key material for improving the writing experience on electronic screens. Paper-like films are designed to simulate the writing feel of paper and provide users with a more natural and comfortable writing experience.

[0003] The damping sense is one of the important indicators of paper-like film to simulate the writing experience of paper. By providing appropriate damping sense, paper-like film simulates the friction when writing on paper, allowing users to experience a more realistic writing experience. Touch is another key factor that affects the use experience of paper-like film. The ideal paper-like film should not only have sufficient damping sense, but also simulate the softness and elasticity of paper in touch, so that users feel comfortable when writing. Wear resistance is also an aspect that cannot be ignored in the application of paper-like film. Since paper-like film needs to withstand frequent writing friction, its wear resistance is directly related to its service life. In addition, optical performance is also one of the important indicators for evaluating the quality of paper-like film. Good optical performance can ensure that the paper-like film does not affect the display effect of the electronic screen while providing a writing experience.

[0004] However, existing paper-like films still have many deficiencies in performance, especially in terms of damping, touch, wear resistance and optical performance. For example, patent application CN115369684A discloses a hardening layer coating liquid and an antibacterial paper-like film. Although a large amount of silicon dioxide is added to provide a damping feeling, this method will result in a stiff touch, and after long-term use, the silicon dioxide will wear, affecting the damping feeling and optical performance.

[0005] Therefore, developing a paper-like film material that can simultaneously meet the requirements of damping, touch, wear resistance and optical performance has become a technical problem that needs to be solved urgently. SUMMARY OF THE INVENTION

[0006] The purpose of the present invention is to solve the problems existing in the prior art and provide a nano-abrasive agent and its preparation method, composition and application in paper-like films.

[0007] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] A nano-abrasive agent, which is composed of hollow TPU fiber particles and a silicon dioxide layer deposited and grown in situ on the outer wall.

[0009] As the preferred technical solution:

[0010] A nano-abrasive as described above, wherein the content of silicon dioxide in the nano-abrasive is 50-60 wt%.

[0011] A nano-abrasive as described above, wherein the particle size of the nano-abrasive is less than 0.5 μm, the inner diameter of the hollow TPU fiber particles is 0.1-0.2 μm and the wall thickness is 0.05 μm, and the thickness of the silicon dioxide layer is 0.05-0.1 μm; the nano-abrasive of this size is denoted as nano-abrasive A.

[0012] A nano-abrasive as described above, wherein the particle size of the nano-abrasive is greater than or equal to 0.5 μm and less than 1 μm, the inner diameter of the hollow TPU fiber particles is 0.2-0.4 μm and the wall thickness is 0.1 μm, and the thickness of the silicon dioxide layer is 0.1-0.2 μm; the nano-abrasive of this size is denoted as nano-abrasive B.

[0013] A nano-abrasive as described above, wherein the particle size of the nano-abrasive is greater than or equal to 1 μm and less than 10 μm, the inner diameter of the hollow TPU fiber particles is 0.4-4 μm and the wall thickness is 0.1-1 μm, and the thickness of the silicon dioxide layer is 0.2-2 μm; the nano-abrasive of this size is denoted as nano-abrasive C.

[0014] A nano-abrasive as described above, wherein the particle size of the nano-abrasive is greater than or equal to 10 μm and less than 20 μm, the inner diameter of the hollow TPU fiber particles is 3-6 μm and the wall thickness is 1.5-3 μm, and the thickness of the silicon dioxide layer is 2-4 μm; the nano-abrasive of this size is denoted as nano-abrasive D.

[0015] A nano-abrasive as described above, wherein the particle size of the nano-abrasive is greater than or equal to 20 μm and less than or equal to 25 μm, the inner diameter of the hollow TPU fiber particles is 6-7 μm and the wall thickness is 3-4 μm, and the thickness of the silicon dioxide layer is 4-5 μm; the nano-abrasive of this size is denoted as nano-abrasive E.

[0016] The present invention also provides a nano-abrasive composition, which is composed of 30-50 wt% of nano-abrasive A, 20-25 wt% of nano-abrasive B, 15-20 wt% of nano-abrasive C, 10-15 wt% of nano-abrasive D, and 5-10 wt% of nano-abrasive E.

[0017] The present invention also provides a method for preparing a nano-abrasive as described in any one of the above, comprising the following steps:

[0018] (a) Preparing hollow TPU fiber particles;

[0019] (b) Dissolving a silicon source in an acidic solution to obtain solution A;

[0020] (c) Add the hollow TPU fiber particles to Solution A. After adding the base, react at 60 °C for 2 - 6 h under stirring conditions to obtain Solution B. Perform post-treatment on Solution B (filtration by suction, washing with pure water, drying), and thus obtain the nano-abrasive agent.

[0021] As a preferred technical solution:

[0022] For the method as described above, step (a) is specifically: Dissolve the TPU particles in N,N-dimethylacetamide to obtain a spinning solution with a concentration of 10 - 30%. After spinning using a hollow fiber spinneret and a wet spinning process, cut to obtain the hollow TPU fiber particles.

[0023] For the method as described above, in step (b), the silicon source is one or more of tetraethyl orthosilicate, tetramethyl orthosilicate, methyltrimethoxysilane, ethyltriethoxysilane, and sodium silicate. The acidic solution is hydrochloric acid solution and / or acetic acid solution. The pH value of Solution A is 2 - 4.

[0024] For the method as described above, in step (c), the mass ratio of the hollow TPU fiber particles to Solution A is 1 - 2:8 - 9. The base is one or more of sodium hydroxide, potassium hydroxide, and calcium hydroxide. The mass of the base is 20 - 70% of the mass of the silicon source.

[0025] The present invention also provides an extruded high-wear-resistant and high-elasticity paper-like film, which includes an upper surface layer, a base layer, and a lower surface layer arranged in sequence from top to bottom; additives are contained in the upper surface layer and the lower surface layer. The additives are a nano-abrasive agent as described in any one of the above or a nano-abrasive agent composition as described above. When the additive is a nano-abrasive agent composition, when the larger particles in the system are slightly worn, the smaller particles have not yet started to participate in the wear. Therefore, its overall friction resistance ability is strong. At the same time, due to the existence of different particle size distributions in the system, this helps to disperse the acting force, thereby greatly reducing the wear of the nano-abrasive agent.

[0026] As a preferred technical solution:

[0027] For an extruded high-wear-resistant and high-elasticity paper-like film as described above, the upper surface layer or the lower surface layer is composed of 65 - 85 wt% of PET and the balance of additives; the base layer is composed of 50 - 62 wt% of PET, 30 - 35 wt% of TPU, 5 - 10 wt% of compatibilizer (polyolefin elastomer POE, maleic anhydride grafted compatibilizer TPU-G-MAH, etc.) and the balance of plasticizer (ethylene terpolymer).

[0028] An extruded high-wear-resistance and high-rebound paper-like film as described above, the thicknesses of the upper surface layer, the base layer, and the lower surface layer are 0.08 - 1.2 mm, 0.2 - 0.24 mm, and 0.08 - 1.2 mm respectively; the haze of the extruded high-wear-resistance and high-rebound paper-like film is 2.1 - 2.7%, the tensile rebound rate is 96.2 - 99.8%, the elongation at break is 320 - 351%, the light transmittance is 92.68 - 95.55%, the number of friction resistance times is 800 - 1600 times, and the dynamic friction coefficient is 0.39 - 0.46.

[0029] The present invention also provides a method for preparing an extruded high-wear-resistance and high-rebound paper-like film as described in any one of the above, comprising the following steps:

[0030] (A)Melting and co-blending the raw materials corresponding to the upper surface layer to obtain modified chip a, melting and co-blending the raw materials corresponding to the base layer to obtain modified chip b, and melting and co-blending the raw materials corresponding to the lower surface layer to obtain modified chip c;

[0031] (B)Melting and extruding modified chip a, modified chip b, and modified chip c respectively through an extruder, extruding through a filter, a melt metering pump, a distributor, and a multi-layer co-extrusion die head, and cooling on a cooling roll to obtain a thick sheet;

[0032] (C)Sequentially longitudinally stretching the thick sheet (the stretching temperature is 80 - 100 °C, the stretching ratio is 3 - 3.6 times), transversely preheating (the temperature is 80 - 120 °C), transversely stretching (the stretching temperature is 100 - 130 °C, the stretching ratio is 3.1 - 4 times), drying and curing (the temperature is 200 - 240 °C), heat setting, and cooling to obtain the extruded high-wear-resistance and high-rebound paper-like film.

[0033] Principle of the invention:

[0034] The nano-abrasive of the present invention contains silicon dioxide, so the paper-like film added with this nano-abrasive has a strong damping feeling.

[0035] The nano-abrasive of the present invention is a double-layer airbag structure with hollow TPU fiber particles as the inner shell and a silicon dioxide layer as the outer shell. After being added to the paper-like film, it can improve the elastic properties of the paper-like film. When a certain position of the paper-like film is subjected to a large external force, the external force will be dispersed in all directions through the double-layer airbag structure, achieving a certain buffering effect on the hand. After the external force disappears, the film surface will return to the original state. And by adding nano-abrasives with different particle sizes, it can effectively improve the different damping feelings brought by different acting forces during the writing process. Therefore, the paper-like film added with this nano-abrasive can improve the writing touch.

[0036] In the nano-abrasive of the present invention, since the silica layer is in-situ deposited and grown on the outer wall of the hollow TPU fiber particles, the hollow TPU fiber particles provide better support for the outer silica layer, disperse the force when in contact, reduce the wear of the silica, and improve the service life of the paper-like film.

[0037] The nano-abrasive of the present invention acts as an anti-blocking agent during the production process of the paper-like film, saving costs and having less impact on the light transmittance of the overall paper-like film.

[0038] Beneficial effects:

[0039] The nano-abrasive of the present invention has a double-layer airbag structure with hollow TPU fiber particles as the inner shell and a silica layer as the outer shell, enabling the paper-like film to provide better damping during writing, simulating the friction during paper writing, while maintaining a soft and elastic touch, giving users a more natural and comfortable writing experience.

[0040] Since the silica layer is in-situ deposited and grown on the outer wall of the hollow TPU fiber particles, it provides good support for the silica layer, effectively disperses the force, thus significantly reducing wear and extending the service life of the paper-like film.

[0041] The nano-abrasive is used as an anti-blocking agent in the paper-like film, not only reducing the production cost, but also having less impact on the light transmittance of the overall paper-like film, ensuring that while providing an excellent writing experience, the paper-like film does not affect the display effect of the electronic screen. Specific embodiments

[0042] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of this application.

[0043] The following are the test methods for relevant performance indicators in each embodiment and comparative example:

[0044] Haze: Tested according to the GB / T 2410-2008 standard.

[0045] Tensile resilience rate: Tested using an ACTS-T300 type full-automatic tensile testing machine. The specific steps are as follows: Cut a 10 cm long paper-like film and PET (as a reference material, manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd., model FG720), clamp both ends of the two samples in the fixture of the tensile testing machine, ensure that the samples are in the correct position during the test, then conduct a tensile test and measure the rebound length, and calculate the tensile resilience rate according to the following formula:

[0046] Tensile resilience rate (%) = (resilience length - initial length) / initial length × 100%;

[0047] Perform 50 parallel tensile tests on the sample and take the average value as the final resilience rate result.

[0048] Elongation at break: Test according to the standard of GB / T 528 - 2009, where the tensile speed is 100 mm / min.

[0049] Transmittance: Test according to the standard of GB / T 2410 - 2008.

[0050] Number of friction resistance times: Use Kunshan Jingjia Instrument A20 - 339 to test according to the standard of JISK - 5600 - 1999. The specific process is as follows: Use 0000# steel wool to wipe the surface of the paper-like film back and forth under the condition of a constant load of 1000 gf / cm², and detect the maximum limit number of times when scratches appear on the film surface.

[0051] Coefficient of kinetic friction: Test according to the standard of JISK - 5600 - 1999. During the test, use a felt with a side length of 5 cm and apply a constant load of 200 g on it. Then, pull the felt uniformly on the surface of the paper-like film, and record and calculate the coefficient of kinetic friction.

[0052] Example 1

[0053] A preparation method of a nano-abrasive, the specific steps are as follows:

[0054] (1) Preparation of raw materials;

[0055] TPU particles: The manufacturer is Wanhua Chemical Group Co., Ltd., and the model is WHT - 1172IC;

[0056] N,N-dimethylacetamide;

[0057] Silicon source: A mixture of tetraethyl orthosilicate and tetramethyl orthosilicate with a mass ratio of 1:1;

[0058] Acidic solution: Hydrochloric acid aqueous solution with a concentration of 20 wt%;

[0059] Base: Sodium hydroxide;

[0060] (2) Preparation of nano-abrasive;

[0061] (2.1) Dissolve TPU particles in N,N-dimethylacetamide to obtain a spinning solution with a concentration of 10%. After spinning using a hollow fiber spinneret and wet spinning process and then cutting, hollow TPU fiber particles are obtained;

[0062] (2.2) Dissolve the silicon source in an acidic solution and stir evenly at 20 °C until no stratification occurs to obtain solution A with a pH value of 2;

[0063] (2.3) Add the hollow TPU fiber particles to solution A, add an alkali, and stir and react at 60 °C for 2 h to obtain solution B. Perform post-treatment on solution B to obtain the nano-abrasive;

[0064] In steps (2.1) to (2.3), the mass ratio of the hollow TPU fiber particles to solution A is 1:9, and the mass of the alkali is 20% of the mass of the silicon source.

[0065] The finally prepared nano-abrasive is composed of hollow TPU fiber particles and a silica layer in-situ deposited and grown on its outer wall. The content of silica in the nano-abrasive is 50 wt%; the particle size of the nano-abrasive is less than 0.5 μm, the inner diameter of the hollow TPU fiber particles is 0.1 - 0.2 μm and the wall thickness is 0.05 μm, and the thickness of the silica layer is 0.05 - 0.1 μm.

[0066] Comparative Example 1

[0067] A preparation method of a nano-abrasive is basically the same as that of Example 1, except that: the TPU particles are replaced by PP (polypropylene) particles (manufactured by Formosa Plastics Corporation, Taiwan, China, grade S1005).

[0068] The finally prepared nano-abrasive is composed of hollow PP particles and a silica layer in-situ deposited and grown on its outer surface; the particle size of the nano-abrasive is less than 0.5 μm, the inner diameter of the hollow PP particles is 0.1 - 0.2 μm and the wall thickness is 0.05 μm, and the thickness of the silica layer is 0.05 - 0.1 μm.

[0069] Comparative Example 2

[0070] A preparation method of a nano-abrasive is as follows:

[0071] (1) Preparation of raw materials;

[0072] Ammonium chloride;

[0073] Methanol aqueous solution: with a concentration of 10 wt%;

[0074] Silicon source: a mixture of tetraethyl orthosilicate and tetramethyl orthosilicate with a mass ratio of 1:1;

[0075] Acidic solution: hydrochloric acid aqueous solution with a concentration of 20 wt%;

[0076] Alkali: sodium hydroxide;

[0077] (2) Preparation of the nano-abrasive;

[0078] (2.1) Dissolve ammonium chloride in an aqueous methanol solution to obtain an ammonium chloride - methanol aqueous solution with a concentration of 10 wt%.

[0079] (2.2) Dissolve the silicon source in an acidic solution, stir evenly at 20 °C until no stratification occurs, and obtain solution A with a pH value of 3.

[0080] (2.3) Add the ammonium chloride - methanol aqueous solution to solution A, stir and react at 0 °C for 3 h, then add the base and stir and react at 60 °C for 6 h, and then raise the temperature to 90 °C and keep warm for 3 h to obtain solution B. Perform post - treatment on solution B (filtration by suction, washing with pure water, drying) to obtain the nano - abrasive.

[0081] In steps (2.1) to (2.3), the mass ratio of the ammonium chloride - methanol aqueous solution to solution A is 1:1, and the mass of the base is 40% of the mass of the silicon source.

[0082] The finally prepared nano - abrasive is hollow silica; the particle size of the nano - abrasive is less than 0.5 μm, and the wall thickness is 0.2 - 0.4 μm.

[0083] Comparative Example 3

[0084] A method for preparing a nano - abrasive, the specific steps are as follows:

[0085] (1) Preparation of raw materials;

[0086] Silicon source: A mixture of tetraethyl orthosilicate and tetramethyl orthosilicate with a mass ratio of 1:1;

[0087] Acidic solution: Hydrochloric acid aqueous solution with a concentration of 20 wt%;

[0088] Base: Sodium hydroxide;

[0089] (2) Preparation of the nano - abrasive;

[0090] (2.1) Dissolve the silicon source in an acidic solution, stir evenly at 20 °C until no stratification occurs, and obtain solution A with a pH value of 3.

[0091] (2.2) After adding the base to solution A, stir and react at 60 °C for 6 h to obtain solution B. Perform post - treatment on solution B (filtration by suction, washing with pure water, drying) to obtain the nano - abrasive; wherein, the mass ratio of the base to solution A is 1:1.

[0092] The finally prepared nano - abrasive is solid silica; the particle size of the nano - abrasive is less than 0.5 μm.

[0093] Example 2

[0094] A method for preparing a nano - abrasive, the specific steps are as follows:

[0095] (1) Preparation of raw materials;

[0096] TPU particles: The manufacturer is Wanhua Chemical Group Co., Ltd., and the model is WHT-1172IC;

[0097] N,N-dimethylacetamide;

[0098] Silicon source: Methyltrimethoxysilane;

[0099] Acidic solution: Aqueous acetic acid solution with a concentration of 20 wt%;

[0100] Base: Potassium hydroxide;

[0101] (2) Preparation of nano-abrasive;

[0102] (2.1) Dissolve the TPU particles in N,N-dimethylacetamide to obtain a spinning solution with a concentration of 20%, and perform spinning and cutting using a hollow fiber spinneret and wet spinning process to obtain hollow TPU fiber particles;

[0103] (2.2) Dissolve the silicon source in the acidic solution and stir evenly at 25 °C until it does not stratify to obtain solution A with a pH value of 2.5;

[0104] (2.3) Add the hollow TPU fiber particles to solution A, add the base, and stir and react at 60 °C for 3 h to obtain solution B, and perform post-treatment on solution B to obtain the nano-abrasive;

[0105] In steps (2.1) to (2.3), the mass ratio of the hollow TPU fiber particles to solution A is 1:9, and the mass of the base is 40% of the mass of the silicon source.

[0106] The finally prepared nano-abrasive is composed of hollow TPU fiber particles and a silica layer in-situ deposited and grown on its outer wall. The content of silica in the nano-abrasive is 52 wt%; the particle size of the nano-abrasive is greater than or equal to 0.5 μm and less than 1 μm, the inner diameter of the hollow TPU fiber particles is 0.2 - 0.4 μm, the wall thickness is 0.1 μm, and the thickness of the silica layer is 0.1 - 0.2 μm.

[0107] Example 3

[0108] A preparation method of a nano-abrasive, the specific steps are as follows:

[0109] (1) Preparation of raw materials;

[0110] TPU particles: The manufacturer is Wanhua Chemical Group Co., Ltd., and the model is WHT-1172IC;

[0111] N,N-dimethylacetamide;

[0112] Silicon source: Ethyltriethoxysilane;

[0113] Acidic solution: A mixture of hydrochloric acid aqueous solution and acetic acid aqueous solution with a mass ratio of 1:1, and the concentrations of both the hydrochloric acid aqueous solution and the acetic acid aqueous solution are 20 wt%;

[0114] Base: Calcium hydroxide;

[0115] (2) Preparation of nano-abrasive;

[0116] (2.1) Dissolve TPU particles in N,N-dimethylacetamide to obtain a spinning solution with a concentration of 25%, and perform spinning and cutting using a hollow fiber spinneret and a wet spinning process to obtain hollow TPU fiber particles;

[0117] (2.2) Dissolve the silicon source in the acidic solution, stir evenly at 28 °C until it does not stratify, and obtain solution A with a pH value of 3;

[0118] (2.3) Add the hollow TPU fiber particles to solution A, add the base, and stir and react at 60 °C for 4 h to obtain solution B, and perform post-treatment on solution B to obtain the nano-abrasive;

[0119] In steps (2.1) to (2.3), the mass ratio of the hollow TPU fiber particles to solution A is 2:8, and the mass of the base is 70% of the mass of the silicon source.

[0120] The finally prepared nano-abrasive is composed of hollow TPU fiber particles and a silica layer in-situ deposited and grown on its outer wall. The content of silica in the nano-abrasive is 56 wt%; the particle size of the nano-abrasive is greater than or equal to 1 μm and less than 10 μm, the inner diameter of the hollow TPU fiber particles is 0.4 - 4 μm, the wall thickness is 0.1 - 1 μm, and the thickness of the silica layer is 0.2 - 2 μm.

[0121] Example 4

[0122] A preparation method of a nano-abrasive, the specific steps are as follows:

[0123] (1) Preparation of raw materials;

[0124] TPU particles: The manufacturer is Wanhua Chemical Group Co., Ltd., and the model is WHT-1172IC;

[0125] N,N-dimethylacetamide;

[0126] Silicon source: A mixture of ethyltriethoxysilane and sodium silicate with a mass ratio of 1:1;

[0127] Acidic solution: Hydrochloric acid aqueous solution, with a concentration of 20 wt%;

[0128] Base: A mixture of sodium hydroxide and potassium hydroxide with a mass ratio of 1:1;

[0129] (2) Preparation of nano-abrasive;

[0130] (2.1) Dissolve the TPU particles in N,N-dimethylacetamide to obtain a spinning solution with a concentration of 30%. After spinning using a hollow fiber spinneret and wet spinning process and then cutting, hollow TPU fiber particles are obtained;

[0131] (2.2) Dissolve the silicon source in an acidic solution, stir evenly at 30 °C until it does not stratify to obtain solution A with a pH value of 4;

[0132] (2.3) Add the hollow TPU fiber particles to solution A, add the base, and stir and react at 60 °C for 5 h to obtain solution B. Perform post-treatment on solution B to obtain the nano-abrasive;

[0133] In steps (2.1) to (2.3), the mass ratio of the hollow TPU fiber particles to solution A is 2:8, and the mass of the base is 70% of the mass of the silicon source.

[0134] The finally prepared nano-abrasive is composed of hollow TPU fiber particles and a silica layer deposited and grown in situ on its outer wall. The content of silica in the nano-abrasive is 58 wt%; the particle size of the nano-abrasive is greater than or equal to 10 μm and less than 20 μm, the inner diameter of the hollow TPU fiber particles is 3 - 6 μm, the wall thickness is 1.5 - 3 μm, and the thickness of the silica layer is 2 - 4 μm.

[0135] Example 5

[0136] A preparation method of a nano-abrasive, the specific steps are as follows:

[0137] (1) Preparation of raw materials;

[0138] TPU particles: The manufacturer is Wanhua Chemical Group Co., Ltd., and the model is WHT-1172IC;

[0139] N,N-dimethylacetamide;

[0140] Silicon source: A mixture of methyltrimethoxysilane and ethyltriethoxysilane with a mass ratio of 1:1;

[0141] Acidic solution: Hydrochloric acid aqueous solution with a concentration of 20 wt%;

[0142] Base: A mixture of sodium hydroxide and potassium hydroxide with a mass ratio of 1:1;

[0143] (2) Preparation of nano-abrasive;

[0144] (2.1) Dissolve TPU particles in N,N-dimethylacetamide to obtain a spinning solution with a concentration of 30%. After spinning using a hollow fiber spinneret and wet spinning process and then cutting, hollow TPU fiber particles are obtained;

[0145] (2.2) Dissolve the silicon source in an acidic solution, stir evenly at 25 °C until no stratification occurs, and obtain solution A with a pH value of 4;

[0146] (2.3) Add the hollow TPU fiber particles to solution A, add an alkali, and stir and react at 60 °C for 6 h to obtain solution B. Perform post-treatment on solution B to obtain a nano-abrasive;

[0147] In steps (2.1) to (2.3), the mass ratio of the hollow TPU fiber particles to solution A is 2:8, and the mass of the alkali is 70% of the mass of the silicon source.

[0148] The finally prepared nano-abrasive is composed of hollow TPU fiber particles and a silica layer in-situ deposited and grown on its outer wall. The content of silica in the nano-abrasive is 60 wt%; the particle size of the nano-abrasive is greater than or equal to 20 μm and less than or equal to 25 μm, the inner diameter of the hollow TPU fiber particles is 6 - 7 μm, the wall thickness is 3 - 4 μm, and the thickness of the silica layer is 4 - 5 μm.

[0149] Example 6

[0150] A preparation method of an extruded high-wear-resistant and high-elasticity paper-like film, the specific steps are as follows:

[0151] (1) Preparation of raw materials;

[0152] Raw materials a and c: Both are composed of 65 wt% of PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FG720) and the balance of the nano-abrasive of Example 1;

[0153] Raw material b: It is composed of 50 wt% of PET, 35 wt% of TPU (manufacturer: Wanhua Chemical Group Co., Ltd., model: WHT-1172IC), 10 wt% of compatibilizer, and the balance of ethylene terpolymer (manufacturer: DuPont Company, USA, model: PTW). The compatibilizer is a mixture of polyolefin elastomer POE (manufacturer: DuPont Company, USA, model: N216) and maleic anhydride grafted compatibilizer TPU-G-MAH (manufacturer: Dongguan Shenghao Plastic Raw Materials Co., Ltd.) with a mass ratio of 1:1;

[0154] (2) Prepare an extruded high-wear-resistant and high-elasticity paper-like film;

[0155] (2.1) Melt and blend raw material a to obtain modified slice a, melt and blend raw material b to obtain modified slice b, and melt and blend raw material c to obtain modified slice c;

[0156] (2.2) Extrude the modified slice a, modified slice b, and modified slice c through an extruder by melting, and extrude through a filter, melt metering pump, distributor, and multi-layer co-extrusion die head, and cool on a cooling roll to obtain a thick sheet;

[0157] (2.3) Longitudinally stretch the thick sheet successively (stretching temperature is 80 °C, stretching ratio is 3.6 times), preheat for transverse stretching (temperature is 80 °C), transversely stretch (stretching temperature is 100 °C, stretching ratio is 4 times), dry and cure (temperature is 200 °C), heat set, and cool to obtain an extruded high wear-resistant and high resilience paper-like film.

[0158] The finally obtained extruded high wear-resistant and high resilience paper-like film consists of an upper surface layer (material is raw material a), a base layer (material is raw material b), and a lower surface layer (material is raw material c) from top to bottom; the thicknesses of the upper surface layer and the lower surface layer are both 0.08 mm, and the thickness of the base layer is 0.2 mm; the haze of the extruded high wear-resistant and high resilience paper-like film is 2.3%, the tensile resilience rate is 96.2%, the elongation at break is 320%, the light transmittance is 92.68%, the number of friction resistance is 800 times, and the dynamic friction coefficient is 0.39.

[0159] Comparative Example 4

[0160] A method for preparing a paper-like film is basically the same as that in Example 6, with the only difference being that the nano-abrasive in Example 1 is replaced by the nano-abrasive in Comparative Example 1.

[0161] The tensile resilience rate of the finally obtained paper-like film is 35.2%, the elongation at break is 110%, the number of friction resistance is 400 times, and the dynamic friction coefficient is 0.24.

[0162] Compared with Example 6, in Comparative Example 4, the tensile resilience rate, elongation at break, friction resistance ability, and dynamic friction coefficient of the paper-like film all decrease significantly. This is because using hollow PP particles as the inner layer of the nano-abrasive cannot provide good elastic ability for the paper-like film, and it cannot provide good support for the external silica layer and effectively disperse external forces. When the paper-like film is subjected to external forces, it cannot disperse and buffer the external forces well, resulting in a significant decrease in the elastic properties of the film, and thus the tensile resilience rate and elongation at break are significantly reduced. Moreover, due to poor elasticity, during the friction process, the surface of the paper-like film cannot well adapt to the pressure changes caused by friction, resulting in a weakening of the friction resistance ability, a decrease in the number of friction resistance, and a reduction in the dynamic friction coefficient.

[0163] Comparative Example 5

[0164] A preparation method of a paper-like film is basically the same as that of Example 6, with the only difference being that the nano-abrasive of Example 1 is replaced by the nano-abrasive of Comparative Example 2.

[0165] The tensile resilience rate of the finally prepared paper-like film is 32.0%, the elongation at break is 92%, the number of friction resistance is 300 times, and the dynamic friction coefficient is 0.25.

[0166] Compared with Example 6, the tensile resilience rate, elongation at break, friction resistance ability, and dynamic friction coefficient of the paper-like film in Comparative Example 5 all decreased significantly. This is because only hollow silica was used as the nano-abrasive in Comparative Example 5, which does not have the ability to effectively disperse external forces in all directions and buffer the hand when subjected to external forces. As a result, when the paper-like film is subjected to external forces, its elastic properties are greatly affected, manifested as a significant reduction in the tensile resilience rate and elongation at break. During the friction process, due to the lack of an effective external force dispersion and buffering mechanism, the adaptability of the surface of the paper-like film to withstand friction pressure becomes poor, resulting in a decrease in the friction resistance ability, the number of friction resistance times, and the dynamic friction coefficient.

[0167] Comparative Example 6

[0168] A preparation method of a paper-like film is basically the same as that of Example 6, with the only difference being that the nano-abrasive of Example 1 is replaced by the nano-abrasive of Comparative Example 3.

[0169] The tensile resilience rate of the finally prepared paper-like film is 30.1%, the elongation at break is 81%, the number of friction resistance is 300 times, and the dynamic friction coefficient is 0.12.

[0170] Compared with Example 6, the tensile resilience rate, elongation at break, friction resistance ability, and dynamic friction coefficient of the paper-like film in Comparative Example 6 all decreased significantly. This is because the nano-abrasive used in Comparative Example 6 is solid silica, which neither has a double-layer airbag structure nor elastic ability. When the paper-like film is subjected to external forces, it cannot buffer the impact of external forces on the film well, resulting in a sharp decline in the elastic properties of the film, manifested as a significant reduction in the tensile resilience rate and elongation at break. During the friction process, due to the lack of an effective external force dispersion and buffering mechanism, the adaptability of the surface of the paper-like film to withstand friction pressure is very poor, resulting in a decrease in the friction resistance ability, the number of friction resistance times, and the dynamic friction coefficient.

[0171] Example 7

[0172] A preparation method of an extruded high-wear-resistant and high-elasticity paper-like film is basically the same as that of Example 6, with the only difference being that both raw material a and raw material c are composed of 65 wt% of PET (manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd., model FG720) and the balance of a nano-abrasive composition. The nano-abrasive composition is composed of 30 wt% of the nano-abrasive of Example 1, 25 wt% of the nano-abrasive of Example 2, 20 wt% of the nano-abrasive of Example 3, 15 wt% of the nano-abrasive of Example 4, and 10 wt% of the nano-abrasive of Example 5.

[0173] The haze of the finally prepared extruded high-wear-resistant and high-elasticity paper-like film is 2.7%, the tensile resilience rate is 99.8%, the elongation at break is 351%, the light transmittance is 92.75%, the number of friction resistance times is 1600 times, and the dynamic friction coefficient is 0.46.

[0174] Example 8

[0175] A preparation method of an extruded high-wear-resistant and high-elasticity paper-like film is as follows:

[0176] (1) Preparation of raw materials;

[0177] Raw material a and raw material c: both are composed of 85 wt% of PET (manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd., model FG720) and the balance of the nano-abrasive of Example 2;

[0178] Raw material b: composed of 62 wt% of PET, 30 wt% of TPU (manufactured by Wanhua Chemical Group Co., Ltd., model WHT-1172IC), 5 wt% of polyolefin elastomer POE (manufactured by DuPont Company of the United States, model N216), and the balance of ethylene terpolymer (manufactured by DuPont Company of the United States, model PTW);

[0179] (2) Preparation of the extruded high-wear-resistant and high-elasticity paper-like film;

[0180] (2.1) Melt-blend and granulate raw material a to obtain modified chip a, melt-blend and granulate raw material b to obtain modified chip b, and melt-blend and granulate raw material c to obtain modified chip c;

[0181] (2.2) Melt-extrude modified chip a, modified chip b, and modified chip c through an extruder respectively, extrude through a filter, a melt metering pump, a distributor, and a multi-layer co-extrusion die head, and cool on a cooling roll to obtain a thick sheet;

[0182] (2.3) The thick sheet is successively subjected to longitudinal stretching (stretching temperature: 100 °C, stretching ratio: 3 times), transverse stretching preheating (temperature: 120 °C), transverse stretching (stretching temperature: 130 °C, stretching ratio: 3.1 times), drying and curing (temperature: 240 °C), heat setting, and cooling, thus obtaining the extruded high wear-resistant and high resilience paper-like film.

[0183] The finally obtained extruded high wear-resistant and high resilience paper-like film consists of a top layer (material: raw material a), a base layer (material: raw material b), and a bottom layer (material: raw material c) from top to bottom; the thicknesses of the top layer and the bottom layer are both 1.2 mm, and the thickness of the base layer is 0.24 mm; the haze of the extruded high wear-resistant and high resilience paper-like film is 2.1%, the tensile resilience rate is 96.9%, the elongation at break is 331%, the light transmittance is 94.92%, the number of friction resistance times is 900 times, and the dynamic friction coefficient is 0.4.

[0184] Example 9

[0185] A preparation method of an extruded high wear-resistant and high resilience paper-like film is basically the same as that of Example 8, with the only difference being that: both raw material a and raw material c consist of 85 wt% of PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FG720) and the balance of the nano-abrasive agent composition, and the nano-abrasive agent composition consists of 50 wt% of the nano-abrasive agent of Example 1, 20 wt% of the nano-abrasive agent of Example 2, 15 wt% of the nano-abrasive agent of Example 3, 10 wt% of the nano-abrasive agent of Example 4, and 5 wt% of the nano-abrasive agent of Example 5.

[0186] The haze of the finally obtained extruded high wear-resistant and high resilience paper-like film is 2.5%, the tensile resilience rate is 98.5%, the elongation at break is 342%, the light transmittance is 95.55%, the number of friction resistance times is 1500 times, and the dynamic friction coefficient is 0.44.

[0187] Example 10

[0188] A preparation method of an extruded high wear-resistant and high resilience paper-like film is as follows:

[0189] (1) Preparation of raw materials;

[0190] Raw material a and raw material c: both consist of 85 wt% of PET (manufacturer: Sinopec Yizheng Chemical Fiber Co., Ltd., model: FG720) and the balance of the nano-abrasive agent of Example 3;

[0191] Raw material b: It consists of 62 wt% of PET, 30 wt% of TPU (manufactured by Wanhua Chemical Group Co., Ltd., model number WHT-1172IC), 5 wt% of maleic anhydride grafted compatibilizer TPU-G-MAH (manufactured by Dongguan Shenghao Plastic Raw Materials Co., Ltd.) and the balance ethylene terpolymer (manufactured by DuPont Company of the United States, model number PTW);

[0192] (2)Prepare an extruded high wear-resistant and high resilience paper-like film;

[0193] (2.1)Melt-blend and pelletize raw material a to obtain modified pellet a, melt-blend and pelletize raw material b to obtain modified pellet b, and melt-blend and pelletize raw material c to obtain modified pellet c;

[0194] (2.2)Melt-extrude modified pellet a, modified pellet b, and modified pellet c respectively through an extruder, and extrude through a filter, a melt metering pump, a distributor, and a multi-layer co-extrusion die head, and cool on a cooling roll to obtain a thick sheet;

[0195] (2.3)Perform longitudinal stretching (stretching temperature is 100 °C, stretching ratio is 3 times), transverse stretching preheating (temperature is 120 °C), transverse stretching (stretching temperature is 130 °C, stretching ratio is 3.1 times), drying and curing (temperature is 240 °C), heat setting, and cooling on the thick sheet in sequence, then the extruded high wear-resistant and high resilience paper-like film is obtained.

[0196] The finally prepared extruded high wear-resistant and high resilience paper-like film consists of a top layer (material is raw material a), a base layer (material is raw material b), and a bottom layer (material is raw material c) from top to bottom; the thicknesses of the top layer and the bottom layer are both 1.2 mm, and the thickness of the base layer is 0.24 mm; the haze of the extruded high wear-resistant and high resilience paper-like film is 2.5%, the tensile resilience rate is 96.7%, the elongation at break is 328%, the light transmittance is 93.68%, the number of friction resistance times is 1000 times, and the dynamic friction coefficient is 0.41.

[0197] Example 11

[0198] A preparation method of an extruded high wear-resistant and high resilience paper-like film, the specific steps are as follows:

[0199] (1)Preparation of raw materials;

[0200] Raw material a and raw material c: Both consist of 85 wt% of PET (manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd., model number FG720) and the balance nano-abrasive of Example 4;

[0201] Raw material b: It consists of 62 wt% of PET, 30 wt% of TPU (manufactured by Wanhua Chemical Group Co., Ltd., model WHT-1172IC), 5 wt% of compatibilizer, and the balance ethylene terpolymer (manufactured by DuPont Company of the United States, model PTW). The compatibilizer is a mixture of polyolefin elastomer POE (manufactured by DuPont Company of the United States, model N216) and maleic anhydride grafted compatibilizer TPU-G-MAH (manufactured by Dongguan Shenghao Plastic Raw Materials Co., Ltd.) with a mass ratio of 1:1;

[0202] (2)Prepare an extruded high wear-resistant and high resilience paper-like film;

[0203] (2.1)Melt-blend and pelletize raw material a to obtain modified pellet a, melt-blend and pelletize raw material b to obtain modified pellet b, and melt-blend and pelletize raw material c to obtain modified pellet c;

[0204] (2.2)Melt-extrude modified pellet a, modified pellet b, and modified pellet c through an extruder respectively, extrude through a filter, melt metering pump, distributor, and multi-layer co-extrusion die head, and cool on a cooling roll to obtain a thick sheet;

[0205] (2.3)Perform longitudinal stretching (stretching temperature is 100 °C, stretching ratio is 3 times), transverse stretching preheating (temperature is 120 °C), transverse stretching (stretching temperature is 130 °C, stretching ratio is 3.1 times), drying and curing (temperature is 240 °C), heat setting, and cooling on the thick sheet in sequence to obtain the extruded high wear-resistant and high resilience paper-like film.

[0206] The finally prepared extruded high wear-resistant and high resilience paper-like film consists of an upper surface layer (material is raw material a), a base layer (material is raw material b), and a lower surface layer (material is raw material c) from top to bottom; the thicknesses of the upper surface layer and the lower surface layer are both 1.2 mm, and the thickness of the base layer is 0.24 mm; the haze of the extruded high wear-resistant and high resilience paper-like film is 2.6%, the tensile resilience rate is 97.2%, the elongation at break is 338%, the light transmittance is 92.69%, the number of friction resistance times is 1100 times, and the dynamic friction coefficient is 0.42.

[0207] Example 12

[0208] A preparation method of an extruded high wear-resistant and high resilience paper-like film, the specific steps are as follows:

[0209] (1)Preparation of raw materials;

[0210] Raw material a and raw material c: Both consist of 85 wt% of PET (manufactured by Sinopec Yizheng Chemical Fiber Co., Ltd., model FG720) and the balance nano-abrasive of Example 5;

[0211] Raw material b: It consists of 62 wt% PET, 30 wt% TPU (manufactured by Wanhua Chemical Group Co., Ltd., model WHT-1172IC), 5 wt% compatibilizer, and the balance ethylene terpolymer (manufactured by DuPont Company of the United States, model PTW). The compatibilizer is a mixture of polyolefin elastomer POE (manufactured by DuPont Company of the United States, model N216) and maleic anhydride grafted compatibilizer TPU-G-MAH (manufactured by Dongguan Shenghao Plastic Raw Materials Co., Ltd.) with a mass ratio of 1:1;

[0212] (2)Prepare an extruded high wear-resistant and high resilience paper-like film;

[0213] (2.1)Melt-blend and pelletize raw material a to obtain modified pellet a, melt-blend and pelletize raw material b to obtain modified pellet b, and melt-blend and pelletize raw material c to obtain modified pellet c;

[0214] (2.2)Melt-extrude modified pellet a, modified pellet b, and modified pellet c through an extruder respectively, extrude through a filter, a melt metering pump, a distributor, and a multi-layer coextrusion die head, and cool on a cooling roll to obtain a thick sheet;

[0215] (2.3)Longitudinally stretch the thick sheet (stretching temperature is 100 °C, stretching ratio is 3 times), preheat for transverse stretching (temperature is 120 °C), transversely stretch (stretching temperature is 130 °C, stretching ratio is 3.1 times), dry and cure (temperature is 240 °C), heat-set, and cool to obtain the extruded high wear-resistant and high resilience paper-like film.

[0216] The finally prepared extruded high wear-resistant and high resilience paper-like film consists of an upper surface layer (material is raw material a), a base layer (material is raw material b), and a lower surface layer (material is raw material c) from top to bottom; the thicknesses of the upper surface layer and the lower surface layer are both 1.2 mm, and the thickness of the base layer is 0.24 mm; the haze of the extruded high wear-resistant and high resilience paper-like film is 2.7%, the tensile resilience rate is 98.2%, the elongation at break is 340%, the light transmittance is 92.71%, the number of friction resistance times is 1200 times, and the dynamic friction coefficient is 0.45.

Claims

1. An extruded high wear-resistant and high resilience paper film, characterized in that: It comprises an upper surface layer, a base layer and a lower surface layer which are arranged in sequence from top to bottom; the upper surface layer and the lower surface layer contain additives, and the additives are nano-abrasives or nano-abrasives compositions; The nano-abrasive agent is composed of hollow TPU fiber particles and a silicon dioxide layer deposited and grown in situ on its outer wall; The nano-abrasive composition is composed of 30-50 wt% of nano-abrasive I, 20-25 wt% of nano-abrasive II, 15-20 wt% of nano-abrasive III, 10-15 wt% of nano-abrasive IV and 5-10 wt% of nano-abrasive V; The particle size of the nano-abrasive agent I is less than 0.5 μm; in the nano-abrasive agent I, the inner diameter of the hollow TPU fiber particles is 0.1-0.2 μm and the wall thickness is 0.05 μm, and the thickness of the silicon dioxide layer is 0.05-0.1 μm; The particle size of the nano-abrasive agent II is greater than or equal to 0.5 μm and less than 1 μm; in the nano-abrasive agent II, the inner diameter of the hollow TPU fiber particles is 0.2-0.4 μm and the wall thickness is 0.1 μm, and the thickness of the silicon dioxide layer is 0.1-0.2 μm; The particle size of the nano-scrubber III is greater than or equal to 1 μm and less than 10 μm; in the nano-scrubber III, the inner diameter of the hollow TPU fiber particles is 0.4-4 μm and the wall thickness is 0.1-1 μm, and the thickness of the silicon dioxide layer is 0.2-2 μm; The particle size of the nano-abrasive agent IV is greater than or equal to 10 μm and less than 20 μm; in the nano-abrasive agent IV, the inner diameter of the hollow TPU fiber particles is 3-6 μm and the wall thickness is 1.5-3 μm, and the thickness of the silicon dioxide layer is 2-4 μm; The particle size of the nano-abrasive agent V is greater than or equal to 20 μm and less than or equal to 25 μm; in the nano-abrasive agent V, the inner diameter of the hollow TPU fiber particles is 6-7 μm and the wall thickness is 3-4 μm, and the thickness of the silicon dioxide layer is 4-5 μm.

2. The extruded high wear-resistant and high resilience paper film according to claim 1, characterized in that: The content of silicon dioxide in the nano-abrasive agent is 50-60wt%.

3. Preparation of an extruded high wear-resistant and high resilience paper film as claimed in claim 1 or 2, characterized in that: The preparation of the nano-scrub comprises the following steps: (a) preparing hollow TPU fiber particles; (b) dissolving a silicon source in an acidic solution to obtain a solution A; (c) adding the hollow TPU fiber particles to solution A, adding alkali, reacting at 60° C. for 2-6 h under stirring conditions to obtain solution B, and post-treating solution B to obtain a nano-abrasive.