Basalt fiber composite TPU high and low temperature film and preparation method thereof

Abstract

The invention discloses a basalt fiber composite TPU (thermoplastic polyurethane) high-low temperature film and a preparation method thereof. The composite film sequentially comprises a basalt fiber mesh cloth layer roughened by plasma etching, a heat-resistant bonding layer, a rheological optimization TPU hot melt adhesive layer, a low-temperature hot melt adhesive functional layer and a colored PU (polyurethane) decorative layer, the basalt fiber mesh cloth is subjected to radio frequency plasma treatment; the heat-resistant bonding layer is prepared from ternary synergistic interface modified slurry containing gamma-aminopropyltriethoxysilane, aluminum hypophosphite, nano SiO2 and the like; the TPU hot melt adhesive layer is prepared by taking polycaprolactone glycol as a main raw material and cooperating with 4, 4 '-dicyclohexylmethane diisocyanate and the like; the preparation method comprises the steps of plasma etching, ultrasonic-vacuum impregnation, elastic micro-convex pressing roller compounding and the like. The interface peel strength of the composite film is larger than or equal to 35 N / cm, and the composite film has excellent high and low temperature resistance and interface bonding strength and is suitable for the field of composite materials needing weather resistance, such as automotive trim and building decoration.

Description

Technical Field

[0001] This invention relates to the field of composite membrane technology, specifically to a basalt fiber composite TPU high and low temperature membrane and its preparation method. Background Technology

[0002] Basalt fiber, as a novel inorganic fiber material, possesses excellent properties such as high strength, high temperature resistance, corrosion resistance, and environmental friendliness, making it a promising candidate for applications in the field of composite materials. Thermoplastic polyurethane (TPU), due to its superior elasticity, abrasion resistance, and processing properties, is widely used in film material preparation. Combining basalt fiber with TPU to prepare high-performance film materials can fully leverage the advantages of both materials, meeting the needs of high-end applications such as sports protection, military inflatable tents, and high-temperature decoration.

[0003] Currently, various preparation technologies for basalt fiber composite materials exist. Chinese patent CN114213984B discloses a BOPP pre-coated film, in which modified basalt fibers are treated with plasma and silane coupling agents to improve their bonding performance with the polymer matrix. Chinese patent CN219279781U discloses a self-healing TPU high and low temperature film, comprising a multi-layer structure design of a TPU carrier layer, a decorative layer, and a hot melt adhesive layer. Chinese patent CN113861460B proposes a basalt fiber / polypropylene composite material based on surface roughening and interface reinforcement, achieving fiber surface modification through acrylic impregnation and electron beam irradiation. Chinese patent CN108790333B describes a high peel strength fiber composite material, employing a structure where a TPU film and a fiber base fabric are composited through a TPU hot melt adhesive layer. Chinese patent CN109624422B discloses a method for preparing a TPU high and low temperature film composite mesh, achieving film-fabric composite through initial composite and vacuum texturing processes.

[0004] However, existing technologies for preparing basalt fiber and TPU composite film materials still suffer from numerous technical shortcomings. First, the surface of basalt fiber is chemically inert, relying solely on van der Waals forces for bonding with TPU, resulting in interfacial peel strength generally less than 10 N / cm, which is insufficient for high-strength applications. Second, traditional silane coupling agent treatment methods are highly susceptible to environmental humidity, with an interfacial bonding density variation coefficient exceeding 15% and poor batch stability. Third, existing interfacial modifiers are prone to thermal degradation at TPU processing temperatures (180-220℃), leading to interfacial bonding failure. Furthermore, TPU melt exhibits poor wettability on smooth basalt surfaces, with a wetting angle greater than 60° and a penetration depth less than 3 μm, resulting in weak mechanical anchoring. Finally, existing pressing processes have a narrow window, making process parameter control difficult and resulting in a yield rate below 80%, severely hindering industrial applications. Summary of the Invention

[0005] To address the technical challenges of low interfacial bonding strength, poor high-temperature stability, and unsatisfactory batch-to-batch consistency between basalt fiber and thermoplastic polyurethane (TPU), and to achieve an interfacial peel strength ≥35 N / cm and a retention rate ≥90% after boiling at 100℃ for 2 hours, a basalt fiber composite TPU high and low temperature film and its preparation method are provided.

[0006] The objective of this invention is achieved through the following technical solution: a basalt fiber composite TPU high and low temperature film, comprising, in sequence, a basalt fiber mesh layer roughened by plasma etching; a heat-resistant bonding layer located on the surface of the basalt fiber mesh layer; a rheology-optimized TPU hot melt adhesive layer fused to the heat-resistant bonding layer; a low-temperature hot melt adhesive functional layer located on the outside of the TPU; and a colored PU decorative layer located on the outside of the basalt fiber; wherein, the interfacial peel strength of the composite film is ≥35N / cm, the retention rate after boiling in water at 100℃ for 2h is ≥90%, and the interfacial shear strength attenuation is ≤10% after 100 cycles from -40℃ to 120℃.

[0007] In this invention, the composite membrane achieves excellent comprehensive performance through the synergistic effect of its multi-layer structure: the basalt fiber mesh layer provides basic strength and temperature resistance; plasma etching treatment increases surface roughness and active groups, improving interfacial bonding; the heat-resistant bonding layer connects the inorganic fibers and the organic TPU layer through chemical bonding; the rheology-optimized TPU layer provides flexibility and sealing performance; and the multifunctional additive system ensures the stability of the composite membrane under extreme temperature conditions.

[0008] Tests showed that the composite membrane has an interfacial peel strength of ≥35N / cm, a retention rate of ≥90% after boiling in water at 100℃ for 2 hours, and an interfacial shear strength attenuation of ≤10% after 100 cycles from -40℃ to 120℃, fully meeting the requirements for use in high and low temperature environments.

[0009] Preferably, the basalt fiber mesh layer is prepared by the following method: 1.1. The basalt ore is crushed to d50=5-8μm, melted at 1500-1550℃, and drawn at a speed of 200-400m / min using a platinum-rhodium alloy spinneret to form 7-9μm precursor yarn. After cooling and solidification, it is coated with a sizing agent, bundled and dried to form 200-800tex yarn. The above yarn is then twisted to a twist of about 50-300 twists / meter. 1.2. Fabricated using two-dimensional warp knitting, nonwoven, or woven techniques, with a weight of 40-300 g / m². 2 A mesh, nonwoven or woven fabric base with a porosity of 35-55% is coated with acrylic emulsion, water-based polyurethane or styrene-acrylic emulsion for shaping. 1.3. The base fabric is plasma etched using an atmospheric pressure roll-to-roll radio frequency plasma treatment machine with a power of 200-250W, O2 / N2=1:1, corresponding to a single-sided exposure time of 150-400s. After treatment, the surface roughness Ra=1.8-2.5μm and the water contact angle is reduced from 78° to 25°.

[0010] Preferably, the heat-resistant bonding layer is coated with a ternary synergistic interface-modified slurry; the modified slurry comprises the following raw materials in parts by weight: 100 parts of γ-aminopropyltriethoxysilane (KH-550), 400-500 parts of anhydrous ethanol, 10-15 parts of deionized water, 0.5-1.0 parts of acetic acid, 5-10 parts of aluminum hypophosphite (ALHP), 2-4 parts of nano-SiO2, 0.5-1.0 parts of titanate coupling agent, and 80-120 parts of polyetheramine D-2000.

[0011] Preferably, the heat-resistant bonding layer is prepared by the following method: γ-aminopropyltriethoxysilane, anhydrous ethanol, deionized water, acetic acid, aluminum hypophosphite, nano-SiO2, titanate coupling agent and polyetheramine are mixed according to the following parts by weight, heated to 25-30℃ and ultrasonically impregnated (28kHz, 200W) for 10-15min, vacuum degassing at -0.09MPa×15min; cured at 120℃ for 2h and then cured at 80℃ for 1h to obtain a heat-resistant bonding layer with a thickness of 8-12μm, a surface amino density ≥1.2mmol / g, and a roughness Rz=3-5μm.

[0012] Preferably, the TPU hot melt adhesive layer comprises the following raw materials in parts by weight: 100 parts polycaprolactone diol, 45-48 parts 4,4'-dicyclohexylmethane diisocyanate, 11-12 parts 1,4-butanediol, 3.5-4.0 parts 1,4-cyclohexanediethanol, 3-4 parts crosslinking agent, 2-3 parts epoxy end-capping agent, 0.8-1.0 parts anti-hydrolysis agent, 1.5-2.0 parts N,N-dimethylacetamide, 0.01-0.03 parts organic bismuth catalyst, 0.2-0.4 parts antioxidant 1010, and 0.2-0.4 parts light stabilizer 770.

[0013] Preferably, the hydroxyl value of the polycaprolactone diol is 54-58 mgKOH / g.

[0014] Preferably, the epoxy end-capping agent is at least one of γ-glycidyl etheroxypropyltrimethoxysilane, 1,4-butanediol diglycidyl ether, and aqueous epoxy emulsifier EP-530.

[0015] Preferably, the anti-hydrolysis agent is at least one of polycarbodiimide, monomeric carbodiimide, and oxazoline anti-hydrolysis agents.

[0016] This invention also provides a method for preparing a basalt fiber composite TPU high and low temperature film, comprising the following steps: S1. Plasma etching is performed on basalt fiber substrate; S2. Within 24 hours after plasma treatment, the ternary synergistic interface modification slurry is ultrasonically-vacuum impregnated onto the basalt fiber mesh and cured in sections to obtain a modified mesh containing a heat-resistant bonding layer. S3. Heat the modified mesh obtained in step S2 to 90-95℃ for 40-50s, and heat the TPU hot melt adhesive to 140℃ for 30-40s. Under the conditions of 160-190℃, 0.5-0.9MPa and linear speed of 1-5m / min, the rheology-optimized TPU hot melt adhesive and the modified mesh are compounded by an elastic micro-convex pressing roller. S4. Colored PU coating: Apply water-based PU color paste to the basalt fiber surface treated in step S3, heat to 100-110℃ and cure for 2-3 minutes to form a decorative layer with a light transmittance of 20-80% and a texture depth of 20-40μm. S5, Low-temperature hot melt adhesive layer: EVA / PA / TPU film is laminated onto the TPU hot melt adhesive layer, with a thickness of 30-60μm, to form a functional layer.

[0017] Preferably, in step S3, the surface of the elastic micro-convex pressing roller is Shore A80 silicone rubber, the micro-convex height is 0.15-0.25mm, the spacing is 1.5-2.5mm, and the zone pressure is 0.3-0.5MPa at the inlet, 0.6-0.9MPa at the center, and 0.4-0.6MPa at the outlet.

[0018] This invention is the first to synergistically introduce a ternary heat-resistant bonding network of "aminosilane-aluminum hypophosphite-narrowly distributed polyetheramine" and a penetration anchoring mechanism of "plasma micro-roughening-low melt index TPU-micro-convex elastic pressing" into the same system, solving the dual challenges of chemical inertness and physical smoothness at the interface between basalt fiber and TPU. By adopting an ALHP-nano SiO2-titanium ester synergistic scheme, the thermal decomposition rate of the phytic acid-based ionic bond network in the 220℃ processing section is reduced from 35% to <5%, significantly improving the interface's heat resistance stability. Elastic micro-convex pressing + zoned pressure + online infrared closed-loop control increases the TPU melt's wetting depth on the fiber surface from 3μm to 12-15μm, achieving biaxial reinforcement of "chemical bonds + mechanical anchoring" and increasing peel strength by >250%.

[0019] The beneficial effects of this invention are as follows: Through plasma etching roughening treatment and the application of ternary synergistic interface modification slurry, the interfacial peel strength is ≥35 N / cm, an improvement of over 250% compared to the <10 N / cm of the prior art; the retention rate after boiling at 100℃ for 2 hours is ≥90%, a significant improvement compared to the <50% of the prior art; the interfacial shear strength decay is ≤10% after 100 cycles of thermal cycling at -40℃ for 4 hours and 120℃ for 4 hours, a substantial improvement compared to the 52% of the prior art; and the film thickness variation coefficient is ≤5%, a significant improvement compared to the 18% of the prior art. Improvements include: flame retardancy rating reaching VTM-0, oxygen index 32%; adjustable light transmittance from 20-85% to meet different application needs; a qualified product rate of ≥95%, a significant improvement compared to the <80% of existing technologies; the adoption of a synergistic scheme of aluminum hypophosphite-nano SiO2-titanium ester reduces the thermal decomposition rate of the ionic bond network from 35% to <5% in the 220℃ processing section; and through elastic micro-convex pressing + zoned pressure + online infrared closed-loop control, the TPU melt wetting depth on the fiber surface is increased from 3μm to 12-15μm, achieving biaxial reinforcement of "chemical bonds + mechanical anchoring". Detailed Implementation

[0020] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments. The content mentioned in the embodiments is not intended to limit the present invention.

[0021] Example 1 This embodiment provides a basalt fiber composite TPU high and low temperature film, which, from the inside out, includes a basalt fiber mesh layer roughened by plasma etching, a heat-resistant bonding layer, a rheology-optimized TPU hot melt adhesive layer, a low temperature hot melt adhesive functional layer, and a colored PU decorative layer.

[0022] The preparation process of the basalt fiber mesh layer is as follows: S1: Raw material pretreatment: Basalt ore is crushed to d50=6μm, melted at 1525℃, and drawn into 8μm filaments using a platinum-rhodium alloy spinneret at a speed of 300m / min. After cooling and solidification, it is coated with a sizing agent, bundled and dried into 500tex yarn. The above yarn is then twisted to a twist of about 50-300 twists / meter.

[0023] S2: Mesh weaving: woven using two-dimensional warp knitting technology, weighing 150g / m². 2 A mesh, nonwoven or woven base fabric with a porosity of 45% is used, and the surface of the base fabric is coated with acrylic emulsion, waterborne polyurethane or styrene-acrylic emulsion for shaping.

[0024] S3: Plasma Surface Treatment: The base fabric was plasma etched using a normal pressure roll-to-roll RF plasma treatment machine with a treatment power of 250W, O2 / N2=1:1, and a single-sided exposure time of 300s. After treatment, the surface roughness Ra=2.1μm, and the water contact angle decreased from 78° to 25°, significantly improving the wettability and adhesion of the fiber surface.

[0025] The heat-resistant bonding layer was prepared by coating with a ternary synergistic interface modified slurry, which included: 100 parts of γ-aminopropyltriethoxysilane (KH-550), 450 parts of anhydrous ethanol, 12 parts of deionized water, 0.8 parts of acetic acid, 8 parts of aluminum hypophosphite (ALHP), 3 parts of nano-SiO2, 0.8 parts of titanate coupling agent, and 100 parts of polyetheramine D-2000.

[0026] The preparation process of the heat-resistant bonding layer is as follows: S1: Slurry preparation: Mix the above components according to the weight parts, heat to 28℃ and ultrasonically impregnate (28kHz, 200W) for 12min, and then vacuum degas at -0.09MPa for 15min.

[0027] S2: Coating and Curing: The slurry was coated onto the surface of the plasma-treated basalt fiber mesh, cured at 120℃ for 2 hours, and then cured at 80℃ for 1 hour to obtain a heat-resistant bonding layer with a thickness of 10 μm, a surface amino density of 1.3 mmol / g, and a roughness Rz=4 μm. This bonding layer forms chemical bonds with the basalt fiber through a silane coupling agent, while the amino functional groups form hydrogen bonds and chemical crosslinks with the TPU layer, significantly improving the interlayer bonding strength.

[0028] The TPU hot melt adhesive layer is prepared using the following formula: 100 parts polycaprolactone diol, 46 parts 4,4'-dicyclohexylmethane diisocyanate, 11.5 parts 1,4-butanediol, 3.8 parts 1,4-cyclohexanediethanol, 3.5 parts crosslinking agent, 2.5 parts epoxy end-capping agent, 0.9 parts anti-hydrolysis agent, 1.8 parts N,N-dimethylacetamide, 0.02 parts organic bismuth catalyst, 0.3 parts antioxidant (10100), and 0.3 parts light stabilizer (7700).

[0029] The hydroxyl value of polycaprolactone diol is 56 mg KOH / g, providing flexible segments for TPU and ensuring the flexibility of the composite film at low temperatures. The epoxy end-capping agent is γ-glycidyl etheroxypropyltrimethoxysilane, which forms covalent bonds with the amino groups in the bonding layer through the reaction of epoxy groups, improving interfacial bonding strength. The anti-hydrolysis agent is polycarbodiimide, which can capture the carboxylic acid groups generated by hydrolysis, preventing the degradation of TPU under high temperature and high humidity environments.

[0030] In a preferred embodiment, the epoxy end-capping agent may also be 1,4-butanediol diglycidyl ether or aqueous epoxy emulsifier EP-530.

[0031] In a preferred embodiment, the anti-hydrolysis agent may also be a monomeric carbodiimide or an oxazoline-based anti-hydrolysis agent.

[0032] The low-temperature hot melt adhesive functional layer is located on the outside of the TPU layer and uses modified polyurethane hot melt adhesive, which maintains good adhesion performance even at low temperatures. The colored PU decorative layer is located on the outside of the basalt fiber, providing decorative effect and additional protection.

[0033] This composite membrane achieves excellent comprehensive performance through the synergistic effect of its multi-layer structure: the basalt fiber mesh layer provides basic strength and temperature resistance; plasma etching treatment increases surface roughness and active groups, improving interfacial bonding; the heat-resistant bonding layer connects the inorganic fibers and the organic TPU layer through chemical bonding; the rheology-optimized TPU layer provides flexibility and sealing performance; and the multifunctional additive system ensures the stability of the composite membrane under extreme temperature conditions.

[0034] Tests showed that the composite membrane exhibited an interfacial peel strength of 38.5 N / cm, a 91.4% retention rate after boiling in water at 100℃ for 2 hours, and a resistance at -40℃. After 100 cycles at 120℃, the interfacial shear strength attenuation rate is only 9.6%, which fully meets the requirements for use in high and low temperature environments.

[0035] Example 2 This embodiment provides a method for preparing a basalt fiber composite TPU high and low temperature film. Based on the composite film structure described in Embodiment 1, this method achieves precise composite of each layer through specific process steps.

[0036] S1: Plasma etching was performed on the basalt fiber substrate. The same plasma treatment process as in Example 1 was used, employing an atmospheric pressure roll-to-roll RF plasma treatment machine with a processing power of 425W, O2 / N2=1:1, and a single-sided exposure time of 75s. This resulted in a surface roughness of Ra=2.1μm for the basalt fiber mesh and a water contact angle reduced from 78° to 25°, providing an active surface for subsequent interface modification.

[0037] S2: Within 24 hours after plasma treatment, the ternary synergistic interface-modified slurry was ultrasonically-vacuum impregnated onto basalt fiber mesh and cured in stages to obtain a modified mesh containing a heat-resistant bonding layer. Using the modified slurry formulation from Example 1, the slurry was ultrasonically impregnated at 28°C for 12 min (28 kHz, 200 W), followed by vacuum degassing treatment (-0.09 MPa × 15 min). After impregnation, it was first cured at 120°C for 2 h, and then cured at 80°C for 1 h to form a heat-resistant bonding layer with a thickness of 10 μm, a surface amino density of 1.3 mmol / g, and a roughness Rz = 4 μm.

[0038] S3: The modified mesh obtained in step S2 is preheated to 92℃ for 45 seconds, and the TPU hot melt adhesive is preheated to 140℃ for 35 seconds. At 175℃, 0.7MPa, and a linear speed of 3m / min, the rheology-optimized TPU hot melt adhesive is composited with the modified mesh using an elastic micro-convex pressing roller. The surface of the elastic micro-convex pressing roller is made of Shore A80 silicone rubber, with a micro-convex height of 0.2mm and a spacing of 2.0mm. The zoned pressure is set to 0.4MPa at the inlet, 0.75MPa at the center, and 0.5MPa at the outlet. The TPU hot melt adhesive uses the formulation from Example 1, achieving its optimal rheological state during preheating. The zoned pressure control of the micro-convex pressing roller ensures that the TPU hot melt adhesive fully penetrates the pores of the basalt fiber mesh, forming a strong chemical bond and physical anchor with the heat-resistant bonding layer.

[0039] S4: Colored PU Coating Treatment. A water-based PU colorant is applied to the basalt fiber surface treated in step S3 and cured at 105℃ for 2.5 minutes to form a decorative layer with 65% light transmittance and a texture depth of 30μm. This decorative layer not only provides an aesthetic effect but also enhances the surface protection properties of the composite film.

[0040] S5: Low-temperature hot melt adhesive layer lamination. An EVA / PA / TPU film with a thickness of 45μm is laminated onto the TPU hot melt adhesive layer to form a functional layer. This functional layer maintains good adhesion and flexibility even at low temperatures, ensuring stable use of the composite film within a temperature range of -40℃ to 120℃.

[0041] In a preferred embodiment, the preheating temperature of the modified mesh in step S3 can also be other values ​​within the range of 90-95℃, and the preheating time can be 40-50s; the preheating time of the TPU hot melt adhesive can be 30-40s; the temperature of the composite process can be 160-190℃, the pressure can be 0.5-0.9MPa, and the linear speed can be 1-5m / min.

[0042] In a preferred embodiment, the convex height of the elastic micro-convex pressing roller can also be other values ​​in the range of 0.15-0.25mm, the spacing can be 1.5-2.5mm; the partition pressure inlet can be 0.3-0.5MPa, the center can be 0.6-0.9MPa, and the outlet can be 0.4-0.6MPa.

[0043] In a preferred embodiment, the heating temperature in step S4 can also be 100-110℃, the curing time can be 2-3 min, the light transmittance of the formed decorative layer can be 20-80%, and the texture depth can be 20-40 μm.

[0044] In a preferred embodiment, the thickness of the low-temperature hot melt adhesive layer in step S5 can also be other values ​​in the range of 30-60 μm.

[0045] The basalt fiber composite TPU high and low temperature film obtained by the above preparation method has strong interlayer bonding, an interfacial peel strength of 38.5 N / cm, a retention rate of 91.4% after boiling in water at 100℃ for 2 hours, and a temperature of -40℃. After 100 cycles at 120℃, the interfacial shear strength attenuation rate is only 9.6%, fully meeting the requirements for use in high and low temperature environments. This preparation method achieves uniform lamination of TPU hot melt adhesive and modified mesh fabric through precise control of various process parameters, especially the partitioned pressure design of the elastic micro-convex pressing roller, ensuring the high-quality preparation of the composite film.

[0046] Comparative Example 1 The difference between this comparative example and Example 1 above is that this comparative example does not use modified basalt. The rest of the contents of this comparative example are the same as those of Example 1, and will not be repeated here.

[0047] The TPU composite film obtained by the above preparation method was tested and found to have an interfacial peel strength of 9.8 N / cm, 4.1 N / cm after boiling in water, a retention rate of 42%, a decay of 52% after high and low temperature cycling, and a thickness unevenness CV of 18%.

[0048] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A basalt fiber composite TPU high and low temperature film, characterized in that: The product comprises, in sequence, a basalt fiber mesh layer roughened by plasma etching; a heat-resistant bonding layer on the surface of the basalt fiber mesh layer; a rheology-optimized TPU hot melt adhesive layer fused to the heat-resistant bonding layer; a low-temperature hot melt adhesive functional layer on the outside of the TPU; and a colored PU decorative layer on the outside of the basalt fiber.

2. The basalt fiber composite TPU high and low temperature film according to claim 1, characterized in that: The basalt fiber mesh layer is prepared by the following method: 1.

1. The basalt ore is crushed to d50=5-8μm, melted at 1500-1550℃, and drawn at a speed of 200-400m / min using a platinum-rhodium alloy spinneret to form 7-9μm precursor yarn. After cooling and solidification, it is coated with a sizing agent, bundled and dried to form 200-800tex yarn. The above yarn is then twisted to a twist of about 50-300 twists / meter. 1.

2. Fabricated using two-dimensional warp knitting, nonwoven, or woven techniques, with a weight of 40-300 g / m². 2 A mesh, nonwoven or woven fabric base with a porosity of 35-55% is coated with acrylic emulsion, water-based polyurethane or styrene-acrylic emulsion for shaping. 1.

3. The base fabric is plasma etched using an atmospheric pressure roll-to-roll radio frequency plasma treatment machine with a power of 200-250W, O2 / N2=1:1, corresponding to a single-sided exposure time of 150-400s. After treatment, the surface roughness Ra=1.8-2.5μm and the water contact angle is reduced from 78° to 25°.

3. The basalt fiber composite TPU high and low temperature film according to claim 1, characterized in that: The heat-resistant bonding layer is formed by coating with a ternary synergistic interface-modified slurry; the modified slurry comprises the following raw materials in parts by weight: 100 parts of γ-aminopropyltriethoxysilane, 400-500 parts of anhydrous ethanol, 10-15 parts of deionized water, 0.5-1.0 parts of acetic acid, 5-10 parts of aluminum hypophosphite, 2-4 parts of nano-SiO2, 0.5-1.0 parts of titanate coupling agent, and 80-120 parts of polyetheramine.

4. The basalt fiber composite TPU high and low temperature film according to claim 3, characterized in that: The heat-resistant bonding layer is prepared by the following method: γ-aminopropyltriethoxysilane, anhydrous ethanol, deionized water, acetic acid, aluminum hypophosphite, nano-SiO2, titanate coupling agent and polyetheramine are mixed according to the weight parts, heated to 25-30℃ and ultrasonically impregnated for 10-15 min, vacuum degassing at -0.09MPa×15 min; cured at 120℃ for 2 h and then cured at 80℃ for 1 h to obtain a heat-resistant bonding layer with a thickness of 8-12 μm, a surface amino density ≥1.2 mmol / g, and a roughness Rz=3-5 μm.

5. The basalt fiber composite TPU high and low temperature film according to claim 1, characterized in that: The TPU hot melt adhesive layer comprises the following raw materials in parts by weight: 100 parts polycaprolactone diol, 45-48 parts 4,4'-dicyclohexylmethane diisocyanate, 11-12 parts 1,4-butanediol, 3.5-4.0 parts 1,4-cyclohexanediethanol, 3-4 parts crosslinking agent, 2-3 parts epoxy end-capping agent, 0.8-1.0 parts anti-hydrolysis agent, 1.5-2.0 parts N,N-dimethylacetamide, 0.01-0.03 parts organic bismuth catalyst, 0.2-0.4 parts antioxidant 1010, and 0.2-0.4 parts light stabilizer 770.

6. The basalt fiber composite TPU high and low temperature film according to claim 5, characterized in that: The hydroxyl value of the polycaprolactone diol is 54-58 mg KOH / g.

7. The basalt fiber composite TPU high and low temperature film according to claim 5, characterized in that: The epoxy end-capping agent is at least one of γ-glycidyl etheroxypropyltrimethoxysilane, 1,4-butanediol diglycidyl ether, and aqueous epoxy emulsifier EP-530.

8. The basalt fiber composite TPU high and low temperature film according to claim 5, characterized in that: The anti-hydrolysis agent is at least one of polycarbodiimide, monomeric carbodiimide, and oxazoline anti-hydrolysis agents.

9. A method for preparing a basalt fiber composite TPU high and low temperature film as described in any one of claims 1-8, characterized in that: Includes the following steps: S1. Plasma etching is performed on basalt fiber substrate; S2. Within 24 hours after plasma treatment, the ternary synergistic interface modification slurry is ultrasonically-vacuum impregnated onto the basalt fiber mesh and cured in sections to obtain a modified mesh containing a heat-resistant bonding layer. S3. Heat the modified mesh obtained in step S2 to 90-95℃ for 40-50s, and heat the TPU hot melt adhesive to 140℃ for 30-40s. Under the conditions of 160-190℃, 0.5-0.9MPa and linear speed of 1-5m / min, the rheology-optimized TPU hot melt adhesive and the modified mesh are compounded by an elastic micro-convex pressing roller. S4. Colored PU coating: Apply water-based PU color paste to the basalt fiber surface treated in step S3, heat to 100-110℃ and cure for 2-3 minutes to form a decorative layer with a light transmittance of 20-80% and a texture depth of 20-40μm. S5, Low-temperature hot melt adhesive layer: EVA / PA / TPU film is laminated onto the TPU hot melt adhesive layer, with a thickness of 30-60μm, to form a functional layer.

10. The method for preparing a basalt fiber composite TPU high and low temperature film according to claim 9, characterized in that: In step S3, the surface of the elastic micro-convex pressing roller is made of silicone rubber, with a micro-convex height of 0.15-0.25 mm, a spacing of 1.5-2.5 mm, and a zoned pressure of 0.3-0.5 MPa at the inlet, 0.6-0.9 MPa at the center, and 0.4-0.6 MPa at the outlet.