Anti-skid master batch for improving friction coefficient of non-woven fabric and preparation method of anti-skid master batch

Abstract

The invention discloses an anti-skid master batch for improving the friction coefficient of non-woven fabric and a preparation method thereof, and relates to the technical field of anti-skid master batches, the anti-skid master batch comprises a matrix resin system, a core-shell structure composite filler and a functional additive; the matrix resin system is prepared from the following raw materials in parts by weight: 15 to 25 parts of low-density polyethylene, 30 to 40 parts of polypropylene and 25 to 35 parts of POE; the core-shell structure composite filler is prepared from the following raw materials in parts by weight: 10 to 15 parts of composite modified glass fiber core and 8 to 12 parts of microencapsulated silicon dioxide shell layer. Through the design of the core-shell structure composite filler, the composite modified glass fiber of the core part has a cavity structure, a bearing platform is provided for the tetrapod-like zinc oxide whisker and graphene, a three-dimensional network skeleton structure is formed, and the mechanical strength and the structural stability of the material are effectively enhanced.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-skid masterbatch, in particular to an anti-skid masterbatch for improving the friction coefficient of non-woven fabrics and a preparation method thereof. Background Art

[0002] As an important textile material, non-woven fabrics are widely used in building waterproofing, geotechnical engineering, packaging materials, medical and health care, and other fields. However, in actual use, the low surface friction coefficient of non-woven fabrics has become increasingly prominent. This is especially true in applications requiring anti-slip properties, such as building roof waterproofing materials and floor paving materials. The insufficient friction coefficient can lead to safety hazards and reduced performance.

[0003] Poor filler dispersibility is a common problem in existing anti-slip masterbatch products. Traditional single filler structures struggle to achieve uniform dispersion within the matrix resin, easily forming agglomerates. This not only impairs anti-slip performance but also creates stress concentration points within the material, reducing overall performance. Furthermore, insufficient interfacial bonding between the filler and the matrix resin is another significant factor impacting the stability of anti-slip masterbatch performance. Summary of the Invention

[0004] In view of the problems existing in the existing anti-slip masterbatch for improving the friction coefficient of non-woven fabrics and the preparation method thereof, the present invention is proposed.

[0005] Therefore, the problem to be solved by the present invention is that the traditional single filler structure is difficult to achieve uniform dispersion in the matrix resin and is prone to form agglomerates.

[0006] In order to solve the above technical problems, the present invention provides the following technical solutions: In a first aspect, the present invention provides an anti-slip masterbatch for improving the friction coefficient of a non-woven fabric, wherein the anti-slip masterbatch comprises a matrix resin system, a core-shell structure composite filler, and a functional additive; The matrix resin system is composed of the following raw materials in parts by weight: Low-density polyethylene: 15-25 parts, polypropylene: 30-40 parts, POE: 25-35 parts; The core-shell structure composite filler is composed of the following raw materials in parts by weight: Composite modified glass fiber core: 10-15 parts, microencapsulated silica shell: 8-12 parts; The functional additive is composed of the following raw materials in parts by weight: Maleic anhydride grafted polypropylene compatibilizer: 5-10 parts, silane coupling agent: 0.5-2 parts, lubricant: 1-3 parts, antioxidant: 0.5-2 parts, weathering agent: 1-3 parts; The composite modified glass fiber core is prepared by compositely modifying glass fiber with four-needle zinc oxide whiskers and graphene, and the interior of the composite modified glass fiber core is a cavity structure; the microencapsulated silica shell layer forms a protective shell layer on the surface of the composite modified glass fiber core.

[0007] As a preferred embodiment of the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, the structure of the microencapsulated silica shell layer is a porous structure with a porosity of 40-60% and an average pore diameter of 5-50 nanometers.

[0008] The beneficial effects of this preferred technical solution are: the porous structure increases the specific surface area, provides more friction contact points, and improves the anti-slip effect; the nanoscale pore size is conducive to forming a mechanical anchor with the matrix resin and enhancing the interface bonding force.

[0009] As a preferred embodiment of the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, the length of the four-needle zinc oxide whiskers is 5-10 microns and the diameter is 50-200 nanometers; The graphene has 3 to 10 layers and a lateral size of 0.5 to 5 microns.

[0010] The beneficial effects of this preferred technical solution are: the high aspect ratio of the four-needle zinc oxide whiskers provides an enhancement effect; the two-dimensional structure of graphene enhances the electrical and thermal conductivity; the two work synergistically to form a three-dimensional network structure, thereby improving the overall performance of the material.

[0011] As a preferred solution of the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, the grafting rate of the maleic anhydride grafted polypropylene compatibilizer is 0.8-1.5%, and the melt index is 80-120 grams per 10 minutes.

[0012] As a preferred solution of the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, the mass ratio of the matrix resin system, the core-shell structure composite filler and the functional additive is 60-65:20-25:12-15.

[0013] As a preferred embodiment of the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, the low-density polyethylene has a density of 0.85 g / cm3 and a melt index of 1-4 g / 10 min; The POE has a density of 0.9 g / cm3 and a melt index of 0.5-2 g / 10 min.

[0014] The beneficial effects of this preferred technical solution are: the differences in density and melt index of the two polyethylenes form a gradient structure, which improves toughness and impact resistance; and the combination of different fluidities improves the adaptability of the processing technology.

[0015] As a preferred embodiment of the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, the silane coupling agent is γ-aminopropyltriethoxysilane or γ-glycidoxypropyltrimethoxysilane; The lubricant is zinc stearate or polyethylene wax; The antioxidant is 2,6-di-tert-butyl-4-methylphenol or pentaerythritol tetra-β-3,5-di-tert-butyl-4-hydroxyphenyl propionate; The weathering agent is 2-2'-hydroxy-5'-methylphenylbenzotriazole or bis-2,2,6,6-tetramethyl-4-piperidinyl sebacate.

[0016] In a second aspect, the present invention provides a method for preparing an anti-slip masterbatch for improving the friction coefficient of a non-woven fabric, comprising the following steps: The core-shell structure composite filler is vacuum dried at 50-70° C. for 4-6 hours to remove surface adsorbed moisture; Add the matrix resin system to a mixer, set the speed to 1000-1500 rpm, and raise the temperature to 110-130°C; add the core-shell structure composite filler to the molten matrix resin system in batches, with each batch adding 20-30% of the total amount, and the interval time is 2-3 minutes; after all the core-shell structure composite fillers are added, continue mixing for 5-10 minutes; After mixing, cool to 90-110°C, add maleic anhydride grafted polypropylene compatibilizer and silane coupling agent in sequence, mix well, then add lubricant, antioxidant and weathering agent, mix well and cool the mixture to 20-25°C; The obtained mixture is added to an extruder, the temperature of the extruder is controlled at 160-220° C., pelletized by an underwater pelletizing system, the cooling water temperature is controlled at 5-10° C., and the pellets are dried at 80-100° C. for 2-4 hours to obtain the anti-slip masterbatch.

[0017] As a preferred embodiment of the method for preparing the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, the method for preparing the core-shell structure composite filler comprises the following steps: Dissolving the silane coupling agent in an ethanol aqueous solution to prepare a modification solution, immersing the glass fiber in the modification solution and ultrasonically oscillating for 30-60 minutes, filtering and washing, and then vacuum drying at 60-80° C. for 4-6 hours to obtain a pretreated glass fiber; The tetrapod-shaped zinc oxide whiskers and graphene are mixed in a non-polar solvent for surface activation treatment; the pretreated glass fiber and the activated tetrapod-shaped zinc oxide whiskers and graphene mixture are subjected to a composite reaction at a pH of 7.0-8.0 for 2-4 hours, and filtered and dried to obtain a composite modified glass fiber core having a cavity structure; The nano-silica was mixed and dispersed with a surfactant in an ice bath to form a stable emulsion, and a mixed solution of a silane coupling agent and a polyol was added dropwise to the stable emulsion at a rate of 1-2 drops per second. The pH value was adjusted to 6.5-7.5 and the mixture was reacted at a constant temperature for 3-5 hours to obtain a microencapsulated silica precursor. The obtained composite modified glass fiber core is dispersed in a mixed solvent of methanol and water, and the obtained microencapsulated silica precursor is added to the dispersion. The temperature is controlled at 45-55°C and the pH value is 7.0-8.0. The mixture is stirred for reaction for 4-6 hours, filtered and washed, and vacuum dried at 70-90°C for 8-12 hours to obtain the core-shell structure composite filler.

[0018] The beneficial effects of this preferred technical solution are: ensuring the complete formation of the core-shell structure through surface treatment and composite technology, improving the dispersibility of the filler and the compatibility with the matrix, and achieving excellent anti-slip performance.

[0019] As a preferred embodiment of the method for preparing the anti-slip masterbatch for improving the friction coefficient of non-woven fabrics according to the present invention, nitrogen or carbon dioxide is injected into the extruder when the mixed material is added to the extruder; The injection pressure is 0.5-2 MPa, and the injection amount is 0.1-0.5 weight percent of the total mass of the material.

[0020] The beneficial effects of this preferred technical solution are: the formed micro-foam structure enhances the porosity of the internal structure of the anti-slip masterbatch, thereby improving the anti-slip performance, while reducing the material density, reducing the weight and improving the economy.

[0021] The beneficial effects of the present invention are: Through the design of a core-shell composite filler, the core composite modified glass fiber has a cavity structure, providing a load-bearing platform for the tetrapod-shaped zinc oxide whiskers and graphene, forming a three-dimensional network skeleton structure, effectively enhancing the material's mechanical strength and structural stability. The outer microencapsulated silica shell has a porous structure, which not only provides more effective contact points for frictional contact, but also forms a mechanical anchoring effect with the matrix resin through nanoscale pores, improving the interfacial bonding strength between the filler and the matrix.

[0022] The high aspect ratio of the tetrapod-shaped zinc oxide whiskers and the two-dimensional lamellar structure of graphene create a synergistic effect, providing not only anti-slip properties but also excellent electrical and thermal conductivity and antistatic properties. The addition of graphene improves the material's toughness and fatigue resistance, extending its service life. The core-shell design effectively protects the active components, preventing performance loss during processing and ensuring a long-lasting and stable anti-slip effect.

[0023] The matrix resin system adopts a ternary blend design of low-density polyethylene, polypropylene and POE. Low-density polyethylene provides flexibility and impact resistance, polypropylene contributes excellent processing fluidity and chemical resistance, and low-density polyethylene and POE provide the necessary rigidity, wear resistance, viscosity and elasticity. The three work synergistically to form a matrix system with excellent performance. DETAILED DESCRIPTION

[0024] To make the above-mentioned objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with specific embodiments of the present invention. It is obvious that the embodiments described are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary persons in this field without creative work should fall within the scope of protection of the present invention.

[0025] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0026] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0027] Example 1: This example provides an anti-slip masterbatch for improving the friction coefficient of a non-woven fabric, comprising a matrix resin system, a core-shell structure composite filler, and a functional additive; The mass ratio of the matrix resin system, the core-shell structure composite filler and the functional additive is 60:20:12.

[0028] The matrix resin system is composed of the following raw materials in parts by weight: low-density polyethylene: 15 parts, polypropylene: 30 parts, POE (high-density polyethylene): 25 parts; The core-shell structure composite filler is composed of the following raw materials in parts by weight: composite modified glass fiber core: 10 parts, microencapsulated silica shell: 8 parts; The functional additive is composed of the following raw materials in parts by weight: maleic anhydride grafted polypropylene compatibilizer: 5 parts, silane coupling agent: 0.5 parts, lubricant: 1 part, antioxidant: 0.5 parts, weathering agent: 1 part; Among them, the composite modified glass fiber core is made by compositely modifying glass fiber with four-needle zinc oxide whiskers and graphene. The interior of the composite modified glass fiber core is a cavity structure; the microencapsulated silica shell layer forms a protective shell layer on the surface of the composite modified glass fiber core.

[0029] The structure of the microencapsulated silica shell is a porous structure with a porosity of 40% and an average pore diameter of 5 nanometers.

[0030] The four-needle ZnO whiskers are 5 μm long and 50 nm in diameter; The graphene has three layers and a lateral size of 0.5 micrometers.

[0031] The grafting rate of the maleic anhydride grafted polypropylene compatibilizer was 0.8%, and the melt index was 80 g / 10 min.

[0032] The density of low-density polyethylene is 0.85 grams per cubic centimeter and the melt index is 1 gram per 10 minutes; The density of POE is 0.9 g / cm3 and the melt index is 0.5 g / 10 min.

[0033] Wherein, the silane coupling agent is γ-aminopropyltriethoxysilane; The lubricant is zinc stearate; The antioxidant is 2,6-di-tert-butyl-4-methylphenol; The weathering agent is 2-2'-hydroxy-5'-methylphenylbenzotriazole.

[0034] Example 2: This example provides an anti-slip masterbatch for improving the friction coefficient of a non-woven fabric, comprising a matrix resin system, a core-shell structure composite filler, and a functional additive; The mass ratio of the matrix resin system, the core-shell structure composite filler and the functional additive is 65:20:12.

[0035] The matrix resin system is composed of the following raw materials in parts by weight: low-density polyethylene: 20 parts, polypropylene: 35 parts, POE: 30 parts; The core-shell structure composite filler is composed of the following raw materials in parts by weight: composite modified glass fiber core: 13 parts, microencapsulated silica shell: 10 parts; The functional additive is composed of the following raw materials in parts by weight: maleic anhydride grafted polypropylene compatibilizer: 7 parts, silane coupling agent: 1 part, lubricant: 2 parts, antioxidant: 1 part, weathering agent: 2 parts; Among them, the composite modified glass fiber core is made by compositely modifying glass fiber with four-needle zinc oxide whiskers and graphene. The interior of the composite modified glass fiber core is a cavity structure; the microencapsulated silica shell layer forms a protective shell layer on the surface of the composite modified glass fiber core.

[0036] The structure of the microencapsulated silica shell is a porous structure with a porosity of 50% and an average pore diameter of 25 nanometers.

[0037] The four-needle ZnO whiskers are 7 microns long and 100 nanometers in diameter; The graphene has 6 layers and a lateral size of 2 microns.

[0038] The grafting rate of the maleic anhydride grafted polypropylene compatibilizer is 1%, and the melt index is 100 g per 10 minutes.

[0039] The density of low-density polyethylene is 0.85 grams per cubic centimeter and the melt index is 2 grams per 10 minutes; The density of POE is 0.9 g / cm3 and the melt index is 1 g / 10 minutes.

[0040] Wherein, the silane coupling agent is γ-aminopropyltriethoxysilane; The lubricant is polyethylene wax; The antioxidant is pentaerythritol tetra-β-3,5-di-tert-butyl-4-hydroxyphenylpropionate; The weathering agent is 2-2'-hydroxy-5'-methylphenylbenzotriazole.

[0041] Example 3: This example provides an anti-slip masterbatch for improving the friction coefficient of a non-woven fabric, comprising a matrix resin system, a core-shell structure composite filler, and a functional additive; The mass ratio of the matrix resin system, the core-shell structure composite filler and the functional additive is 60:25:15.

[0042] The matrix resin system is composed of the following raw materials in parts by weight: low-density polyethylene: 25 parts, polypropylene: 40 parts, POE: 35 parts; The core-shell structure composite filler is composed of the following raw materials in parts by weight: composite modified glass fiber core: 15 parts, microencapsulated silica shell: 12 parts; The functional additive is composed of the following raw materials in parts by weight: maleic anhydride grafted polypropylene compatibilizer: 10 parts, silane coupling agent: 2 parts, lubricant: 3 parts, antioxidant: 2 parts, weathering agent: 3 parts; Among them, the composite modified glass fiber core is made by compositely modifying glass fiber with four-needle zinc oxide whiskers and graphene. The interior of the composite modified glass fiber core is a cavity structure; the microencapsulated silica shell layer forms a protective shell layer on the surface of the composite modified glass fiber core.

[0043] The structure of the microencapsulated silica shell is a porous structure with a porosity of 60% and an average pore size of 50 nanometers.

[0044] The four-needle ZnO whiskers are 10 microns long and 200 nanometers in diameter; The graphene has 10 layers and a lateral size of 5 microns.

[0045] The grafting rate of the maleic anhydride grafted polypropylene compatibilizer was 1.5%, and the melt index was 120 g / 10 min.

[0046] The density of low-density polyethylene is 0.85 grams per cubic centimeter and the melt index is 4 grams per 10 minutes; The density of POE is 0.9 g / cm3 and the melt index is 2 g / 10 min.

[0047] Wherein, the silane coupling agent is γ-glycidyloxypropyltrimethoxysilane; The lubricant is polyethylene wax; The antioxidant is 2,6-di-tert-butyl-4-methylphenol; The weathering agent is bis-2,2,6,6-tetramethyl-4-piperidinyl sebacate.

[0048] The anti-slip masterbatch of Example 1 to Example 3 was mixed with a polypropylene matrix resin at an addition amount of 5%, and a non-woven fabric sample was prepared by a melt spinning process. The thickness was 0.8-1.2 mm and the surface density was 80-120 g / m 2 , preparing non-woven fabrics.

[0049] The friction coefficient of Examples 1 to 3 was tested, and the test standard adopted GB / T 10006-2021 "Determination of the coefficient of friction of plastic films and sheets"; the test conditions were room temperature 23±2°C and relative humidity 50±5%; the test parameters were static friction coefficient and dynamic friction coefficient; the test load was 200N; and the sliding speed was 150mm / min. Through the experiment, a friction coefficient comparison table was obtained. Five points were tested for each sample, and the average value was taken as the final result. The static friction coefficient was obtained by measuring the maximum static friction force at the moment the slider started to slide, and the dynamic friction coefficient was calculated by measuring the average friction force during the stable sliding process of the slider; Table 1: Friction coefficient comparison table Test samples Static friction coefficient Dynamic friction coefficient Example 1 0.48 0.44 Example 2 0.52 0.47 Example 3 0.50 0.45 Taking Example 2 as an example, three groups of comparative examples are set up to compare Example 2 with the three groups of comparative examples; Comparative Example 1: Ordinary nano-silica was used to replace the core-shell structure composite filler, and the total amount of filler remained unchanged at 20 parts. The other components were exactly the same as those in Example 2; Comparative Example 2: The core-shell structure design was maintained, but only four-needle zinc oxide whiskers were used in the composite modified glass fiber core, and no graphene was added. Other parameters remained the same as in Example 2. Comparative Example 3: The same core-shell structure composite filler as in Example 2 was used, but without adding the maleic anhydride grafted polypropylene compatibilizer and the silane coupling agent.

[0050] Table 2: Friction coefficient comparison test results Sample type Static friction coefficient Dynamic friction coefficient Example 2 0.52 0.47 Comparative Example 1 0.38 0.34 Comparative Example 2 0.43 0.39 Comparative Example 3 0.41 0.37 As can be seen from Table 2, Example 2 has a static friction coefficient of 0.52 and a kinetic friction coefficient of 0.47. Comparative Example 1, using a traditional single filler, has significantly lower friction coefficients, with static friction coefficients of only 0.38 and kinetic friction coefficients of 0.34, representing decreases of 26.9% and 27.7%, respectively, compared to Example 2. This demonstrates that the core-shell structure design effectively increases friction contact points and surface roughness through the porous structure of the microencapsulated silica shell.

[0051] The friction coefficient performance of Comparative Example 2 lies between that of Comparative Example 1 and Example 2, with a static friction coefficient of 0.43 and a kinetic friction coefficient of 0.39, representing decreases of 17.3% and 17.0%, respectively, compared to Example 2. This demonstrates that the addition of graphene significantly contributes to the improved anti-slip performance, as its two-dimensional lamellar structure forms a synergistic reinforcement network with the tetrapod-shaped zinc oxide whiskers, improving the surface micromorphology.

[0052] The performance of Comparative Example 3 was slightly better than that of Comparative Example 1 but significantly lower than that of Example 2, with a static friction coefficient of 0.41 and a kinetic friction coefficient of 0.37, respectively, which were 21.2% and 21.3% lower than those of Example 2. The lack of a compatibilizer system resulted in insufficient interfacial bonding between the filler and the matrix resin. While the physical advantages of the core-shell structure were maintained, poor interfacial compatibility limited the full potential of the anti-slip performance.

[0053] Through comparative analysis, it can be seen that the three technical elements of core-shell structure design, graphene synergistic reinforcement and compatibilizer interface modification in Example 2 work synergistically to achieve the best anti-slip performance.

[0054] In the mechanical properties comparison experiment, anti-slip masterbatches were prepared according to the formulations of Example 2 and Comparative Examples 1-3. Each masterbatch was mixed with a polypropylene matrix resin at a 5% addition rate, and standard test specimens were prepared by injection molding. The molded specimens were conditioned at a temperature of 23±2°C and a relative humidity of 50±5% for 48 hours. Specimens were prepared according to GB / T 1040.2-2006 and tested using a testing machine at a tensile speed of 50 mm / min for tensile properties. Specimens were prepared according to GB / T 9341-2008 with a span of 64 mm and a loading speed of 2 mm / min for flexural properties. Notched specimens were prepared according to GB / T 1043.1-2008, and the notched impact strength of simply supported beams was measured using a pendulum impact tester.

[0055] Table 3: Mechanical properties comparison test results Sample type Tensile strength (MPa) Flexural strength (MPa) <![CDATA[Impact strength (kJ / m 2 )]]> Flexural modulus (GPa) Example 2 26.7 42.3 8.6 1.85 Comparative Example 1 21.2 35.1 6.2 1.52 Comparative Example 2 23.8 38.7 7.4 1.68 Comparative Example 3 22.5 36.9 6.9 1.61 Example 2 has a tensile strength of 26.7 MPa, a flexural strength of 42.3 MPa, and an impact strength of 8.6 kJ / m 2 , flexural modulus 1.85 GPa. Comparative Example 1, using a traditional single filler, exhibited significantly lower mechanical properties, with a tensile strength of only 21.2 MPa, a 20.6% decrease compared to Example 2. This demonstrates that the reinforcing effect of the core-shell composite filler is significantly superior to that of traditional fillers, and that the composite modified glass fiber core provides excellent load-bearing capacity.

[0056] The mechanical properties of Comparative Example 2 were between those of Comparative Example 1 and Example 2, with a tensile strength of 23.8 MPa, a 10.9% decrease compared to Example 2. The absence of graphene resulted in an incomplete reinforcement network structure. While the tetrapod-shaped zinc oxide whiskers provided some reinforcement, they could not achieve the performance level achieved by the synergistic enhancement of graphene. The two-dimensional lamellar structure of graphene effectively increased stress transfer efficiency and significantly improved the toughness of the material.

[0057] The tensile strength of Comparative Example 3 is 22.5MPa, and the flexural strength is 36.9MPa, which are respectively reduced by 15.7% and 12.8% compared with Example 2. The lack of the compatibilizer system causes insufficient interfacial bonding between the filler and the matrix resin, and reduces the stress transfer efficiency. Although the physical advantages of the core-shell structure and graphene are maintained, the interface defects become stress concentration points, which limits the full play of mechanical properties.

[0058] Impact strength test results show that Example 2's impact strength is 38.7%, 16.2%, and 24.6% higher than Comparative Examples 1, 2, and 3, respectively. This demonstrates that the synergistic effects of the core-shell structure design, graphene synergistic reinforcement, and compatibilizer interface modification not only enhance the material's strength and modulus but, more importantly, significantly improve its toughness, achieving a good balance between strength and toughness.

[0059] In the wear resistance comparison experiment, taking Example 2 as an example, three groups of comparative examples were set up to compare Example 2 with the three groups of comparative examples; Comparative Example 4: 65 parts of low-density polyethylene were used as the matrix resin system, and the core-shell structure composite filler and functional additives remained the same as those in Example 2.

[0060] Comparative Example 5: 65 parts of polypropylene were used as the matrix resin system, and the other components were the same as those in Example 2.

[0061] Comparative Example 6: 30 parts of low-density polyethylene and 35 parts of POE were used as the matrix resin system without adding polypropylene.

[0062] Anti-slip masterbatch was prepared according to the formulations of Example 2 and Comparative Examples 4-6. The masterbatch was mixed with the corresponding matrix resin at a 5% addition rate, and standard test specimens with a thickness of 4 mm were prepared by injection molding. The specimens were conditioned at a temperature of 23±2°C and a relative humidity of 50±5% for 48 hours. Wear resistance testing was conducted in accordance with GB / T 1689-2014 using a reciprocating friction and wear tester with a load of 10 N, a stroke of 25 mm, and a frequency of 1 Hz. Surface hardness was measured using a Yishi hardness tester in accordance with GB / T 2411-2008. Mass loss before and after wear was measured using a precision electronic balance weighing method, and the wear rate was calculated.

[0063] Table 4: Comparative test results of wear resistance Sample type Wear rate (mg / 1000 times) Surface hardness (HV) Mass loss after 10,000 cycles (mg) Surface roughness change rate (%) Example 2 2.1 78.5 21.2 15.3 Comparative Example 4 4.6 62.4 46.8 35.7 Comparative Example 5 3.2 71.2 32.4 24.6 Comparative Example 6 2.8 75.1 28.3 19.8 Table 4 shows that Example 2 exhibits a wear rate of only 2.1 mg / 1000 cycles, a surface hardness of 78.5 HV, and a mass loss of only 21.2 mg after 10,000 friction cycles. Comparative Example 4, using a single low-density polyethylene matrix, exhibits the worst wear resistance, with a wear rate of 4.6 mg / 1000 cycles, a 119% increase compared to Example 2. While Comparative Example 4 exhibits good flexibility, it lacks sufficient rigidity and wear resistance, and is prone to plastic deformation and material transfer during friction.

[0064] Comparative Example 5, using a single polypropylene matrix, exhibited better wear resistance than Comparative Example 4, but still lower than Example 2, with a wear rate of 3.2 mg / 1000 cycles. Polypropylene has good chemical resistance and a certain degree of rigidity, but lacks toughness regulation, making it prone to fatigue cracking under repeated friction loads, leading to increased wear.

[0065] Comparative Example 6, using low-density polyethylene and POE, showed improved wear resistance, with the wear rate dropping to 2.8 mg / 1000 times, but still 33% higher than that of Example 2. While Comparative Example 6 achieved a balance between flexibility and rigidity, it lacked the excellent processing fluidity and interfacial compatibility provided by polypropylene, resulting in less uniform filler dispersion than in Example 2.

[0066] The surface hardness test results correlate well with the wear resistance. Example 2 achieved the highest hardness, demonstrating that the ternary blend matrix effectively enhances surface rigidity while maintaining toughness. The surface roughness change rate was minimal, indicating that the surface topography remained relatively stable during wear, resulting in minimal degradation of anti-slip properties.

[0067] The flexibility of low-density polyethylene ensures impact resistance, the rigidity of POE provides a foundation for wear resistance, and the processing fluidity of polypropylene improves filler dispersion uniformity. The synergistic effect of these three factors achieves optimal wear resistance and verifies the scientific and effective nature of the matrix design.

[0068] Example 4: This embodiment provides a method for preparing an anti-slip masterbatch, comprising the following steps: S1, core-shell structure composite filler vacuum drying at 50 ° C for 6 hours to remove surface adsorbed moisture; By removing surface moisture, bubble defects and decreased interface bonding strength caused by moisture in subsequent processing can be avoided.

[0069] S2. Add the matrix resin system to the mixer, set the speed to 1500 rpm, and raise the temperature to 110° C.; add the core-shell structure composite filler to the molten matrix resin system in batches, with each batch adding 20% of the total amount, and the interval time is 3 minutes; after all the core-shell structure composite fillers are added, continue mixing for 7 minutes; The batch addition strategy improves filler dispersion. A 20% addition per batch, combined with a 3-minute interval, ensures that the previous batch of filler is fully dispersed before adding the next batch, effectively preventing filler agglomeration. A 7-minute follow-up mixing time ensures thorough mixing of all components and complete interfacial reactions, forming a stable composite system.

[0070] S3. After mixing, cool to 100°C, add maleic anhydride grafted polypropylene compatibilizer and silane coupling agent in sequence, mix well, then add lubricant, antioxidant and weathering agent, mix well and cool the mixture to 25°C; S4. Add the obtained mixture into an extruder, control the extruder temperature at 200° C., cut the pellets into pellets through an underwater pelletizing system, control the cooling water temperature at 7° C., and dry the pellets at 90° C. for 2 hours to obtain anti-slip masterbatch.

[0071] When the mixed material is added to the extruder, nitrogen or carbon dioxide is injected into the extruder; wherein, the injection pressure is 1 MPa, and the injection amount is 0.2 weight percent of the total mass of the material.

[0072] A nitrogen injection pressure of 1 MPa and an injection volume of 0.2% form an ideal micro-foam structure, further increasing the specific surface area and surface roughness of the material. The micro-foam structure not only improves the anti-slip performance, but also reduces the material density and improves economic benefits. At the same time, the microporous structure helps to improve the sound absorption and noise reduction performance of the material and expands its application areas.

[0073] The preparation method of the core-shell structure composite filler comprises the following steps A1 to A4: A1, dissolving the silane coupling agent in an ethanol aqueous solution to prepare a modifying solution, immersing the glass fiber in the modifying solution and ultrasonically oscillating for 30 minutes, filtering and washing, and then vacuum drying at 60° C. for 6 hours to obtain a pretreated glass fiber; A2. Mixing tetrapod-shaped zinc oxide whiskers and graphene in a non-polar solvent for surface activation treatment; reacting the pretreated glass fiber with the activated tetrapod-shaped zinc oxide whiskers and graphene mixture at a pH of 8.0 for 4 hours, filtering and drying to obtain a composite modified glass fiber core having a cavity structure; A3, mixing and dispersing nano-silica with a surfactant in an ice bath to form a stable emulsion, adding a mixed solution of a silane coupling agent and a polyol dropwise to the stable emulsion at a rate of 2 drops per second, adjusting the pH value to 6.5, and reacting at a constant temperature for 5 hours to obtain a microencapsulated silica precursor; A4. Disperse the obtained composite modified glass fiber core in a mixed solvent of methanol and water, then add the obtained microencapsulated silica precursor to the dispersion, control the temperature at 55°C and the pH value at 7.0, stir and react for 4 hours, filter and wash, and vacuum dry at 90°C for 8 hours to obtain the core-shell structure composite filler.

[0074] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, and all of these should be included in the scope of the present invention.

Claims

1. An anti-slip masterbatch for increasing the friction coefficient of non-woven fabrics, characterized by: The anti-slip masterbatch includes a matrix resin system, a core-shell structure composite filler, and a functional additive; The matrix resin system is composed of the following raw materials in parts by weight: Low-density polyethylene: 15-25 parts, polypropylene: 30-40 parts, POE: 25-35 parts; The core-shell structure composite filler is composed of the following raw materials in parts by weight: Composite modified glass fiber core: 10-15 parts, microencapsulated silica shell: 8-12 parts; The functional additive is composed of the following raw materials in parts by weight: Maleic anhydride grafted polypropylene compatibilizer: 5-10 parts, silane coupling agent: 0.5-2 parts, lubricant: 1-3 parts, antioxidant: 0.5-2 parts, weathering agent: 1-3 parts; The composite modified glass fiber core is prepared by compositely modifying glass fiber with four-needle zinc oxide whiskers and graphene, and the interior of the composite modified glass fiber core is a cavity structure; the microencapsulated silica shell layer forms a protective shell layer on the surface of the composite modified glass fiber core.

2. The anti-slip masterbatch for increasing the friction coefficient of non-woven fabrics according to claim 1, characterized in that: The structure of the microencapsulated silica shell layer is a porous structure with a porosity of 40-60% and an average pore diameter of 5-50 nanometers.

3. The anti-slip masterbatch for increasing the friction coefficient of non-woven fabric according to claim 2, characterized in that: The four-needle zinc oxide whiskers have a length of 5-10 microns and a diameter of 50-200 nanometers; The graphene has 3 to 10 layers and a lateral size of 0.5 to 5 microns.

4. The anti-slip masterbatch for increasing the friction coefficient of non-woven fabric according to claim 3, characterized in that: The maleic anhydride grafted polypropylene compatibilizer has a grafting rate of 0.8-1.5% and a melt index of 80-120 grams per 10 minutes.

5. The anti-slip masterbatch for increasing the friction coefficient of non-woven fabric according to claim 4, characterized in that: The mass ratio of the matrix resin system, the core-shell structure composite filler and the functional additive is 60-65:20-25:12-15.

6. The anti-slip masterbatch for increasing the friction coefficient of non-woven fabric according to claim 5, characterized in that: The low-density polyethylene has a density of 0.85 g / cm3 and a melt index of 1-4 g / 10 minutes; The POE has a density of 0.9 g / cm3 and a melt index of 0.5-2 g / 10 min.

7. The anti-slip masterbatch for increasing the friction coefficient of non-woven fabric according to claim 6, characterized in that: The silane coupling agent is γ-aminopropyltriethoxysilane or γ-glycidyloxypropyltrimethoxysilane; The lubricant is zinc stearate or polyethylene wax; The antioxidant is 2,6-di-tert-butyl-4-methylphenol or pentaerythritol tetra-β-3,5-di-tert-butyl-4-hydroxyphenyl propionate; The weathering agent is 2-2'-hydroxy-5'-methylphenylbenzotriazole or bis-2,2,6,6-tetramethyl-4-piperidinyl sebacate.

8. A method for preparing the anti-slip masterbatch according to any one of claims 1 to 7, characterized in that: The following steps are involved: The core-shell structure composite filler is vacuum dried at 50-70° C. for 4-6 hours to remove surface adsorbed moisture; Add the matrix resin system to a mixer, set the speed to 1000-1500 rpm, and raise the temperature to 110-130°C; add the core-shell structure composite filler to the molten matrix resin system in batches, with each batch adding 20-30% of the total amount, and the interval time is 2-3 minutes; after all the core-shell structure composite fillers are added, continue mixing for 5-10 minutes; After mixing, cool to 90-110°C, add maleic anhydride grafted polypropylene compatibilizer and silane coupling agent in sequence, mix well, then add lubricant, antioxidant and weathering agent, mix well and cool the mixture to 20-25°C; The obtained mixture is added to an extruder, the temperature of the extruder is controlled at 160-220° C., pelletized by an underwater pelletizing system, the cooling water temperature is controlled at 5-10° C., and the pellets are dried at 80-100° C. for 2-4 hours to obtain the anti-slip masterbatch.

9. The method for preparing the anti-slip masterbatch according to claim 8, wherein: The preparation method of the core-shell structure composite filler comprises the following steps: Dissolving the silane coupling agent in an ethanol aqueous solution to prepare a modification solution, immersing the glass fiber in the modification solution and ultrasonically oscillating for 30-60 minutes, filtering and washing, and then vacuum drying at 60-80° C. for 4-6 hours to obtain a pretreated glass fiber; The tetrapod-shaped zinc oxide whiskers and graphene are mixed in a non-polar solvent for surface activation treatment; the pretreated glass fiber and the activated tetrapod-shaped zinc oxide whiskers and graphene mixture are subjected to a composite reaction at a pH of 7.0-8.0 for 2-4 hours, and filtered and dried to obtain a composite modified glass fiber core having a cavity structure; The nano-silica was mixed and dispersed with a surfactant in an ice bath to form a stable emulsion, and a mixed solution of a silane coupling agent and a polyol was added dropwise to the stable emulsion at a rate of 1-2 drops per second. The pH value was adjusted to 6.5-7.5 and the mixture was reacted at a constant temperature for 3-5 hours to obtain a microencapsulated silica precursor. The obtained composite modified glass fiber core is dispersed in a mixed solvent of methanol and water, and the obtained microencapsulated silica precursor is added to the dispersion. The temperature is controlled at 45-55°C and the pH value is 7.0-8.

0. The mixture is stirred for reaction for 4-6 hours, filtered and washed, and vacuum dried at 70-90°C for 8-12 hours to obtain the core-shell structure composite filler.

10. The method for preparing the anti-slip masterbatch according to claim 8, wherein: When the mixed material is added to the extruder, nitrogen or carbon dioxide is injected into the extruder; The injection pressure is 0.5-2 MPa, and the injection amount is 0.1-0.5 weight percent of the total mass of the material.