Waterproof coating coiled material

Abstract

The invention discloses a waterproof coating coiled material, and belongs to the technical field of waterproof materials. The coiled material comprises a matrix and a gel-state waterproof coating impregnated and attached to the matrix, and the coating is prepared by in-situ physical cross-linking reaction of base stock slurry containing a polymer emulsion, an inorganic filler, a polyvinyl alcohol solution and a hydrophilic modified isocyanate curing agent and a boron-containing cross-linking initiator solution. The preparation method comprises the following steps: dipping a matrix into base stock slurry, applying an initiator solution to the surface of the coating, inducing the coating to be quickly converted from a liquid state to a gel state, laminating, cutting, and sealing and packaging. According to the invention, a dual mechanism of physical gel and chemical crosslinking is utilized, coiled prefabrication and baking-free low-energy-consumption production of the liquid coating are realized, and the product has excellent storage stability, microscopic full viscosity with concrete and long-term water resistance.

Description

Technical Field

[0001] This invention relates to the field of waterproof materials technology, specifically to a waterproof coating roll material. Background Technology

[0002] Underground waterproofing projects require high levels of material adhesion and ease of construction. Pre-laid reverse bonding technology is widely used because it allows for a tight bond between the waterproofing layer and the main structure. Currently, pre-laid waterproofing membranes on the market mainly use polymer sheets (such as HDPE and TPO) as the base material, covered with a polymer adhesive film layer. While these polymer sheets possess good tensile strength and puncture resistance, their material rigidity is relatively high, relying primarily on the pressure-sensitive adhesive of the adhesive film layer to bond with concrete. In practical applications, due to the surface roughness of concrete during pouring and curing shrinkage, rigid sheets struggle to achieve complete microscopic adhesion to the structural layer. Once the waterproofing layer experiences localized damage, moisture can easily diffuse laterally through the tiny gaps between the membrane and the concrete interface, causing water seepage and leading to large-area waterproofing failure.

[0003] To improve interfacial adhesion, the industry has experimented with using non-curing or semi-curing coatings with creep properties as adhesive layers. These materials are closer to liquid in rheology, enabling them to better wet the capillaries of concrete. However, pre-forming such high-viscosity coatings into roll products presents a contradiction between process and performance. If traditional solvent evaporation or heat drying processes are used, the production line is not only energy-intensive and inefficient, but the fully dried coating often loses its rheological properties, reducing its self-healing and micro-adhesion capabilities. If the coating is rolled directly while retaining its wet properties, the material remains in a viscous flow state at room temperature, making it highly susceptible to cold flow deformation during storage, transportation, and vertical stacking. This can lead to slippage of the release liner, roll collapse, or interlayer adhesion, failing to meet the requirements of industrialized finished products.

[0004] Therefore, how to make waterproof materials have the morphological stability of solid rolls during storage and restore the interfacial wetting and bonding properties of liquid coatings during application without using high-energy-consuming drying processes is an urgent problem to be solved in the field of waterproof materials. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a waterproof coating roll material, which solves the problems of existing pre-laid reverse-adhesive waterproof materials. Polymer sheet products have good dimensional stability but are difficult to form a microscopic full bond with concrete, leading to the risk of water seepage between layers. Coating products have good adhesion but cannot be prefabricated into roll form for storage and transportation, and on-site construction is greatly affected by the environment.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] In a first aspect, the present invention provides a waterproof coating roll material, which adopts the following technical solution:

[0008] A waterproof coating roll includes a substrate and a gel-like waterproof coating impregnated and attached to the substrate; the gel-like waterproof coating is formed by contacting a waterproof coating base slurry with a crosslinking initiator solution and undergoing an in-situ physical crosslinking reaction; wherein, relative to 100 parts by weight of the waterproof coating base slurry, the amount of the crosslinking initiator solution is 1.0 to 3.0 parts by weight; the waterproof coating base slurry is made from raw materials comprising the following parts by weight: 40 to 60 parts of polymer emulsion; 24 to 34 parts of inorganic filler; 15 to 25 parts of polyvinyl alcohol solution; 1.0 to 2.5 parts of hydrophilic modified isocyanate curing agent; and 0.4 to 0.8 parts of dispersant and defoamer; the crosslinking initiator solution is an aqueous solution containing a boron compound.

[0009] By employing the above technical solution, this invention combines physical gelation and chemical cross-linking mechanisms, achieving both solid-state retention of the waterproof material during storage and liquid wetting during application. The specific mechanism and effects are as follows:

[0010] Structural stability during storage: When the polyvinyl alcohol solution in the system comes into contact with the boron-containing compound solution, the borate ions undergo a complexation reaction with the hydroxyl groups on the polyvinyl alcohol molecular chain to form a borate ester complex. This complex establishes a physical network structure in the polymer emulsion system, increasing the system's zero-shear viscosity and yield stress. This structure allows the coating to remain in a gel state under static storage conditions, preventing the roll material from flowing or deforming when rolled or stored vertically.

[0011] Interface wettability during construction: The aforementioned borate ester bonds exhibit reversible breakage and recombination characteristics. During construction, the shear force generated by the fresh concrete disrupts the physical cross-linking nodes, reducing the coating viscosity and restoring its fluidity. The fluid coating can wet the concrete interface and fill capillary pores, forming a physically anchored structure after the concrete has cured.

[0012] Self-healing and water-blocking properties: The gel coating exhibits creep characteristics. When the roll material is damaged and pores are formed, the gel material flows towards the center of the pores, and physical sealing is achieved through the recombination of borate ester bonds. At the same time, the dense gel layer forms a water-blocking barrier at the interface, preventing the lateral flow of water between the roll material and the substrate.

[0013] Water resistance during service life: The hydrophilic modified isocyanate curing agent included in the system functions after the roll material is laid. The isocyanate groups react with the remaining hydroxyl groups on the polyvinyl alcohol segments, the emulsion functional groups, and ambient moisture to form a chemical cross-linking network. This chemical network further stabilizes the physical gel structure, improves the cohesive strength of the coating, and prevents the gel layer from dissociating under long-term water immersion.

[0014] Preferably, the waterproof coating base slurry is made from raw materials comprising the following parts by weight: 45-55 parts polymer emulsion; 28-32 parts inorganic filler; 18-22 parts polyvinyl alcohol solution; 1.2-2.0 parts hydrophilic modified isocyanate curing agent; and 0.5-0.7 parts dispersant and defoamer.

[0015] By adopting the above technical solution, the formulation balances the film-forming properties of the emulsion, the gel strength of PVA, and the skeletal support of the inorganic filler, giving the roll material both flexibility and puncture resistance.

[0016] Preferably, the solid content of the polyvinyl alcohol solution is 10% to 15%, and the solvent is water; the concentration of the boron-containing compound in the crosslinking initiator solution is 1.5% to 4.5%; the boron-containing compound is selected from one or more of sodium tetraborate, sodium metaborate, or potassium borate.

[0017] By employing the above technical solution, the solid content and borate concentration of the PVA solution are limited to control the reaction rate. Too low a concentration will result in insufficient gel network strength, making it unable to resist gravitational sagging; too high a concentration will lead to excessively rapid gelation, affecting the interfacial wetting effect.

[0018] Preferably, the substrate is a polyester filament substrate, a glass fiber reinforced polyester felt, or a high-strength polypropylene nonwoven fabric, with a unit area mass of 120-200 g / m²; the amount of the gel-state waterproof coating adhering to the substrate is 1.5-2.5 kg / m², based on wet weight.

[0019] By adopting the above technical solutions, the matrix provides mechanical strength and dimensional stability; the limited coating adhesion ensures that there is sufficient gel material for interface wetting and defect filling.

[0020] Secondly, the present invention provides a waterproof coating roll material prepared by the following method:

[0021] A method for preparing a waterproof coating roll material includes the following steps:

[0022] (1) Introduce the tire body into the production line and set the tension;

[0023] (2) The substrate is introduced into an impregnation device containing waterproof coating base slurry for impregnation and extrusion, and the amount of coating adhering to the substrate is controlled.

[0024] (3) Before the impregnated carcass is rolled up, a crosslinking initiator solution is applied to the coating surface to initiate an in-situ gelation reaction;

[0025] (4) After the coating changes from liquid to gel, cover, cut and seal the packaging.

[0026] By adopting the above technical solution, this method solves the problem of difficult coating and processing of high-viscosity gels. The specific process principle and effects are as follows:

[0027] Separation of processing and molding: This method separates the coating process from the gelation process. The waterproof coating base slurry remains in a low-viscosity liquid state in the impregnation tank, which facilitates penetration into the substrate and surface leveling, ensuring production line operating speed and coating uniformity.

[0028] In-situ rapid gelation: Utilizing the diffusion effect of borate ions in the wet coating, an initiator solution is applied to the surface to induce a phase transition in the coating within seconds, changing it from a liquid state to a gel state with yield strength.

[0029] Continuous online production: The rapid phase change characteristics enable the coating to withstand the pressure of the coating rollers without dripping. This process enables continuous production from liquid coatings to solid roll-to-roll materials, eliminating the traditional drying tunnel process and reducing energy consumption.

[0030] Preferably, in step (2), the temperature of the waterproof coating base slurry in the impregnation device is controlled at 20-35℃; the production line running speed is 8-15m / min; the extrusion pressure is 0.2-0.5MPa; in step (3), the crosslinking initiator solution is applied by high-pressure atomization spraying or micro-roll coating.

[0031] By adopting the above technical solutions, temperature control ensures the rheological stability of the base slurry; spraying or micro-roll coating methods ensure that the initiator solution is evenly distributed and quickly penetrates inward, forming a gel structure with uniform thickness.

[0032] Preferably, in step (1), the tension is set to 50-100N; in step (4), the gel transition time is controlled within 2-5 seconds; and the packaging material is a PE bag or an aluminum-plastic composite bag with light-shielding properties.

[0033] By adopting the above technical solutions, tension control prevents tire deformation; controlling the gel transition time to match the linear velocity ensures the coating has structural strength before lamination; and light-proof packaging prevents side reactions caused by light exposure, ensuring product shelf life.

[0034] This invention provides a waterproof coating roll material. It has the following beneficial effects:

[0035] 1. This invention involves applying a boron-containing initiator in situ after impregnation with a liquid slurry. Utilizing the rapid complexation reaction between borate and polyvinyl alcohol, the coating transforms from a liquid state to a gel state with yield strength within 2 to 5 seconds. This in-situ gelation process eliminates the heating, drying, or solvent evaporation steps required in traditional coating preparation of roll materials, significantly reducing energy consumption and increasing production line speed. Simultaneously, the resulting physical gel network imparts morphological stability to the product at room temperature, ensuring that the roll material does not deform or stick during packaging, transportation, and storage.

[0036] 2. The gel coating of this invention exhibits significant thixotropic properties. During construction, the shear forces generated by concrete pouring and vibration disrupt the physical cross-linking nodes, reducing the coating viscosity and restoring its fluidity, thereby fully wetting the concrete surface and filling capillary pores. As the shearing ceases, the physical bonds recombine, restoring the gel state and forming a seamless microscopic interlock between the membrane and the concrete. This physical anchoring structure eliminates interfacial gaps, effectively blocking the lateral migration path of moisture between the waterproofing layer and the structural layer.

[0037] 3. The gel coating of this invention utilizes the creep migration ability and dynamic bond exchange mechanism of polymer chain segments to automatically fill pores after being punctured, maintaining the integrity of the waterproof layer. Simultaneously, the hydrophilic modified isocyanate curing agent introduced into the system undergoes a chemical cross-linking reaction with polyvinyl alcohol and emulsion in the later stages of application, constructing an irreversible chemical network. This dual mechanism of early physical gelation and later chemical curing ensures self-healing during the construction phase and improves the cohesive strength of the coating under long-term immersion conditions, preventing the material from absorbing water, swelling, or decomposing. Attached Figure Description

[0038] Figure 1 This is a flowchart of the present invention. Detailed Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] Please see the appendix Figure 1 This invention provides a waterproof coating roll material. The main raw materials and reagents used in the following examples and comparative examples are as follows. Reagents not specifically mentioned are all commercially available analytical grade or higher grade products.

[0041] Styrene-acrylate copolymer emulsion, industrial grade, solid content 50±1%, glass transition temperature -10℃ to -5℃, Brookfield viscosity (25℃) 500~2000mPa·s, pH value 7.0~9.0, commercially available.

[0042] Polyvinyl alcohol type 17-88, CAS number 9002-89-5, degree of alcoholysis 87.0%~89.0% (mol / mol), average degree of polymerization 1700±50, viscosity of 4% aqueous solution (20℃) 20.0~26.0 mPa·s.

[0043] Polyvinyl alcohol type 24-88, CAS number 9002-89-5, degree of alcoholysis 87.0%~89.0% (mol / mol), average degree of polymerization 2400±50, viscosity of 4% aqueous solution (20℃) 44.0~52.0 mPa·s.

[0044] Sodium tetraborate decahydrate, CAS No. 1303-96-4, analytical grade, main content ≥99.5%.

[0045] The hydrophilic modified polyisocyanate curing agent, whose main component is hydrophilic modified hexamethylene diisocyanate trimer, has the CAS number 28182-81-2. It is solvent-free, with an NCO group content of 17.0% to 19.0%, and is water-dispersible.

[0046] Heavy calcium carbonate, CAS No. 471-34-1, industrial grade, fineness 800 mesh, calcium carbonate content ≥98%.

[0047] Sodium polycarboxylate dispersant, CAS No. 9003-04-7, industrial grade, solid content 40±1%.

[0048] Mineral oil defoamer, industrial grade, the main components are a mixture of mineral oil and hydrophobic particles, with a non-volatile content of ≥98%.

[0049] Polyester filament base fabric, industrial grade, with a unit area mass of 180g / m², conforming to the requirements of GB / T18840-2002 standard.

[0050] Glass fiber reinforced polyester felt, industrial grade, with a unit area weight of 120g / m², suitable for waterproof coating reinforcement layers.

[0051] Preparation Example 1:

[0052] This preparation example provides a rheology control modifier solution (B1 solution), including the following steps:

[0053] Add 88 parts of deionized water to a reactor equipped with a heating jacket and a mechanical stirrer, start stirring, set the speed to 400 rpm, slowly add 12 parts of polyvinyl alcohol type 17-88 powder, heat to 90°C, keep warm and stir continuously for 2.5 hours until the solid particles are completely dissolved, and cool naturally to below 40°C to obtain a rheology control modifier solution B1 with a solid content of 12%.

[0054] Preparation Example 2:

[0055] This preparation example provides a rheology control modifier solution (B2 solution), including the following steps:

[0056] Add 90 parts of deionized water to a reactor equipped with a heating jacket and a mechanical stirrer, start stirring, set the speed to 400 rpm, slowly add 10 parts of polyvinyl alcohol 17-88 powder, heat to 90°C, keep warm and stir continuously for 2 hours until the solid particles are completely dissolved, and cool naturally to below 40°C to obtain rheology control modifier solution B2 with a solid content of 10%.

[0057] Preparation Example 3:

[0058] This preparation example provides a rheology control modifier solution (B3 solution), including the following steps:

[0059] Add 85 parts of deionized water to a reactor equipped with a heating jacket and a mechanical stirrer, start stirring, set the speed to 500 rpm, slowly add 15 parts of polyvinyl alcohol 24-88 powder, heat to 95°C, keep warm and stir continuously for 3.5 hours until the solid particles are completely dissolved, and cool naturally to below 40°C to obtain a rheology control modifier solution B3 with a solid content of 15%.

[0060] Preparation Example 4:

[0061] This preparation example provides a crosslinking initiator solution (C1 solution), including the following steps:

[0062] At room temperature, 1.5 parts of sodium tetraborate decahydrate were added to 98.5 parts of deionized water and mechanically stirred for 10 minutes until the solid was completely dissolved, thus obtaining a 1.5% crosslinking initiator solution C1.

[0063] Preparation Example 5:

[0064] This preparation example provides a crosslinking initiator solution (C2 solution), including the following steps:

[0065] At room temperature, 3.0 parts of sodium tetraborate decahydrate were added to 97.0 parts of deionized water and mechanically stirred for 15 minutes until the solid was completely dissolved, to obtain a 3.0% crosslinking initiator solution C2.

[0066] Preparation Example 6:

[0067] This preparation example provides a crosslinking initiator solution (C3 solution), including the following steps:

[0068] At room temperature, 4.5 parts of sodium tetraborate decahydrate were added to 95.5 parts of deionized water and mechanically stirred for 20 minutes until the solid was completely dissolved, thus obtaining a 4.5% crosslinking initiator solution C3.

[0069] Preparation Example 7:

[0070] This preparation example provides a waterproof coating base slurry (A1 slurry), which is a standard balanced formulation, including the following steps:

[0071] In a high-speed dispersion vessel, 48 parts of styrene-acrylate copolymer emulsion, 0.3 parts of sodium polycarboxylate dispersant, and 0.2 parts of mineral oil defoamer were added sequentially, and the mixture was stirred at a low speed of 400 rpm for 5 minutes. Then, 30 parts of heavy calcium carbonate were slowly added, and the speed was adjusted to 1200 rpm for 25 minutes. The fineness was measured to be less than 50 micrometers. The speed was reduced to 500 rpm, and 20 parts of the rheology control modifier solution B1 prepared in Preparation Example 1 were added. After stirring evenly, 1.5 parts of hydrophilic modified polyisocyanate curing agent were added, and stirring was continued for 10 minutes to obtain the waterproof coating base slurry A1.

[0072] Preparation Example 8:

[0073] This preparation example provides a waterproof coating base slurry (A2 slurry), which is a highly flexible, high-emulsion formulation, including the following steps:

[0074] In a high-speed dispersion vessel, 58 parts of styrene-acrylate copolymer emulsion, 0.4 parts of sodium polycarboxylate dispersant, and 0.2 parts of mineral oil defoamer were added sequentially, and the mixture was stirred at a low speed of 400 rpm for 5 minutes. Then, 24 parts of heavy calcium carbonate were slowly added, and the speed was adjusted to 1200 rpm for 20 minutes. The fineness was measured to be less than 50 micrometers. The speed was reduced to 500 rpm, and 15 parts of the rheology control modifier solution B2 prepared in Preparation Example 2 were added. After stirring evenly, 2.5 parts of hydrophilic modified polyisocyanate curing agent were added, and stirring was continued for 10 minutes to obtain waterproof coating base slurry A2.

[0075] Preparation Example 9:

[0076] This preparation example provides a waterproof coating base slurry (A3 slurry), which is a high-thixotropic and high-strength formulation, including the following steps:

[0077] In a high-speed dispersion vessel, 40 parts of styrene-acrylate copolymer emulsion, 0.2 parts of sodium polycarboxylate dispersant, and 0.2 parts of mineral oil defoamer were added sequentially, and the mixture was stirred at a low speed of 400 rpm for 5 minutes. Then, 34 parts of heavy calcium carbonate were slowly added, and the speed was adjusted to 1200 rpm for 30 minutes. The fineness was measured to be less than 50 micrometers. The speed was reduced to 500 rpm, and 25 parts of the rheology control modifier solution B3 prepared in Preparation Example 3 were added. After stirring evenly, 1.0 part of hydrophilic modified polyisocyanate curing agent was added, and stirring was continued for 10 minutes to obtain waterproof coating base slurry A3.

[0078] Example 1:

[0079] This embodiment provides a waterproof coating roll material, which is a standard product with balanced comprehensive performance, including the following steps:

[0080] (1) Pretreatment of the tire body: The polyester filament tire base fabric with a unit area mass of 180g / m² is loaded onto the unwinding frame, and the tension is set to 80N by the tension controller before being introduced into the production line.

[0081] (2) Multi-stage extrusion impregnation: The substrate is introduced into an impregnation mother tank containing the waterproof coating base slurry A1 prepared in Preparation Example 7. The temperature of the mother tank is controlled at 25°C. The substrate is repeatedly impregnated and extruded by three rollers. The extrusion pressure is set to 0.3 MPa and the production line speed is 10 m / min. The final coating adhesion amount (wet weight) on the substrate is controlled to be 2.0 kg / m².

[0082] (3) In-situ thixotropic initiation: Before the impregnated carcass leaves the last extrusion wheel and is rolled up, the crosslinking initiator solution C2 (concentration 3.0%) prepared in Example 5 is uniformly sprayed onto the upper and lower surfaces of the coating through a high-pressure atomizing nozzle; the total amount of C2 solution sprayed is controlled to be 2.0% of the weight of A1 slurry.

[0083] (4) Gel formation and encapsulation: Within about 3 seconds after spraying, the coating surface was observed to change from a flowing liquid state to a non-flowing gel state; then, PE release film was covered on the upper and lower surfaces of the roll, and after being leveled by a soft rubber roller with a pressure of 0.1MPa, it was cut into 10-meter / roll specifications and immediately packed into a black PE light-blocking bag and vacuum-sealed.

[0084] Example 2:

[0085] This embodiment provides a waterproof coating roll material, which is a low-coating-weight, highly flexible product, including the following steps:

[0086] (1) Pretreatment of the tire body: The polyester filament tire base fabric with a unit area mass of 180g / m² is loaded onto the unwinding frame, the tension is set to 60N, and it is introduced into the production line.

[0087] (2) Multi-stage extrusion impregnation: The substrate is introduced into an impregnation mother tank containing the waterproof coating base slurry A2 (high emulsion content) prepared in Example 8. The temperature of the mother tank is controlled at 20°C. The substrate is impregnated by two roller extrusion wheels. The extrusion pressure is set to 0.2 MPa and the production line running speed is 8 m / min. The final coating adhesion amount (wet weight) on the substrate is controlled to be 1.5 kg / m².

[0088] (3) In-situ thixotropic initiation: After the impregnated carcass leaves the last extrusion roller, the crosslinking initiator solution C1 (concentration 1.5%) prepared in Preparation Example 4 is applied to the coating surface by a micro-roll coating device; the total amount of C1 solution applied is controlled to be 1.0% of the weight of A2 slurry.

[0089] (4) Gelification and encapsulation: The gelation transformation is completed within about 5 seconds after the initiator is applied; cover with PET release film, smooth with rubber rollers, cut and double-layer light-proof sealed packaging.

[0090] Example 3:

[0091] This embodiment provides a waterproof coating roll material, which is a high-coverage, high-strength, heavy-duty product, including the following steps:

[0092] (1) Pretreatment of the tire body: A glass fiber reinforced polyester felt with a unit area mass of 120g / m² is loaded onto the unwinding rack, the tension is set to 50N, and it is introduced into the production line.

[0093] (2) Multi-stage extrusion impregnation: The substrate is introduced into an impregnation mother tank containing waterproof coating base slurry A3 (high PVA content) prepared in Preparation Example 9. The temperature of the mother tank is controlled at 30°C. The substrate is impregnated by four roller extrusion wheels. The extrusion pressure is set to 0.5 MPa and the production line speed is 12 m / min. The final coating adhesion amount (wet weight) on the substrate is controlled to be 2.5 kg / m².

[0094] (3) In-situ thixotropic initiation: After the impregnated carcass leaves the last extrusion wheel, the crosslinking initiator solution C3 (concentration 4.5%) prepared in Example 6 is sprayed onto the upper and lower surfaces of the coating through a multi-head atomizing nozzle; the total amount of C3 solution sprayed is controlled to be 3.0% of the weight of A3 slurry.

[0095] (4) Gel formation and encapsulation: The coating rapidly gels within about 2 seconds after spraying, presenting a highly viscous, euplastic solid state; cover with PE release film, flatten, cut and double-layer light-proof sealed packaging.

[0096] Example 4:

[0097] This embodiment provides a waterproof coating roll material, designed to verify the process stability under high production speeds, including the following steps:

[0098] (1) Pretreatment of the tire body: The polyester filament tire base fabric with a unit area mass of 180g / m² is loaded onto the unwinding frame and the tension is set to 100N.

[0099] (2) Multi-stage extrusion impregnation: The waterproof coating base slurry A1 prepared in Preparation Example 7 was selected, the mother tank temperature was 35℃; the number of extrusion rollers was increased to five, the extrusion pressure was 0.4MPa, and the production line speed was increased to 15m / min; the coating adhesion amount (wet weight) was controlled to be 2.2kg / m².

[0100] (3) In-situ thixotropic initiation: The high-concentration crosslinking initiator solution C3 (concentration 4.5%) prepared in Preparation Example 6 was applied by spraying, and the amount applied was 1.5% of the weight of the A1 slurry (the initiator concentration was increased to compensate for the insufficient reaction time under high linear velocity).

[0101] (4) Gel formation and encapsulation: The coating gels instantly during rapid movement, and the subsequent coating, cutting and packaging steps are the same as in Example 1.

[0102] Example 5:

[0103] This embodiment provides a waterproof coating roll material and verifies the effect of different initiator ratios on the intermediate state, including the following steps:

[0104] (1) Pretreatment of fetus: Same as in Example 1.

[0105] (2) Multi-stage extrusion impregnation: The waterproof coating base slurry A2 prepared in Example 8 was selected, and the process parameters were the same as in Example 1. The coating adhesion amount (wet weight) was controlled to be 1.8 kg / m².

[0106] (3) In-situ thixotropic initiation: The crosslinking initiator solution C2 (concentration 3.0%) prepared in Preparation Example 5 was selected and the amount applied was adjusted to 2.5% of the weight of A2 slurry.

[0107] (4) Gel formation and encapsulation: The subsequent steps are the same as in Example 1.

[0108] Comparative Example 1:

[0109] Compared with Example 1, the difference is that the "in-situ thixotropic initiation" operation in step (3) is omitted, that is, the crosslinking initiator solution C2 is not sprayed on the coating surface, and the coating is directly coated and packaged while keeping the original state after impregnation. The other raw materials and preparation processes are the same.

[0110] Comparative Example 2:

[0111] Compared with Example 1, the difference is that: when preparing the waterproof coating base slurry (A1 slurry), an equal weight of deionized water is used to replace the rheology control modifier solution (B1 liquid), and the crosslinking initiator solution C2 sprayed in step (3) is replaced with an equal weight of deionized water, that is, the system does not contain polyvinyl alcohol and borax components, and the other raw materials and preparation processes are the same.

[0112] Comparative Example 3:

[0113] Compared with Example 1, the difference is that the mixing order of raw materials is changed. Before impregnation in step (2), the crosslinking initiator solution C2 is directly added to the waterproof coating base slurry A1 in the impregnation mother pool for mixing, in an attempt to prepare a mixed slurry for direct impregnation. The other raw materials and process parameters are the same.

[0114] Comparative Example 4:

[0115] Compared with Example 1, the difference is that after impregnation in step (2), the roll material is heated and dried in a 120°C oven for 5 minutes to allow the moisture in the coating to evaporate and undergo a chemical cross-linking reaction. After the coating is completely dried and cured into a solid sheet, it is then coated and packaged. Thus, the resulting material is a dry prefabricated roll material rather than a gel-state roll material. All other raw materials and preparation processes are the same.

[0116] Test Example 1: Process Feasibility and Rheological Properties Test

[0117] This test case primarily verifies the phase change response rate of the waterproof coating roll during its preparation process and the rheological behavior of the finished product under different shear conditions. An AntonPaar MCR302 rotational rheometer was used, equipped with a PP25 parallel plate rotor system. The test spacing was set to 1.0 mm, and the test temperature was controlled at 25℃. Test samples were taken from the middle section of the production line of Examples 1 to 5 and Comparative Examples 1 to 3, i.e., the wet coating layer after initiator spraying or mixing; Comparative Example 4 was a cured sheet, which was not suitable for fluid rheology testing.

[0118] The experiment first determined the gelation time of the system. Simulating the production line mixing ratio, the A slurry and C liquid components were instantaneously mixed and timed, observing the time required for the mixture to transition from a liquid state to a non-flowing state at a 45-degree angle. Subsequently, steady-state flow curve tests were performed, eliminating sample loading history, and the gelation time was measured within 0.1 s. -1 up to 100s -1 The scan was performed within the range of shear rates, and records were taken at 0.1 s. -1 (Simulated static storage) and 100s -1 The apparent viscosity under simulated construction pressure was measured. Finally, a three-stage shear thixotropic (3ITT) test was performed, with the program set as follows: first stage 0.1s. -1 Cutting time 60 seconds, second stage 100 seconds-1 Shearing for 30 seconds, third stage for 0.1 seconds. -1 After shearing for 60 seconds, the viscosity recovery rate was determined by calculating the ratio of the viscosity at the end of the third stage to the viscosity at the end of the first stage.

[0119] The relevant rheological parameters and gelation time test data are detailed in Table 1.

[0120] Table 1 Summary of rheological properties and gelation time test data for each embodiment and comparative example.

[0121] Group gelation time (s) low shear viscosity High shear viscosity Shear thinning index Viscosity recovery rate (%) after 30 seconds Example 1 3.2 68,425 4.3 15,912 96.4 Example 2 5.5 45,180 3.9 11,584 93.8 Example 3 1.9 89,950 6.8 13,227 97.9 Example 4 2.6 72,050 4.7 15,329 95.5 Example 5 3.9 61,240 4.1 14,936 94.1 Comparative Example 1 >1800 8.6 6.3 1.36 99.8 Comparative Example 2 >1800 7.8 5.9 1.32 99.9 Comparative Example 3 <0.8 N / A (Reunion) N / A ～ ～ Comparative Example 4 ～ solid solid ～ ～

[0122] Based on the rheological test data and experimental phenomena in Table 1, the mechanism and effects of the technical solution of this invention are analyzed as follows:

[0123] Data from Examples 1 to 5 show that by introducing polyvinyl alcohol and borate into the styrene-acrylic / pure acrylic emulsion system, an effective dynamic physical crosslinking network was established. This network was effective at low shear rates (0.1 s⁻¹). -1 Under these conditions, the viscosity range of the example samples was maintained at 4.5 × 10⁻⁶. 4 Pa·s up to 9.0 × 10 4 The viscosity ranges from Pa·s. This high viscosity indicates that boron ions form high-density complex nodes with the hydroxyl groups on the polyvinyl alcohol molecular chain, transforming the liquid emulsion into a gel structure with solid-like properties. This structure endows the roll material with extremely high yield stress in a static state, enabling it to resist gravity and thus ensuring that the internal coating layer does not settle, flow cold, or overflow from the edges of the roll material during long-term vertical storage or transportation.

[0124] At high shear rates (100 s⁻¹) -1 Under these conditions, the viscosity of the example samples dropped sharply to single digits (3.9–6.8 Pa·s), and the shear thinning index reached 10. 4 The magnitude is significant. This indicates that boronic acid ester bonds are typical weak interactions, sensitive to shear stress. When external force is applied, the physical cross-linked network rapidly disintegrates, the gel system transforms into a sol state, releasing the water and emulsion particles bound by the network. This characteristic corresponds to the construction process, where the gel layer on the surface of the roll material liquefies under the pressure of a scraper or roller, restoring wettability and allowing it to penetrate into the capillary pores of the concrete substrate.

[0125] The 3ITT test results showed that after the high shear force was removed, the viscosity recovery rate of the sample samples exceeded 93%, and the recovery process was completed within seconds. This confirms the rapid and reversible nature of the breakage and recombination of borate ester bonds. Once the external construction force disappeared, the physical network was rapidly rebuilt, allowing the coating layer to return to a high-viscosity gel state, effectively preventing sagging during vertical surface construction.

[0126] In contrast, Comparative Examples 1 and 2, lacking borax initiator or PVA rheology control agent, failed to construct a physical cross-linked network, exhibiting a low shear viscosity of only about 8 Pa·s, displaying liquid behavior close to that of a Newtonian fluid. If such materials are made into prepreg rolls, they cannot maintain a fixed physical morphology, inevitably leading to storage flow failure. Comparative Example 3 attempted to premix the initiator directly into the impregnation tank, resulting in a gelation time of less than 1 second, with the material instantly agglomerating and clumping within the tank, confirming the necessity of the "impregnation first, then surface in-situ initiation" process route of this invention for achieving continuous production. Comparative Example 4 was a fully cured dry sheet; although morphologically stable, it lost its rheological response capability and could not achieve the liquefaction and full adhesion effect described in this invention.

[0127] In summary, this invention utilizes the shear-sensitive properties of boron-PVA complexes and employs an in-situ gelation process to resolve the contradiction between "morphological stability during storage" and "interfacial wettability during construction" in precast liquid coating rolls.

[0128] Test Example 2: Thermal Stability and Adhesion Performance Test

[0129] This test primarily examines the dimensional stability of waterproof membranes under high-temperature storage conditions, as well as their peel strength and water resistance under wet-lay application. The test subjects were the finished membranes from Examples 1 to 5 and Comparative Examples 1, 2, and 4; Comparative Example 3 was not suitable for testing because it could not be formed into a uniform membrane.

[0130] The experiment consisted of two parts: heat resistance testing and peel strength testing. In the heat resistance (anti-sagging) test, each group of rolls was cut into 100mm×100mm pieces. After removing the surface release film, they were vertically suspended in a 70℃ electric heating drying oven and kept at a constant temperature for 48 hours. The vertical slippage distance of the lower end of the coating layer relative to the substrate was measured. If the coating layer peeled off entirely or flowed beyond the length of the specimen, it was considered a failure. The peel strength test was conducted according to GB / T23457-2017 "Pre-laid Waterproof Membranes" standard, using the wet-laying method: the roll was laid flat with the adhesive side facing up. After removing the release film, C30 ordinary silicate cement mortar was directly poured onto its gel surface. After vibration and air removal, it was cured for 7 days according to standard. The test was divided into two groups: Group A was tested directly for 180-degree peel strength after standard curing; Group B was tested for 180-degree peel strength after 7 days of standard curing, with the specimens immersed in 23°C water for 168 hours, the surface dried, and the strength retention rate calculated. The maximum peel force value and failure mode (cohesive failure of the coating layer or interfacial failure) were recorded.

[0131] The relevant physical performance test data are shown in Table 2.

[0132] Table 2 Summary of heat resistance and peel strength test data for each embodiment and comparative example

[0133] Group Slip distance (mm) at 70℃ for 48 hours Status Description Peel strength under standard conditions (N / mm) Failure mode (standard conditions) Peel strength after immersion in water (N / mm) Strength retention rate (%) Example 1 0.6 Slightly sticky surface, no dripping 1.85 Cohesive failure of coating layer 1.69 91.4 Example 2 0 Slightly sticky surface, no dripping 1.56 Cohesive failure of coating layer 1.43 91.7 Example 3 0 Surface dry, shape fixed 2.18 Cohesive failure of coating layer 2.08 95.4 Example 4 0.9 Slightly sticky and slightly deformed surface 1.74 Cohesive failure of coating layer 1.58 90.8 Example 5 0.4 Slightly sticky surface, no dripping 1.95 Cohesive failure of coating layer 1.76 90.3 Comparative Example 1 >100 Flowing and falling off 0.24 Interface destruction ～ ～ Comparative Example 2 >100 Flowing and falling off 0.27 Interface destruction ～ ～ Comparative Example 4 0 The surface is dry and stiff. 0.46 Interface destruction 0.42 91.3

[0134] Based on the physical performance data and failure phenomena in Table 2, the mechanism analysis of the technical solution is as follows:

[0135] Regarding heat resistance stability, Examples 1 to 5 were suspended at 70°C for 48 hours, and the slippage distance was controlled within 1.0 mm. This result indicates that the physical cross-linking network formed by borate and polyvinyl alcohol in the system maintains sufficient structural strength at high temperatures. Under static vertical suspension conditions, the yield stress generated by this network structure can overcome the gravity of the coating itself, limiting the macroscopic movement of polymer chain segments. In contrast, Comparative Examples 1 and 2, lacking effective physical cross-linking nodes, exhibited a viscous flow state in their coating layers, resulting in significant flow under gravity, demonstrating that physical gelation is a necessary condition for achieving pre-forming of liquid coatings.

[0136] Regarding adhesion performance, the peel strength of all examples exceeded 1.5 N / mm, and the failure mode was cohesive failure of the coating layer, meaning the strength of the bonding interface was higher than the strength of the coating itself. The mechanism lies in the thixotropic properties of the physical gel: when cement mortar is poured, the weight of the mortar and the shear force generated by vibration disrupt the gel structure on the surface of the roll material, causing localized liquefaction of the coating. The liquefied coating wets the cement mortar interface and penetrates into the capillary pores. As the shear force disappears and moisture diffuses, the physical network reorganizes, achieving physical anchoring at the microscopic level. Comparative Example 4, a fully cured dry sheet, lost its rheological response capability and could not effectively wet the wet concrete interface, resulting in low interfacial adhesion.

[0137] Regarding water resistance, the strength retention rate of the example groups was over 90% after immersion in water for 168 hours. This indicates that the pre-added hydrophilic modified isocyanate curing agent in the system played a role during the curing period. The isocyanate groups underwent a chemical cross-linking reaction with the hydroxyl groups on the polyvinyl alcohol molecular chain and the functional groups on the surface of the emulsion particles, forming an irreversible cross-linked network, while simultaneously consuming the hydrophilic groups in the system. This late-stage chemical cross-linking locked the physical structure and improved the stability of the material under long-term immersion conditions.

[0138] Test Example 3: Puncture Resistance, Self-Healing Properties, and Water Transit Prevention Test

[0139] This test primarily verifies the self-healing ability of waterproof membranes after being damaged by external forces and their performance in preventing water seepage between layers. Finished membranes from Examples 1 to 5 and Comparative Example 4 were selected as the test subjects; Comparative Examples 1 and 2 could not be molded and therefore did not meet the conditions for water pressure resistance testing. The experiment consisted of two parts: a puncture resistance self-healing test and a water seepage prevention performance test.

[0140] First, a puncture resistance and self-healing test was conducted: the membrane sample was fixed to the bottom of a dedicated test container, with the coating layer facing upwards. A 2mm diameter nail was used to vertically penetrate the center of the membrane, and then the nail was removed. The membrane was left to stand at room temperature for 20 minutes to allow the gel layer to recover through creep. Then, a water pressure of 0.2MPa was applied above the membrane and maintained for 2 hours. The back of the membrane was observed for water seepage. Next, a water-resistant performance test was conducted: a 5mm diameter through-hole was pre-drilled on the surface of a C30 concrete specimen. A membrane with pre-drilled 10mm diameter holes was wet-laid on the concrete surface, ensuring that the membrane holes and the concrete through-holes were misaligned and overlapped to simulate construction damage points. After 7 days of curing, 0.2MPa pressurized water was introduced through the through-holes on the back of the concrete and maintained for 24 hours. After the test, the bonding interface was dissected, and the diffusion distance of water between the membrane and concrete interface (water-seepage radius) was measured and observed under a microscope.

[0141] The relevant test data are shown in Table 3.

[0142] Table 3 Summary of self-healing and water-blocking performance test data for each embodiment and comparative example

[0143] Group Impermeability after nail removal (0.2MPa, 2h) Phenomenon description Water leakage radius at the interface (mm) Assessment Results Example 1 Waterproof Perforation hole gel backfill sealing 0 No water seepage Example 2 Waterproof Perforation hole gel backfill sealing 0 No water seepage Example 3 Micro-osmosis The puncture site closed slowly. 3.5 Micro-channel water Example 4 Waterproof Perforation hole gel backfill sealing 0 No water seepage Example 5 Waterproof Perforation hole gel backfill sealing 0 No water seepage Comparative Example 4 Severe water spray The puncture site cannot be closed >50 (Water seepage across the entire interface) Severe water leakage

[0144] Conclusions and Mechanism Analysis

[0145] Based on the test results in Table 3, the self-healing and water-blocking mechanisms of the material are analyzed as follows:

[0146] Regarding the puncture resistance and self-healing properties, Examples 1, 2, 4, and 5 all passed a 0.2 MPa water pressure test after the nail was removed and the system was left to stand. This result is attributed to the dynamic equilibrium characteristics of the physical cross-linked network in the system. The borate ester bonds are in a state of continuous breakage and recombination at the microscopic level (bond exchange mechanism), which endows the material with significant creep resistance. When the material is punctured and a hole is formed, the gel around the hole flows towards the center under the drive of internal stress, and the polymer chain segments re-entangle and cross-link across the damaged interface, achieving physical closure. A small amount of water seepage occurred in Example 3 because its high PVA content and high cross-linking density increased the rigidity modulus of the network, limiting the creep migration rate of the chain segments, resulting in the inability to completely fill the hole within the specified time.

[0147] Regarding the anti-water-crossing performance, the water-crossing radius of the example group was almost zero. This is because the gel layer formed a seamless micro-scale bond with the concrete substrate during the wet-laying and curing process. When high-pressure water attempted to enter the interface through the damaged points, the high-viscosity gel layer further compressed the concrete capillaries under water pressure, and the gel structure, being insoluble in water, effectively blocked the lateral migration channels of water. In contrast, Comparative Example 4 was a dry sheet material with frozen molecular chain segments, lacking self-healing ability, and the puncture holes formed permanent channels; at the same time, it only had limited physical contact with the substrate, and micro-voids existed at the interface, causing water to diffuse rapidly along the voids, resulting in large-area water-crossing failure.

Claims

1. A waterproof coating roll material, characterized in that, Includes the tire carcass and a gel-like waterproof coating impregnated and attached to the tire carcass; The gel-state waterproof coating is made by contacting a waterproof coating base slurry with a crosslinking initiator solution and undergoing an in-situ physical crosslinking reaction. The amount of the crosslinking initiator solution is 1.0 to 3.0 parts by weight relative to 100 parts by weight of the waterproof coating base slurry. The waterproof coating base slurry is made from raw materials comprising the following parts by weight: 40-60 parts of polymer emulsion; 24-34 parts of inorganic filler; 15-25 parts of polyvinyl alcohol solution; 1.0–2.5 parts of hydrophilic modified isocyanate curing agent; Dispersant and defoamer: 0.4–0.8 parts; The crosslinking initiator solution is an aqueous solution of a boron-containing compound.

2. The waterproof coating roll material according to claim 1, characterized in that, The waterproof coating base slurry is made from raw materials comprising the following parts by weight: 45-55 parts of polymer emulsion; 28-32 parts of inorganic filler; 18-22 parts of polyvinyl alcohol solution; 1.2–2.0 parts of hydrophilic modified isocyanate curing agent; Dispersant and defoamer: 0.5-0.7 parts.

3. The waterproof coating roll according to claim 1, characterized in that, The polymer emulsion is a styrene-acrylate copolymer emulsion or a pure acrylate emulsion; The inorganic filler is one or more of heavy calcium carbonate, talc, or kaolin.

4. The waterproof coating roll material according to claim 1, characterized in that, The solid content of the polyvinyl alcohol solution is 10% to 15%, and its solvent is water; The polyvinyl alcohol solution is prepared by the following steps: adding polyvinyl alcohol powder to deionized water, heating to 90-95°C and stirring to dissolve, and then cooling to below 40°C.

5. The waterproof coating roll according to claim 1, characterized in that, The concentration of boron-containing compounds in the crosslinking initiator solution is 1.5% to 4.5%; The boron-containing compound is selected from one or more of sodium tetraborate, sodium metaborate, or potassium borate.

6. The waterproof coating roll according to claim 1, characterized in that, The substrate is a polyester filament base fabric, glass fiber reinforced polyester felt or high-strength polypropylene nonwoven fabric, with a unit area mass of 120-200 g / m². The amount of the gel-like waterproof coating adhering to the tire body is 1.5 to 2.5 kg / m², based on wet weight.

7. The waterproof coating roll according to claim 1, characterized in that, The roll material also includes a release film covering the upper and lower surfaces of the gel-state waterproof coating, and the roll material is sealed and stored in a light-proof vacuum packaging bag.

8. The waterproof coating roll according to claim 1, characterized in that, Including methods for preparing roll materials: (1) Introduce the tire body into the production line and set the tension; (2) The substrate is introduced into an impregnation device containing waterproof coating base slurry for impregnation and extrusion, and the amount of coating adhering to the substrate is controlled. (3) Before the impregnated carcass is rolled up, a crosslinking initiator solution is applied to the coating surface to initiate an in-situ gelation reaction; (4) After the coating changes from liquid to gel, cover, cut and seal the packaging.

9. A waterproof coating roll according to claim 8, characterized in that, In step (2), the temperature of the waterproof coating base slurry in the impregnation device is controlled at 20-35℃; the production line operating speed is 8-15m / min; and the extrusion pressure is 0.2-0.5MPa. In step (3), the crosslinking initiator solution is applied by high-pressure atomization spraying or micro-roll coating.

10. A waterproof coating roll according to claim 8, characterized in that, In step (1), the tension is set to 50-100N; In step (4), the transition time of the gel state is controlled within 2 to 5 seconds; The packaging material is PE plastic bag with light-blocking properties.

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