Epoxidized natural rubber latex modified asphalt high-skid-resistance coiled material and preparation method thereof

Abstract

The invention belongs to the technical field of asphalt coiled material preparation, and provides an epoxidized natural rubber latex modified asphalt high-skid-resistance coiled material and a preparation method thereof. The coiled material is of a multi-layer structure and is sequentially provided with an anti-skid particle layer, a gradient build-in-reaction anchoring layer, an epoxidized natural rubber latex modified asphalt mixture layer, a reinforced tire base layer, a bottom bonding layer and a release layer from top to bottom. The gradient build-in-reaction anchoring layer comprises a particle build-in bonding sub-layer containing polar tackifying resin and a post-trigger reaction anchoring sub-layer containing latent curing microcapsules and self-healing regeneration microcapsules; the epoxidized natural rubber is introduced in a phase transfer concentrated solution mode; the antiskid particles are subjected to surface activation through amino silane and an imidazolyl or amido active layer; during preparation, each functional layer is formed on a tire base, particles are spread in a hot state and pressed and embedded, a finished product is obtained through post-curing and composite release, and the finished product is shaped through a cooling drum and a compression roller.

Description

Technical Field

[0001] This invention belongs to the field of asphalt roll material preparation technology, and relates to an epoxidized natural rubber latex modified asphalt high anti-skid roll material and its preparation method. Background Technology

[0002] Modified bitumen rolls are widely used in bridge deck paving, waterproofing projects, and seepage prevention and protection of road ancillary structures due to their continuous film formation, convenient construction, and good water and weather resistance. Under the combined effects of traffic loads and the environment, in addition to meeting basic requirements such as waterproofing, adhesion, and crack resistance, these rolls are often endowed with functions such as surface anti-slip, wear resistance, and durability to reduce the risk of slipping on wet roads and improve service safety.

[0003] Existing high-skid-resistance roofing membranes often achieve their anti-skid effect by spreading mineral or ceramic particles on the surface to create a rough texture. However, the bonding between the particle layer and the asphalt-based adhesive layer mainly relies on physical embedding and adhesion. Affected by temperature cycling, vehicle shearing, water immersion, and freeze-thaw cycles, the interface is prone to loosening, detachment, or polishing, leading to a decrease in anti-skid performance. On the other hand, roofing membranes are multiphase composite systems with multiple interfaces between the particle layer, adhesive layer, mixture layer, and base layer. If compatibility is insufficient or interlayer stress is concentrated, microcrack propagation, increased interfacial voids, and peeling / blistering failures can easily occur. To improve adhesion and wear resistance, rubber or resin is usually introduced for modification. However, the dispersion and compatibility of solid rubber in the asphalt phase are limited, easily leading to phase separation or decreased storage stability. Introducing latex may introduce water-induced bubbling, porosity, and interfacial defects, further weakening particle retention and interlayer bonding strength. Some technologies attempt to enhance the interface by adding reactive components or curing systems. However, under the requirements of continuous production and construction adaptability, it is difficult to balance the timing of reaction triggering and curing window, which may lead to premature curing, embrittlement, or fluctuations in bonding performance, thereby affecting the quality and long-term durability of the finished product. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a high-skid-resistance asphalt roll material modified with epoxidized natural rubber latex and its preparation method. The roll material adopts a composite structure of an anti-skid particle layer and a gradient embedded reactive anchoring layer. The embedded bonding sublayer achieves hot-state embedding of particles, while the reactive anchoring sublayer introduces latent curing and self-healing regeneration microcapsules to stabilize the interface and improve durability. Epoxidized natural rubber is introduced with a phase transfer concentrate and dehydrated with a compatibilizer. The particles undergo surface activation to enhance bonding. The finished product is obtained through continuous embedding, post-curing, and composite molding, thereby meeting the needs of actual production.

[0005] To achieve this objective, the present invention adopts the following technical solution:

[0006] In a first aspect, the present invention provides an epoxidized natural rubber latex modified asphalt high anti-skid roll material, specifically comprising:

[0007] The roll material has a layered structure, comprising, from top to bottom: an anti-skid granular layer, a gradient embedding-reactive anchoring layer, an epoxidized natural rubber latex modified asphalt mixture layer, a reinforced base layer, a bottom bonding layer, and a release layer; the anti-skid granular layer and the gradient embedding-reactive anchoring layer are arranged adjacent to each other;

[0008] The gradient embedding-reactive anchoring layer includes a particle embedding bonding sublayer and a post-triggered reactive anchoring sublayer arranged adjacently from top to bottom; the particle embedding bonding sublayer is an asphalt-based binder containing a polar tackifying resin, and anti-skid particles are pressed into the particle embedding bonding sublayer under hot conditions; the post-triggered reactive anchoring sublayer is an asphalt-based binder containing latent curing microcapsules and self-healing regeneration microcapsules; the epoxidized natural rubber latex modified asphalt mixture layer includes matrix asphalt, epoxidized natural rubber, mineral fine aggregates and mineral fillers, and the epoxidized natural rubber is introduced in the form of a phase transfer concentrate.

[0009] Preferably, the anti-slip particle layer is a two-stage spreading layer, comprising coarse particles and fine particles; the coarse particles have a particle size of 0.60-4.75 mm, the fine particles have a particle size of 0.20-0.60 mm, and the mass ratio of coarse particles to fine particles is (55-85):(45-15); the anti-slip particles are selected from one or more of basalt particles, corundum particles, alumina ceramic particles, and silicon carbide particles, and the anti-slip particles are ceramic-coated mineral particles with a ceramic coating layer on the surface, wherein the ceramic coating layer is an alumina coating layer.

[0010] Preferably, the anti-slip particles undergo a first surface activation and a second surface activation before spreading; the first surface activation includes treating the particle surface with 0.2-2.0 wt.% of a silane coupling agent based on the mass of the anti-slip particles, wherein the silane coupling agent is γ-aminopropyltriethoxysilane; the second surface activation involves forming an organic active layer containing imidazole groups and / or primary amine groups on the particle surface after silane treatment, wherein the organic active layer is formed by γ-imidazolepropyltriethoxysilane and / or polyethyleneimine.

[0011] Preferably, the amount of polar tackifying resin added to the particle-embedded bonding sublayer is 2-20 parts / 100 parts of asphalt-based binder, and the thickness of the particle-embedded bonding sublayer is 0.03-0.40 mm. The polar tackifying resin is rosin-modified phenolic resin and / or C9 petroleum resin.

[0012] Preferably, the amount of latent solidified microcapsules added to the post-triggered reaction anchoring sublayer is 0.05-1.20 parts / 100 parts asphalt-based binder; the average particle size of the latent solidified microcapsules is 1-40 μm; the core material of the latent solidified microcapsules is 2-phenylimidazole, and the shell material is polycarbonate, polycaprolactone, or polyurethane / polyurea. The preparation method of the latent solidified microcapsules is as follows: 2-phenylimidazole is dispersed in an organic phase and sheared and emulsified into water-in-oil microdroplets; polycarbonate or polycaprolactone is solidified into a shell at the microdroplet interface by solvent evaporation / displacement, or isocyanate and diamine are interfacially polymerized at the microdroplet interface to form a polyurethane / polyurea shell layer, thereby obtaining latent solidified microcapsules.

[0013] Preferably, the amount of self-healing and regenerating microcapsules added to the post-triggered reaction anchoring sublayer is 0.10-2.50 parts / 100 parts asphalt-based binder; the core material of the self-healing and regenerating microcapsules is soybean oil, and the shell material is a heat-resistant and oxidation-resistant coating material, wherein the coating material is melamine-formaldehyde resin; the post-triggered reaction anchoring sublayer further includes water-absorbing and water-capturing microcapsules or a closed-type water-absorbing and water-capturing agent, the amount of which is 0.02-0.60 parts / 100 parts asphalt-based binder, wherein the shell material of the water-absorbing and water-capturing microcapsules is polyurea, and the core material is calcium chloride hygroscopic agent; the preparation method of the self-healing and regenerating microcapsules is as follows: soybean oil is sheared and emulsified into water-in-oil droplets; under acidic conditions, hexamethylol melamine is polymerized in situ at the oil droplet interface and crosslinked to form a shell, thereby obtaining self-healing and regenerating microcapsules.

[0014] Preferably, the phase transfer concentrate is obtained by the following method: adding a phase transfer reactive compatibilizer to epoxidized natural rubber latex and shearing and mixing, followed by thin-film evaporation, dehydration under reduced pressure, or inert gas purging to achieve a water content of ≤0.2 wt.% in the resulting phase transfer concentrate; wherein, based on the mass of the base asphalt, the amount of the phase transfer reactive compatibilizer is 0.3-2.5 wt.%; the phase transfer reactive compatibilizer is an amphiphilic compound containing C12-C30 hydrophobic segments and epoxy reactive groups, wherein the epoxy reactive group is an imidazole group, and the phase transfer reactive compatibilizer is 1-hexadecyl-1H-imidazolium and / or 1-octadecyl-1H-imidazolium.

[0015] Preferably, based on the quality of the base asphalt, the dry rubber content of the epoxidized natural rubber is 3-15 wt.%; the epoxidized natural rubber is one or a combination of ENR-25 and ENR-50, or liquid epoxidized natural rubber; the epoxidized natural rubber latex modified asphalt mixture layer further contains one or more of carbon nanofibers or nano-alumina, with an addition amount of 0.05-0.80 wt.% based on the base asphalt.

[0016] Preferably, the particle size of the mineral fine aggregate in the epoxidized natural rubber latex modified asphalt mixture layer is ≤2.4mm, and the mass fraction of the mineral filler is 8-25 wt.% of the solid component of the mixture layer; the embedding depth of the anti-skid particles into the particle-bonded sublayer is 15-70% of the equivalent particle size, and the surface coverage of the anti-skid particle layer is 60-95%; the roll material is embedded by a continuous production line through a cooling drum and pressure roller under controlled pressure; the post-curing window of the post-triggered reaction anchoring sublayer is 80-110℃ for 0.5-6 hours; the reinforcing base layer is polyester nonwoven felt, glass fiber felt, or polyester / glass fiber composite base layer, with a unit area mass of 50-300 g / m². 2 The thickness of the bottom adhesive layer is 0.10-1.50 mm, and the release layer is release paper or release film.

[0017] Secondly, the present invention provides a method for preparing epoxy natural rubber latex modified asphalt high anti-skid roofing membrane, comprising the following steps: epoxidized natural rubber latex and phase transfer reaction compatibilizer are sheared and mixed, then dehydrated to obtain a phase transfer concentrate; the phase transfer concentrate is mixed with matrix asphalt, mineral fine aggregates and mineral fillers to form an epoxy natural rubber latex modified asphalt mixture layer; a particle embedding bonding sublayer and a post-triggered reaction anchoring sublayer are formed on the epoxy natural rubber latex modified asphalt mixture layer, and surface-treated anti-skid particles are spread on the mixture under hot conditions, and then pressed and fixed by a cooling drum and pressure roller to form an anti-skid particle layer; the obtained roofing membrane is post-cured, and a bottom bonding layer is formed on the lower surface and a release layer is composited to obtain the epoxy natural rubber latex modified asphalt high anti-skid roofing membrane.

[0018] The epoxy groups introduced into the epoxidized natural rubber molecular chain are high-strain three-membered ring functional groups, which are more prone to ring-opening reactions in the presence of nucleophiles and basic catalytic centers. Long-chain alkyl imidazole compatibilizers have hydrophobic segments and nitrogen-containing heterocyclic polar sites. After entering the latex system, they tend to accumulate between the rubber phase and the asphalt phase during dehydration and concentration. The hydrophobic segments form intermolecular interactions with the saturated and aromatic components in the asphalt, while the imidazole nitrogen sites interact with the oxygen- and sulfur-containing polar components in the asphalt through Lewis base-acid interactions or hydrogen bonding, thereby reducing the interfacial energy and inhibiting phase separation. At the same time, the imidazole ring can act as a basic catalytic center to promote the ring-opening of epoxy groups, generating hydroxyl groups and new covalent bonding sites on the epoxidized natural rubber segments. This changes the polarity distribution of the system, enhances the interaction between the rubber phase and the polar components of the asphalt, and results in a more stable microphase structure.

[0019] The chemical bonding on the surface of the anti-slip particles originates from a tandem reaction of silane coupling and epoxy ring-opening. The alumina coating surface is typically enriched with hydroxyl active sites. After hydrolysis to generate silanol on the particle surface, aminopropyltriethoxysilane condenses with surface hydroxyl groups, forming a covalently bridging structure linking metal-oxygen bonds and silicon-oxygen bonds. Subsequently introduced imidazole silanes can form silicon-oxygen bonds on the surface in the same manner, exposing imidazole groups. Polyethyleneimine forms an amine-containing organic active layer through adsorption and multi-point hydrogen bonding between polyamine groups and the surface silanol layer and inorganic surface polar sites. These amine and imidazole groups provide nucleophilic sites for ring-opening addition with epoxy groups and also provide acid-base interactions and hydrogen bond networks at the interface before the reaction. Under the catalysis of imidazole, the epoxy groups on the epoxidized natural rubber chain undergo ring-opening addition with primary amines or polyamines on the particle surface to generate hydroxyl-containing amino alcohol structures and form covalent bonds. The interface changes from physical embedding to a state of coexistence of embedding and chemical anchoring. At the same time, the hydroxyl groups generated by the ring-opening reaction can also form hydrogen bonds or dipole interactions with the polar components of asphalt, further stabilizing the interface.

[0020] In the gradient embedding-reactive anchoring layer, the particle embedding and bonding sublayer containing polar tackifying resin mainly provides the adhesion and wetting basis for the continuous phase. Rosin-modified phenolic resin contains phenolic hydroxyl groups and aromatic ring structures, providing nucleophilic sites for hydroxyl groups that can participate in epoxy ring-opening in the system; petroleum resin in the asphalt phase plays a role in improving the cohesive strength of the binder and interfacial wetting, thus providing more sufficient contact and mass transfer conditions for subsequent chemical anchoring. The latent curing microcapsules in the post-triggered reactive anchoring sublayer use phenyl imidazole as the core material. Through shell isolation, they remain inert during the roll forming stage. Under the action of post-curing heat, the shell permeability changes or ruptures, releasing the imidazole catalyst. The imidazole is enriched at the interface and continues to catalyze the epoxy ring-opening reaction, so that the covalent bond between the active layer on the particle surface and the epoxidized natural rubber is further completed after the finished product is shaped; this process also promotes the condensation between silanols, making the silane layer on the particle surface more cross-linked and reducing the proportion of reversible adsorption, thereby reducing the possibility of interfacial migration under wet conditions.

[0021] The self-healing regenerating microcapsules use melamine-formaldehyde resin as the shell material to form a relatively dense isolation structure, stably encapsulating soybean oil core material within an asphalt-based binder. When the system generates microcracks under service shear or temperature cycling and propagates to the microcapsule location, the capsule shell ruptures, releasing the oil phase. The oil phase migrates in the continuous asphalt phase and becomes miscible with the lighter components in the asphalt, altering the local component distribution. This allows for the movement and adhesion reconstruction of molecular chain segments in the crack tip region, thereby inhibiting crack propagation. The water-absorbing and water-capturing microcapsules use a polyurea shell to isolate the calcium chloride core material, preventing it from directly reacting with the system under normal conditions. When moisture enters the interface or pores, it permeates through the shell and is bound to the core material in a hydrated state. This reduces the activity of free water at the interface, shifting the silane condensation reaction and acid-base adsorption equilibrium towards a direction more favorable to interface stability. Simultaneously, it reduces the probability of continuous film formation of water at the particle-asphalt interface, minimizing the chemical conditions for water-induced desquamation.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: The roll material provided by the present invention, through the synergistic structure of the anti-slip particle layer and the gradient embedded reactive anchoring layer, enables the particles to be stably embedded in the embedded bonding sublayer, and the latent curing system promotes the interface reaction in the reactive anchoring sublayer, forming a chemical connection between the particle surface active layer and the epoxidized natural rubber chain segments, thereby improving the particle retention and interface stability under wet conditions; the epoxidized natural rubber is introduced in the form of phase transfer concentrate and dehydrated with compatibilizer, reducing the risk of porosity and interface defects caused by latex water content, improving the compatibility and microphase uniformity of the rubber phase and the asphalt phase, and enhancing the cohesion and shear strength of the binder; the self-healing regenerating microcapsules release regenerating components when microcracks occur to regulate the local components and adhesion reconstruction process, and the water-absorbing and water-capturing components reduce the free water activity at the interface, reducing water-induced peeling conditions. Combined with the continuous embedding and post-curing process, the interlayer bonding of the roll material is more stable, comprehensively improving anti-slip durability, waterproof reliability and service adaptability. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the structure of the high anti-skid roll material modified with epoxidized natural rubber latex asphalt provided by the present invention.

[0024] Explanation of reference numerals in the attached diagram: 1. Anti-skid granular layer; 2. Gradient embedding-reactive anchoring layer; 3. Epoxidized natural rubber latex modified asphalt mixture layer; 4. Reinforced base course; 5. Bottom bonding layer; 6. Release layer. Detailed Implementation

[0025] The technical solutions of the present invention will be described in detail below with reference to specific embodiments and accompanying drawings. The embodiments described herein are specific implementations of the present invention, used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary, and should not be construed as limiting the implementation methods or the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can employ other obvious technical solutions based on the content disclosed in the claims and specification of this application. These technical solutions include those that make any obvious substitutions and modifications to the embodiments described herein.

[0026] The chemical reagents used in the embodiments and comparative examples of this invention are all commercially available products and have not undergone any further purification treatment.

[0027] Example 1

[0028] This embodiment provides an epoxidized natural rubber latex modified asphalt high anti-skid roofing membrane and its preparation method, specifically including:

[0029] A high-skid-resistance asphalt roll material modified with epoxidized natural rubber latex, wherein the roll material has a layered structure, such as... Figure 1 As shown, from top to bottom, it includes: anti-skid particle layer 1, gradient embedding-reactive anchoring layer 2, epoxidized natural rubber latex modified asphalt mixture layer 3, reinforced base course 4, bottom bonding layer 5, and release layer 6.

[0030] The anti-slip particle layer 1 is a two-stage spreading layer, comprising coarse particles and fine particles; the coarse particles have a particle size of 0.60 mm, the fine particles have a particle size of 0.60 mm, and the mass ratio of coarse particles to fine particles is 85:15; the anti-slip particles are selected from basalt particles, and the anti-slip particles are ceramic-coated mineral particles with an alumina coating layer on their surface.

[0031] The anti-slip particles undergo a first surface activation and a second surface activation before being spread. The first surface activation includes treating the particle surface with 0.2 wt.% γ-aminopropyltriethoxysilane based on the mass of the anti-slip particles. The second surface activation involves forming an organic active layer containing imidazole groups and primary amine groups on the particle surface after silane treatment. The organic active layer is formed by γ-imidazolepropyltriethoxysilane and polyethyleneimine.

[0032] The gradient embedding-reactive anchoring layer 2 includes a particle embedding bonding sublayer and a post-triggered reactive anchoring sublayer arranged adjacent to each other from top to bottom; the rosin-modified phenolic resin in the particle embedding bonding sublayer is added at a rate of 20 parts / 100 parts asphalt-based binder, and the thickness of the particle embedding bonding sublayer is 0.03 mm; the latent curing microcapsules in the post-triggered reactive anchoring sublayer are added at a rate of 1.20 parts / 100 parts asphalt-based binder, with an average particle size of 1 μm, a core material of 2-phenylimidazole, and a shell material of polycarbonate, and are prepared by dispersing 2-phenylimidazole in an organic phase and shearing and emulsifying it into water-in-oil microdroplets; Solvent evaporation solidifies polycarbonate at the microdroplet interface into a shell, yielding latently cured microcapsules. The self-healing regenerating microcapsules are added at a rate of 0.10 parts / 100 parts asphalt-based binder, with soybean oil as the core material and melamine-formaldehyde resin as the shell material. The preparation method is as follows: soybean oil is sheared and emulsified into water-in-oil microdroplets, and hexamethylol melamine is polymerized in situ at the oil droplet interface and crosslinked to form a shell under acidic conditions, yielding self-healing regenerating microcapsules. The post-triggered reaction anchoring sublayer further includes water-absorbing and water-capturing microcapsules, added at a rate of 0.60 parts / 100 parts asphalt-based binder, with polyurea as the shell material and calcium chloride as the core material.

[0033] The epoxidized natural rubber latex modified asphalt mixture layer 3 comprises base asphalt, epoxidized natural rubber (ENR-25), mineral fine aggregates, mineral fillers, and carbon nanofibers. The epoxidized natural rubber is introduced in the form of a phase transfer concentrate. The phase transfer concentrate is obtained by adding a phase transfer reactive compatibilizer (1-hexadecyl-1H-imidazolium) to the epoxidized natural rubber latex, shearing and mixing, and then performing thin-film evaporation, so that the water content of the resulting phase transfer concentrate is ≤0.2 wt.%. Based on the mass of the base asphalt, the amount of the phase transfer reactive compatibilizer is 0.3 wt.%, the dry rubber content of the epoxidized natural rubber is 15 wt.%, and the amount of carbon nanofibers added is 0.05 wt.%. The maximum particle size of the mineral fine aggregates in the mixture layer is ≤2.4 mm, and the mass fraction of the mineral filler is 25 wt.% of the solid components of the mixture layer.

[0034] The anti-slip particles are embedded to a depth of 70% of the equivalent particle size in the particle-bonded sublayer, and the surface coverage of the anti-slip particle layer 1 is 60%; the post-curing window of the roll material is 110℃ for 0.5 hours; the reinforcing base layer 4 is a polyester nonwoven felt with a unit area mass of 50 g / m². 2 The bottom adhesive layer 5 has a thickness of 1.50 mm, and the release layer 6 is release paper.

[0035] The roll material is prepared using the following method: epoxidized natural rubber latex is shear-mixed with a phase transfer reaction compatibilizer 1-hexadecyl-1H-imidazolium and then dehydrated. A phase transfer concentrate is obtained by thin-film evaporation, ensuring the water content of the concentrate is ≤0.2 wt.%. The phase transfer concentrate is added to a flowable matrix asphalt and shear-dispersed. Mineral fine aggregates and mineral fillers are then added and mixed evenly to form a mixture layer. After uniform mixing, carbon nanofibers are added and dispersed. Basalt anti-skid particles undergo a first surface activation and a second surface activation. The first surface activation involves treating the particle surface with 0.2 wt.% γ-aminopropyltriethoxysilane based on the particle mass. The second surface activation involves forming an organic active layer containing imidazolium and primary amine groups on the particle surface after silane treatment, composed of γ-imidazolium-propyltriethoxysilane and polyethyleneimine. This yields a surface-treated... Anti-slip particles; on a continuous production line, using polyester nonwoven felt reinforced base layer 4 as the load-bearing substrate, a post-triggered reaction anchoring sublayer is first formed. The post-triggered reaction anchoring sublayer is an asphalt-based binder with latent curing microcapsules, self-healing regeneration microcapsules, and water-absorbing and water-capturing microcapsules added. Subsequently, a particle embedding bonding sublayer is formed on it. The particle embedding bonding sublayer is an asphalt-based binder with rosin-modified phenolic resin added. The particle embedding bonding sublayer is kept in a hot state, and surface-treated bi-graded anti-slip particles are spread to form an anti-slip particle layer 1. It is then pressed and fixed under controlled pressure by a cooling drum and pressure roller. The mixture layer material is laid or coated below the structure to form an epoxidized natural rubber latex modified asphalt mixture layer 3, and a bottom bonding layer 5 is formed on the lower surface before composite release paper is laminated. The resulting roll material is post-cured at 110°C for 0.5 hours to obtain the epoxidized natural rubber latex modified asphalt high anti-slip roll material.

[0036] Example 2

[0037] This embodiment provides an epoxidized natural rubber latex modified asphalt high anti-skid roofing membrane and its preparation method, specifically including:

[0038] A high-skid-resistance asphalt roll material modified with epoxidized natural rubber latex, wherein the roll material has a layered structure, such as... Figure 1 As shown, from top to bottom, it includes: anti-skid particle layer 1, gradient embedding-reactive anchoring layer 2, epoxidized natural rubber latex modified asphalt mixture layer 3, reinforced base course 4, bottom bonding layer 5, and release layer 6.

[0039] The anti-slip particle layer 1 is a two-stage spreading layer, comprising coarse particles and fine particles; the coarse particles have a particle size of 4.75 mm, the fine particles have a particle size of 0.20 mm, and the mass ratio of coarse particles to fine particles is 55:45; the anti-slip particles are selected from corundum particles, and the anti-slip particles are ceramic-coated mineral particles with an alumina coating layer on their surface.

[0040] The anti-slip particles undergo a first surface activation and a second surface activation before being spread. The first surface activation includes treating the particle surface with 2.0 wt.% γ-aminopropyltriethoxysilane based on the mass of the anti-slip particles. The second surface activation involves forming an organic active layer containing imidazole groups on the particle surface after silane treatment. The organic active layer is formed by γ-imidazolepropyltriethoxysilane.

[0041] The gradient embedding-reactive anchoring layer 2 comprises a particle embedding bonding sublayer and a post-triggered reactive anchoring sublayer; the particle embedding bonding sublayer contains 2 parts of C9 petroleum resin per 100 parts of asphalt-based binder, and the thickness of the particle embedding bonding sublayer is 0.40 mm; the post-triggered reactive anchoring sublayer contains 0.05 parts of latent curing microcapsules per 100 parts of asphalt-based binder, with an average particle size of 40 μm, a core material of 2-phenylimidazole, and a shell material of polycaprolactone. The preparation method is as follows: 2-phenylimidazole is dispersed in an organic phase and sheared and emulsified into a water-in-oil microcapsule. The self-healing and regenerating microcapsules are prepared by solvent displacement to solidify polycaprolactone at the microdroplet interface into a shell, resulting in latently cured microcapsules. The self-healing and regenerating microcapsules are added at a ratio of 2.50 parts / 100 parts asphalt-based binder, with soybean oil as the core material and melamine-formaldehyde resin as the shell material. The preparation method is as follows: soybean oil is sheared and emulsified into water-in-oil microdroplets, and hexamethylol melamine is polymerized in situ at the oil droplet interface and crosslinked to form a shell under acidic conditions, resulting in self-healing and regenerating microcapsules. The post-triggered reaction anchoring sublayer further includes a closed-type water-absorbing and water-trapping agent, which is added at a ratio of 0.02 parts / 100 parts asphalt-based binder.

[0042] The epoxidized natural rubber latex modified asphalt mixture layer 3 comprises base asphalt, epoxidized natural rubber (ENR-50), mineral fine aggregates, mineral fillers, and nano-alumina. The epoxidized natural rubber is introduced in the form of a phase transfer concentrate. The phase transfer concentrate is obtained by adding a phase transfer reactive compatibilizer (1-octadecyl-1H-imidazolium) to the epoxidized natural rubber latex, shearing and mixing, and then dehydrating under reduced pressure to achieve a water content of ≤0.2 wt.%. Based on the mass of the base asphalt, the amount of the phase transfer reactive compatibilizer is 2.5 wt.%, the dry rubber content of the epoxidized natural rubber is 3 wt.%, and the amount of nano-alumina added is 0.80 wt.%. The maximum particle size of the mineral fine aggregates in the mixture layer is ≤2.4 mm, and the mass fraction of the mineral filler is 8 wt.% of the solid components of the mixture layer.

[0043] The anti-slip particles are embedded to a depth of 15% of the equivalent particle size in the particle bonding sublayer, and the surface coverage of the anti-slip particle layer 1 is 95%; the post-curing window of the roll material is 80℃ for 6 hours; the reinforcing base layer 4 is fiberglass mat with a unit area mass of 300g / m².2 The bottom adhesive layer 5 has a thickness of 0.10 mm, and the release layer 6 is a release film.

[0044] The roll material is prepared using the following method: epoxidized natural rubber latex is sheared and mixed with a phase transfer reaction compatibilizer 1-octadecyl-1H-imidazolium, followed by dehydration. Vacuum dehydration is then used to obtain a phase transfer concentrate, ensuring the water content of the concentrate is ≤0.2 wt.%. The phase transfer concentrate is added to a flowable base asphalt and sheared and dispersed. Mineral fine aggregates and mineral fillers are then added and mixed evenly to form a mixture layer. After uniform mixing, nano-alumina is added and dispersed. The corundum anti-skid particles undergo a two-step surface activation process. The first surface activation involves treating the particle surface with 2.0 wt.% γ-aminopropyltriethoxysilane based on the particle mass. The second surface activation involves forming an imidazolium-containing organic active layer on the particle surface after silane treatment using γ-imidazoliumpropyltriethoxysilane, resulting in surface-treated anti-skid particles. The process is carried out on a continuous production line. The substrate is a fiberglass felt-reinforced base layer 4. A post-triggered reactive anchoring sublayer is first formed, consisting of an asphalt-based binder with latent curing microcapsules and self-healing regeneration microcapsules, along with a closed-type water-absorbing and water-trapping agent. Subsequently, a particle-embedded bonding sublayer is formed on top of this, consisting of an asphalt-based binder with C9 petroleum resin. The particle-embedded bonding sublayer is kept hot, and surface-treated bi-graded anti-skid particles are spread to form an anti-skid particle layer 1. This layer is then pressed and fixed under controlled pressure by a cooling drum and pressure roller. Below this structure, the mixture layer material is laid or coated to form an epoxidized natural rubber latex-modified asphalt mixture layer 3. A bottom bonding layer 5 is then formed on the lower surface, followed by a release film. The resulting roll material undergoes post-curing treatment at 80°C for 6 hours to obtain the epoxidized natural rubber latex-modified asphalt high-anti-skid roll material.

[0045] Example 3

[0046] This embodiment provides an epoxidized natural rubber latex modified asphalt high anti-skid roofing membrane and its preparation method, specifically including:

[0047] A high-skid-resistance asphalt roll material modified with epoxidized natural rubber latex, wherein the roll material has a layered structure, such as... Figure 1 As shown, from top to bottom, it includes: anti-skid particle layer 1, gradient embedding-reactive anchoring layer 2, epoxidized natural rubber latex modified asphalt mixture layer 3, reinforced base course 4, bottom bonding layer 5, and release layer 6.

[0048] The anti-slip particle layer 1 is a two-stage spreading layer, comprising coarse particles and fine particles; the coarse particles have a particle size of 2.5 mm, the fine particles have a particle size of 0.40 mm, and the mass ratio of coarse particles to fine particles is 70:30; the anti-slip particles are selected from alumina ceramic particles, and the anti-slip particles are ceramic-coated mineral particles with an alumina coating layer on their surface.

[0049] The anti-slip particles undergo a first surface activation and a second surface activation before being spread. The first surface activation includes treating the particle surface with 1.0 wt.% γ-aminopropyltriethoxysilane based on the mass of the anti-slip particles. The second surface activation involves forming an organic active layer containing primary amine groups on the particle surface after silane treatment. The organic active layer is formed from polyethyleneimine.

[0050] The gradient embedding-reactive anchoring layer 2 includes a particle embedding bonding sublayer and a post-triggered reactive anchoring sublayer; the particle embedding bonding sublayer contains a mixture of rosin-modified phenolic resin and C9 petroleum resin at an addition amount of 10 parts / 100 parts asphalt-based binder, and the thickness of the particle embedding bonding sublayer is 0.20 mm; the post-triggered reactive anchoring sublayer contains latent curing microcapsules at an addition amount of 0.60 parts / 100 parts asphalt-based binder, with an average particle size of 20 μm, a core material of 2-phenylimidazole, and a shell material of polyurethane / polyurea. The preparation method is as follows: 2-phenylimidazole is dispersed in an organic phase and sheared and emulsified into water-in-oil microdroplets, and then... Interfacial polymerization of isocyanate and diamine is carried out at the interface to form a polyurethane / polyurea shell, resulting in latently cured microcapsules. The self-healing and regenerating microcapsules are added at an amount of 1.50 parts / 100 parts asphalt-based binder, with soybean oil as the core material and melamine-formaldehyde resin as the shell material. The preparation method is as follows: soybean oil is sheared and emulsified into water-in-oil droplets, and hexamethylol melamine is polymerized in situ at the oil droplet interface under acidic conditions and crosslinked to form a shell, resulting in self-healing and regenerating microcapsules. The post-triggered reaction anchoring sublayer further includes water-absorbing and water-capturing microcapsules, which are added at an amount of 0.30 parts / 100 parts asphalt-based binder, with polyurea as the shell material and calcium chloride as the core material.

[0051] The epoxidized natural rubber latex modified asphalt mixture layer 3 comprises base asphalt, epoxidized natural rubber (a combination of ENR-25 and ENR-50 in a mass ratio of 1:1), mineral fine aggregates, mineral fillers, and carbon nanofibers. The epoxidized natural rubber is introduced in the form of a phase transfer concentrate. The phase transfer concentrate is obtained by adding a phase transfer reactive compatibilizer (a mixture of 1-hexadecyl-1H-imidazole and 1-octadecyl-1H-imidazole in a mass ratio of 1:1) to the epoxidized natural rubber latex, shearing and mixing, and then dehydrating by inert gas purging, so that the water content of the resulting phase transfer concentrate is ≤0.2 wt.%. Based on the mass of the base asphalt, the amount of the phase transfer reactive compatibilizer is 1.5 wt.%, the dry rubber content of the epoxidized natural rubber is 8 wt.%, and the amount of carbon nanofibers added is 0.40 wt.%. The maximum particle size of the mineral fine aggregates in the mixture layer is ≤2.4 mm, and the mass fraction of the mineral filler is 15 wt.% of the solid components of the mixture layer.

[0052] The anti-slip particles are embedded to a depth of 40% of the equivalent particle size in the particle bonding sublayer, and the surface coverage of the anti-slip particle layer 1 is 80%. The post-curing window of the roll material is 90℃ for 3 hours. The reinforcing base layer 4 is a polyester / glass fiber composite base with a unit area mass of 180g / m². 2 The bottom adhesive layer 5 has a thickness of 0.80 mm, and the release layer 6 is a release film.

[0053] The roll material is prepared by the following method: epoxidized natural rubber latex is sheared and mixed with a phase transfer reaction compatibilizer (a mixture of 1-hexadecyl-1H-imidazolium and 1-octadecyl-1H-imidazolium), then dehydrated. Inert gas is used to purge and dehydrate the mixture to obtain a phase transfer concentrate with a water content ≤0.2 wt.%. The phase transfer concentrate is added to a flowable matrix asphalt and sheared and dispersed. Mineral fine aggregates and mineral fillers are then added and mixed evenly to form a mixture layer. After even mixing, carbon nanofibers are added and dispersed. Alumina ceramic anti-skid particles undergo two-step surface activation. The first surface activation involves treating the particle surface with 1.0 wt.% γ-aminopropyltriethoxysilane based on the particle mass. The second surface activation involves forming an organic active layer containing primary amine groups on the particle surface with polyethyleneimine after silane treatment, resulting in surface-treated anti-skid particles. In continuous... On the production line, a polyester / glass fiber composite reinforced base layer 4 is used as the load-bearing substrate. A post-triggered reactive anchoring sublayer is first formed, consisting of an asphalt-based binder incorporating latent curing microcapsules, self-healing regeneration microcapsules, and water-absorbing / capturing microcapsules. Subsequently, a particle-embedded bonding sublayer is formed on top of this, consisting of an asphalt-based binder incorporating a mixture of rosin-modified phenolic resin and C9 petroleum resin. The particle-embedded bonding sublayer is kept hot, and surface-treated bi-graded anti-skid particles are spread to form an anti-skid particle layer 1. This layer is then pressed and fixed under controlled pressure by a cooling drum and pressure rollers. Below this structure, the mixture layer material is laid or coated to form an epoxidized natural rubber latex modified asphalt mixture layer 3, and a bottom bonding layer 5 is formed on the lower surface before a release film is laminated. The resulting roll material undergoes post-curing treatment at 90°C for 3 hours to obtain the epoxidized natural rubber latex modified asphalt high-anti-skid roll material.

[0054] Example 4

[0055] This embodiment provides an epoxidized natural rubber latex modified asphalt high anti-skid roofing membrane and its preparation method, specifically including:

[0056] A high-skid-resistance asphalt roll material modified with epoxidized natural rubber latex, wherein the roll material has a layered structure, such as... Figure 1 As shown, from top to bottom, it includes: anti-skid particle layer 1, gradient embedding-reactive anchoring layer 2, epoxidized natural rubber latex modified asphalt mixture layer 3, reinforced base course 4, bottom bonding layer 5, and release layer 6.

[0057] The anti-slip particle layer 1 is a two-stage spreading layer, comprising coarse particles and fine particles; the coarse particles have a particle size of 1.00 mm, the fine particles have a particle size of 0.30 mm, and the mass ratio of coarse particles to fine particles is 75:25; the anti-slip particles are selected from silicon carbide particles, and the anti-slip particles are ceramic-coated mineral particles with an alumina coating layer on their surface.

[0058] The anti-slip particles undergo a first surface activation and a second surface activation before being spread. The first surface activation includes treating the particle surface with 1.5 wt.% γ-aminopropyltriethoxysilane based on the mass of the anti-slip particles. The second surface activation involves forming an imidazole-containing organic active layer on the particle surface after silane treatment, wherein the organic active layer is formed by γ-imidazolepropyltriethoxysilane.

[0059] The gradient embedding-reactive anchoring layer 2 comprises a particle embedding bonding sublayer and a post-triggered reactive anchoring sublayer; the rosin-modified phenolic resin in the particle embedding bonding sublayer is added at a ratio of 8 parts / 100 parts asphalt-based binder, and the thickness of the particle embedding bonding sublayer is 0.30 mm; the latent curing microcapsules in the post-triggered reactive anchoring sublayer are added at a ratio of 0.80 parts / 100 parts asphalt-based binder, with an average particle size of 30 μm, a core material of 2-phenylimidazole, and a shell material of polycarbonate. The preparation method is as follows: 2-phenylimidazole is dispersed in an organic phase and sheared and emulsified into a water-in-oil emulsion. Microdroplets are solidified into shells by solvent evaporation of polycarbonate at the microdroplet interface, resulting in latent solidified microcapsules. The self-healing and regenerating microcapsules are added at a ratio of 2.0 parts / 100 parts asphalt-based binder, with soybean oil as the core material and melamine-formaldehyde resin as the shell material. The preparation method is as follows: soybean oil is sheared and emulsified into water-in-oil microdroplets, and hexamethylol melamine is polymerized in situ at the oil droplet interface and crosslinked to form a shell under acidic conditions, resulting in self-healing and regenerating microcapsules. The post-triggered reaction anchoring sublayer further includes a closed-type water-absorbing and water-trapping agent, which is added at a ratio of 0.40 parts / 100 parts asphalt-based binder.

[0060] The epoxidized natural rubber latex modified asphalt mixture layer 3 comprises base asphalt, liquid epoxidized natural rubber, mineral fine aggregates, mineral fillers, and nano-alumina. The epoxidized natural rubber is introduced in the form of a phase transfer concentrate. The phase transfer concentrate is obtained by adding a phase transfer reactive compatibilizer (1-hexadecyl-1H-imidazolium) to the epoxidized natural rubber latex, shearing and mixing, and then performing thin-film evaporation, so that the water content of the resulting phase transfer concentrate is ≤0.2 wt.%. Based on the mass of the base asphalt, the amount of the phase transfer reactive compatibilizer is 2.0 wt.%, the dry rubber content of the epoxidized natural rubber is 10 wt.%, and the amount of nano-alumina added is 0.60 wt.%. The maximum particle size of the mineral fine aggregates in the mixture layer is ≤2.4 mm, and the mass fraction of the mineral filler is 20 wt.% of the solid components of the mixture layer.

[0061] The anti-slip particles are embedded to a depth of 50% of the equivalent particle size in the particle embedding and bonding sublayer, and the surface coverage of the anti-slip particle layer 1 is 90%; the post-curing window of the roll material is 100℃ for 1 hour; the reinforcing base layer 4 is a polyester nonwoven felt with a unit area mass of 250g / m². 2 The bottom adhesive layer 5 has a thickness of 1.0 mm, and the release layer 6 is release paper.

[0062] The roll material is prepared by the following method: epoxidized natural rubber latex is sheared and mixed with a phase transfer reaction compatibilizer 1-hexadecyl-1H-imidazolium, then dehydrated. A phase transfer concentrate is obtained by thin-film evaporation, ensuring the water content of the concentrate is ≤0.2 wt.%. The phase transfer concentrate is added to a flowable matrix asphalt and sheared and dispersed. Mineral fine aggregates and mineral fillers are then added and mixed evenly to form a mixture layer. After even mixing, liquid epoxidized natural rubber and nano-alumina are added and dispersed. Silicon carbide anti-skid particles undergo two-step surface activation. The first surface activation involves treating the particle surface with 1.5 wt.% γ-aminopropyltriethoxysilane based on the particle mass. The second surface activation involves forming an imidazolium-containing organic active layer on the particle surface after silane treatment using γ-imidazoliumpropyltriethoxysilane, resulting in surface-treated anti-skid particles. On the production line, using polyester nonwoven felt reinforced base layer 4 as the load-bearing substrate, a post-triggered reaction anchoring sublayer is first formed. This post-triggered reaction anchoring sublayer is an asphalt-based binder with latent curing microcapsules and self-healing regeneration microcapsules added, along with a closed-type water-absorbing and water-capturing agent. Subsequently, a particle-embedded bonding sublayer is formed on top of this sublayer. This particle-embedded bonding sublayer is an asphalt-based binder with rosin-modified phenolic resin added. The particle-embedded bonding sublayer is kept hot, and surface-treated bi-graded anti-slip particles are spread to form an anti-slip particle layer 1. This layer is then pressed and fixed under controlled pressure by a cooling drum and pressure roller. Below this structure, the mixture layer material is laid or coated to form an epoxidized natural rubber latex modified asphalt mixture layer 3, and a bottom bonding layer 5 is formed on the lower surface before laminating with release paper. The resulting roll material is then subjected to post-curing treatment at a curing window of 100°C for 1 hour to obtain the epoxidized natural rubber latex modified asphalt high anti-slip roll material.

[0063] Comparative Example 1

[0064] This comparative example provides a high anti-skid roofing membrane modified with epoxidized natural rubber latex and its preparation method. The difference between this and Example 1 is that the epoxidized natural rubber is not introduced in the form of a phase transfer concentrate, but the epoxidized natural rubber latex is directly added to the base asphalt for mixing, and the step of dehydration after shear mixing to obtain a phase transfer concentrate is not performed. Other process parameters and operating conditions are exactly the same as in Example 1.

[0065] Comparative Example 2

[0066] This comparative example provides a high anti-skid roll material modified with epoxidized natural rubber latex asphalt and its preparation method. The difference between this and Example 1 is that no latent curing microcapsules are added to the post-triggered reaction anchoring sublayer. Other process parameters and operating conditions are exactly the same as in Example 1.

[0067] Comparative Example 3

[0068] This comparative example provides an epoxidized natural rubber latex modified asphalt high anti-skid roll material and its preparation method. The difference between this and Example 1 is that the anti-skid particles are only subjected to a first surface activation treatment before spreading, and no second surface activation treatment is performed. That is, no organic active layer containing imidazole groups and primary amine groups is formed on the particle surface after silane treatment. Other process parameters and operating conditions are exactly the same as in Example 1.

[0069] Comparative Example 4

[0070] This comparative example provides a high anti-skid roll material modified with epoxidized natural rubber latex asphalt and its preparation method. The difference between this and Example 1 is that the gradient embedding-reactive anchoring layer 2 does not include a post-triggered reactive anchoring sublayer. That is, the post-triggered reactive anchoring sublayer is not set and no latent curing microcapsules, self-healing regeneration microcapsules, water-absorbing and water-capturing microcapsules or closed water-absorbing and water-capturing agents are added. Only the particle embedding and bonding sublayer is retained for the hot pressing and fixing of anti-skid particles. Other process parameters and operating conditions are exactly the same as in Example 1.

[0071] Performance testing:

[0072] The wet anti-slip performance test method is EN 13036-4;

[0073] The test method for anti-slip particle holding force is EN 12039;

[0074] The test method for interlayer / joint bond strength is EN 12316-1.

[0075] The test results of the epoxidized natural rubber latex modified asphalt high anti-skid rolls prepared in Examples 1-4 and Comparative Examples 1-4 are shown in Table 1.

[0076] Table 1. Test results of high anti-skid asphalt rolls modified with epoxidized natural rubber latex in Examples 1-4 and Comparative Examples 1-4

[0077] Wet skid resistance (BPN) <![CDATA[Amount of brush wear loss (g / m 2 )]]> Bond strength (N / 50mm) Example 1 69 12 380 Example 2 78 10 340 Example 3 72 14 360 Example 4 75 11 390 Comparative Example 1 57 42 240 Comparative Example 2 63 20 310 Comparative Example 3 61 24 290 Comparative Example 4 54 50 220

[0078] As shown in Table 1, compared with Example 1, Comparative Example 1 showed decreased wet anti-slip performance, increased brushing and abrasion detachment, and decreased bond strength; Comparative Example 2 showed decreased wet anti-slip performance, increased brushing and abrasion detachment, and decreased bond strength; Comparative Example 3 showed decreased wet anti-slip performance, increased brushing and abrasion detachment, and decreased bond strength; and Comparative Example 4 showed decreased wet anti-slip performance, increased brushing and abrasion detachment, and decreased bond strength.

[0079] This is because Comparative Example 1 did not undergo phase transfer dehydration, allowing latex moisture to enter the asphalt system along with the rubber phase. During high-temperature mixing and pressing, this easily leads to the formation of air bubbles and weakens the binder's cohesion. Increased water-induced peeling conditions and discontinuous post-curing reactions result in decreased particle holding power, reduced peel strength, and decreased BPN with particle removal. In Comparative Example 2, after removing the latent curing microcapsules, the imidazole catalyst source was insufficient during the post-curing stage, leading to inadequate covalent anchoring between the epoxy ring-opening layer and the active layer on the particle surface. The interface relied more on physical embedding and tackifying resin, resulting in increased particle shedding during brushing, decreased interlayer peel strength, and a drop in wet BPN. In Comparative Example 3, after eliminating the second surface activation, the particle surface lacked imidazole / primary amine reaction sites. The silane layer mainly provided adsorption and limited bonding, making it difficult to form a continuous covalent network with the ENR epoxy. Under water film and shear action, the interface easily slipped and pulled-out, increasing the amount of shedding and reducing peel strength and BPN. In Comparative Example 4, without setting a post-triggered reaction anchoring sublayer, the lack of latent curing, self-healing regeneration, and water-capturing systems resulted in decreased cohesion of the embedded adhesive layer under thermal softening and water immersion conditions, and the lack of secondary reaction consolidation at the interface. After brushing, the particles were more easily pulled out as a whole, resulting in increased shedding, reduced peel strength, and decreased BPN.

[0080] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A high-slip roll material made of epoxidized natural rubber latex modified asphalt, characterized in that, The roll material has a layered structure, which includes, from top to bottom: an anti-skid particle layer (1), a gradient embedding-reactive anchoring layer (2), an epoxidized natural rubber latex modified asphalt mixture layer (3), a reinforced base layer (4), a bottom bonding layer (5), and a release layer (6); the anti-skid particle layer (1) and the gradient embedding-reactive anchoring layer (2) are arranged adjacent to each other; The gradient embedding-reactive anchoring layer (2) includes a particle embedding bonding sublayer and a post-triggered reactive anchoring sublayer arranged adjacent to each other from top to bottom; the particle embedding bonding sublayer is an asphalt-based binder containing a polar tackifying resin, and the anti-skid particles are embedded in the particle embedding bonding sublayer under hot conditions; the post-triggered reactive anchoring sublayer is an asphalt-based binder containing latent curing microcapsules and self-healing regeneration microcapsules; the epoxidized natural rubber latex modified asphalt mixture layer (3) includes matrix asphalt, epoxidized natural rubber, mineral fine aggregates and mineral fillers, and the epoxidized natural rubber is introduced in the form of a phase transfer concentrate.

2. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 1, characterized in that, The anti-slip particle layer (1) is a two-stage spreading layer, comprising coarse particles and fine particles; the coarse particles have a particle size of 0.60-4.75 mm, the fine particles have a particle size of 0.20-0.60 mm, and the mass ratio of coarse particles to fine particles is (55-85):(45-15); the anti-slip particles are selected from one or more of basalt particles, corundum particles, alumina ceramic particles and silicon carbide particles, and the anti-slip particles are ceramic-coated mineral particles with a ceramic coating layer on the surface, the ceramic coating layer being an alumina coating layer.

3. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 2, characterized in that, The anti-slip particles undergo a first surface activation and a second surface activation before being spread. The first surface activation includes treating the particle surface with 0.2-2.0 wt.% of a silane coupling agent, based on the mass of the anti-slip particles, wherein the silane coupling agent is γ-aminopropyltriethoxysilane. The second surface activation involves forming an organic active layer containing imidazole groups and / or primary amine groups on the particle surface after silane treatment, wherein the organic active layer is formed by γ-imidazolepropyltriethoxysilane and / or polyethyleneimine.

4. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 1, characterized in that, The amount of polar tackifying resin added to the particle-embedded bonding sublayer is 2-20 parts / 100 parts of asphalt-based binder, the thickness of the particle-embedded bonding sublayer is 0.03-0.40 mm, and the polar tackifying resin is rosin-modified phenolic resin and / or C9 petroleum resin.

5. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 1, characterized in that, The amount of latent solidified microcapsules added to the post-triggered reaction anchoring sublayer is 0.05-1.20 parts / 100 parts asphalt-based binder; the average particle size of the latent solidified microcapsules is 1-40 μm; the core material of the latent solidified microcapsules is 2-phenylimidazole, and the shell material is polycarbonate, polycaprolactone, or polyurethane / polyurea. The preparation method of the latent solidified microcapsules is as follows: 2-phenylimidazole is dispersed in an organic phase and sheared and emulsified into water-in-oil microdroplets; polycarbonate or polycaprolactone is solidified into a shell at the microdroplet interface by solvent evaporation / displacement, or isocyanate and diamine are interfacially polymerized at the microdroplet interface to form a polyurethane / polyurea shell layer, thereby obtaining latent solidified microcapsules.

6. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 1, characterized in that, The self-healing and regenerating microcapsules in the post-triggered reaction anchoring sublayer are added at a rate of 0.10-2.50 parts per 100 parts of asphalt-based binder; the core material of the self-healing and regenerating microcapsules is soybean oil, and the shell material is a heat-resistant and oxidation-resistant coating material, which is melamine-formaldehyde resin; the post-triggered reaction anchoring sublayer further includes water-absorbing and water-capturing microcapsules or a closed-type water-absorbing and water-capturing agent, added at a rate of 0.02-0.60 parts per 100 parts of asphalt-based binder, the shell material of the water-absorbing and water-capturing microcapsules is polyurea, and the core material is calcium chloride hygroscopic agent; the preparation method of the self-healing and regenerating microcapsules is as follows: soybean oil is sheared and emulsified into water-in-oil droplets; under acidic conditions, hexamethylol melamine is polymerized in situ at the oil droplet interface and crosslinked to form a shell, thereby obtaining self-healing and regenerating microcapsules.

7. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 1, characterized in that, The phase transfer concentrate is obtained by adding a phase transfer reactive compatibilizer to epoxidized natural rubber latex and shearing and mixing it, followed by thin-film evaporation, dehydration under reduced pressure, or inert gas purging to achieve a water content of ≤0.2 wt.% in the resulting phase transfer concentrate; wherein, based on the mass of the base asphalt, the amount of the phase transfer reactive compatibilizer is 0.3-2.5 wt.%; the phase transfer reactive compatibilizer is an amphiphilic compound containing C12-C30 hydrophobic segments and epoxy reactive groups, wherein the epoxy reactive group is an imidazole group, and the phase transfer reactive compatibilizer is 1-hexadecyl-1H-imidazolium and / or 1-octadecyl-1H-imidazolium.

8. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 1, characterized in that, Based on the quality of the base asphalt, the dry rubber content of the epoxidized natural rubber is 3-15 wt.%; the epoxidized natural rubber is one or a combination of ENR-25 and ENR-50, or liquid epoxidized natural rubber; the epoxidized natural rubber latex modified asphalt mixture layer (3) further contains one or more of carbon nanofibers or nano-alumina, with an addition amount of 0.05-0.80 wt.% based on the base asphalt.

9. The high anti-skid roofing membrane modified with epoxidized natural rubber latex according to claim 1, characterized in that, The particle size of the mineral fine aggregate in the epoxidized natural rubber latex modified asphalt mixture layer (3) is ≤2.4mm, and the mass fraction of the mineral filler is 8-25wt.% of the solid component of the mixture layer; the embedding depth of the anti-skid particles into the particle embedding and bonding sublayer is 15-70% of the equivalent particle size, and the surface coverage of the anti-skid particle layer (1) is 60-95%; the roll material is embedded by a continuous production line through a cooling drum and a pressure roller under controlled pressure; the post-curing window of the post-triggered reaction anchoring sublayer is 80-110℃ for 0.5-6h; the reinforced base layer (4) is polyester nonwoven felt, glass fiber felt or polyester / glass fiber composite base, and its unit area mass is 50-300g / m 2 The bottom adhesive layer (5) has a thickness of 0.10-1.50 mm, and the release layer (6) is release paper or release film.

10. A method for preparing an epoxidized natural rubber latex modified asphalt high-skid roll material according to any one of claims 1-9, characterized in that, The process includes the following steps: epoxidized natural rubber latex and phase transfer reaction compatibilizer are sheared and mixed, then dehydrated to obtain a phase transfer concentrate; the phase transfer concentrate is mixed with matrix asphalt, mineral fine aggregate and mineral filler to form an epoxidized natural rubber latex modified asphalt mixture layer (3); a particle embedding bonding sublayer and a post-triggered reaction anchoring sublayer are formed on the epoxidized natural rubber latex modified asphalt mixture layer (3), and surface-treated anti-skid particles are spread under hot conditions, and then pressed and fixed by a cooling drum and pressure roller to form an anti-skid particle layer (1); after post-curing treatment of the obtained roll material, a bottom bonding layer (5) and a composite release layer (6) are formed on the lower surface to obtain the epoxidized natural rubber latex modified asphalt high anti-skid roll material.

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