High-temperature-resistant and over-sulfurized impregnation solution, preparation method and impregnation method

Abstract

The application discloses a high-temperature-resistant and over-sulfurized impregnation solution, a preparation method and an impregnation method. The impregnation solution comprises a first bath impregnation solution and a second bath impregnation solution, and comprises the following components in parts by weight: the first bath impregnation solution: deionized water 100 parts, water-soluble epoxy resin 0.1-9 parts, isocyanate 0.5-50 parts, wetting and penetrating agent 0.5-5 parts, and silane coupling agent 0.5-5 parts; and the second bath impregnation solution: deionized water 100 parts, resorcinol 1-10 parts, formaldehyde 1.5-15 parts, sodium hydroxide 0.05-0.4 parts, latex 60-200 parts, and fumed silica 1-10 parts. Compared with a traditional RFL impregnation system, the method of adding the wetting and penetrating agent and the silane coupling agent in the first bath and adding the fumed silica in the second bath is adopted, the adhesion between the fiber and the rubber matrix is significantly improved, the technical problem that the adhesion is not high when the fiber / rubber composite material is operated under harsh conditions and loss and damage are caused is solved, and the use safety and stability of the fiber / rubber composite material are improved.

Description

Technical Field

[0001] This invention belongs to the field of impregnation liquid technology, specifically relating to a high-temperature resistant and over-vulcanization resistant impregnation liquid, its preparation method, and its impregnation method. Background Technology

[0002] In rubber products, fiber-reinforced reinforcing materials primarily function to bear loads and maintain dimensional stability. Their adhesion to rubber plays a decisive role in the performance and lifespan of the rubber products. Common applications include conveyor belts, tires, and hoses. Commonly used reinforcing materials include metals, cellulose, nylon, and polyester.

[0003] For polyester backbone materials, due to the significant differences in polarity and rigidity between polyester fibers and the rubber matrix, an impregnation process is required to create an impregnated layer and improve the interfacial adhesion between the two phases. Currently, the mainstream impregnation system is RFL (resorcinol-formaldehyde resin), where R is resorcinol, F is formaldehyde, and L is latex. This is a composite impregnation emulsion formed by the condensation of resorcinol and formaldehyde to form a phenolic resin, with the latex encapsulated within. This RFL system primarily bonds to the fibers through the intermolecular forces of RF, and crosslinks with the rubber through the co-vulcanization of the latex and the reaction of residual hydroxymethyl groups in the RF resin with the rubber. For nylon containing a large number of amide bonds, only a small amount of RF is needed to generate a large number of intermolecular forces, such as hydrogen bonds; therefore, single-bath RFL can achieve satisfactory bonding results.

[0004] Chinese patent application No. 201811087793.X discloses a nano-reinforced resorcinol-formaldehyde-latex impregnation system for fiber surface treatment and its preparation method. The impregnation system comprises 100 parts deionized water, 1-15 parts resorcinol, 2-20 parts formaldehyde solution, 0.1-1 parts sodium hydroxide, 1-10 parts ammonia solution, 1-10 parts nanofiller, and 50-200 parts rubber latex. The nanofiller in this invention can be well dispersed in the impregnation solution and has a certain reactivity with it. It can form a nano-reinforced interface structure in the cord impregnation treatment, enhancing the adhesion between the fiber and rubber. This invention argues that under high-speed, high-impact loads, the requirements for fiber-rubber interfacial adhesion strength and dynamic fatigue adhesion performance are higher. The current traditional RFL system can no longer adequately meet the interfacial adhesion performance requirements of tires during high-speed operation. It is mainly aimed at easily bonded nylon 66 cord fabric, while the more commonly used tire system is the cheaper polyester cord fabric system. However, for polyester materials such as polyethylene glycol terephthalate (PET), the lack of groups on their surface that can generate intermolecular forces such as hydrogen bonds makes it difficult to produce satisfactory bonding effects.

[0005] In industrial applications, a two-bath impregnation method is generally used, employing epoxy-isocyanate as the first bath and RFL as the second bath. While this two-bath RFL impregnation significantly improves the adhesion between the fiber cord and the rubber, prolonged high-speed driving can lead to tire temperature fluctuations and adhesion failure, resulting in delamination and bulging. Delamination often occurs at the point of impregnation failure. The reasons for this are twofold: the adhesion between the first-bath impregnation layer and the polyester fibers, and the adhesion between the first and second-bath impregnation layers. Because polyester cords use twisted cords, the first-bath impregnation solution cannot fully penetrate, only reaching the surface 1-2 layers. Under prolonged high temperatures, this thin surface layer is easily damaged, leading to adhesion failure. Furthermore, the insufficient adhesion between the first and second impregnation layers also makes them prone to failure under prolonged high temperatures. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a high-temperature and over-vulcanization resistant impregnation solution, its preparation method, and its impregnation method. By adding a wetting and penetrating agent to the first bath impregnation solution, the solution can penetrate more deeply into the polyester cord. A certain amount of silane coupling agent is also added. Simultaneously, water-based fumed silica is added to the second bath to improve the heat resistance of the second bath adhesive layer. Furthermore, the inorganic silica and silane coupling agent act like rivets to enhance the adhesion and durability between the first and second adhesive layers.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] A high-temperature resistant and over-vulcanization resistant impregnation solution, the impregnation solution comprising a first bath impregnation solution and a second bath impregnation solution, comprising the following components by weight:

[0009] First bath impregnation solution: 100 parts deionized water, 0.1-9 parts water-soluble epoxy resin, 0.5-50 parts isocyanate, 0.5-5 parts wetting and penetrating agent, 0.5-5 parts silane coupling agent MP-200;

[0010] Second bath impregnation solution: 100 parts deionized water, 1-10 parts resorcinol, 1.5-15 parts formaldehyde, 0.05-0.4 parts sodium hydroxide, 60-200 parts latex, and 1-10 parts water-soluble fumed silica WV33.

[0011] Preferably, a high-temperature resistant and over-vulcanization resistant impregnation solution comprises the following components by weight:

[0012] First bath impregnation solution: 100 parts deionized water, 0.5-3 parts water-soluble epoxy resin, 5-30 parts isocyanate, 1-3 parts wetting and penetrating agent, 1-3 parts silane coupling agent MP-200;

[0013] Second bath impregnation solution: 100 parts deionized water, 3-8 parts resorcinol, 4.5-12 parts formaldehyde, 0.1-1.3 parts sodium hydroxide, 80-180 parts latex, and 2-8 parts water-soluble fumed silica WV33.

[0014] Preferably, a high-temperature resistant and over-vulcanization resistant impregnation solution comprises the following components by weight:

[0015] First bath impregnation solution: 100 parts deionized water, 1-2 parts water-soluble epoxy resin, 3-10 parts blocked isocyanate, 1-2 parts wetting and penetrating agent, 1-2 parts silane coupling agent MP-200;

[0016] Second bath impregnation solution: 100 parts deionized water, 4-6 parts resorcinol, 6-9 parts formaldehyde, 0.12-0.2 parts sodium hydroxide, 90-150 parts latex, and 3-6 parts water-soluble fumed silica WV33.

[0017] In this invention, the end-capping agent of the blocked isocyanate preferably includes dimethylpyridine, caprolactam, oxadiazine ring, phenol, butanone oxime, diethylpropylamine or diethylmalonic acid.

[0018] Preferably, the epoxy resin is one or more of EX614B, EX512, JF313, JF512, and G1701.

[0019] Preferably, the latex is one or more of butyl rubber latex, styrene-butadiene latex, natural latex, and PVC latex.

[0020] Preferably, the wetting and penetrating agent is one or more of acetylenic diols, HY-1000 low-foaming wetting and penetrating agent, and BYK wetting and dispersing agent.

[0021] Preferably, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexanediisocyanate.

[0022] This invention also protects a method for preparing the high-temperature resistant and over-vulcanization resistant impregnation solution, comprising the following steps:

[0023] Preparation of the first bath impregnation solution: Add deionized water to the reaction vessel, then add water-soluble epoxy resin, stir for 0.5-1.5 h, then add isocyanate, stir for 10-30 min, then add wetting and penetrating agent and silane coupling agent MP-200, stir for 10-20 min, and the first bath impregnation solution is obtained.

[0024] Preparation of the second bath impregnation solution: Add deionized water to the reaction vessel, then add sodium hydroxide and resorcinol, stir until the solid dissolves, then add formaldehyde, stir at 20-30℃ for 3-4 hours, then add latex to the reaction vessel, stir evenly, let stand, then add fumed silica WV33, stir evenly to obtain the second bath impregnation solution.

[0025] Preferably, the settling temperature is 25-30℃ and the settling time is 20-30h.

[0026] This invention also protects a method for impregnating the high-temperature and vulcanization resistant impregnation solution, wherein the fiber skeleton material is subjected to a first bath impregnation treatment with a first bath impregnation solution, and after the treatment is completed, it is subjected to a second bath impregnation treatment with a second bath impregnation solution.

[0027] The conditions for the first-bath impregnation treatment are: drying temperature 140-170℃, tension 500-2000 daN, stretching temperature 230-250℃, tension 1000-4000 daN, and speed 65-95 m / min; the conditions for the second-bath impregnation treatment are: drying temperature 140-170℃, tension 500-2000 daN, setting temperature 230-250℃, tension 300-1000 daN, and speed 65-95 m / min.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] (1) The high-temperature and over-vulcanization resistant impregnation solution provided by the present invention adds a wetting and penetrating agent to the first bath impregnation solution to allow the latex to enter the cord faster and deeper. At the same time, the addition of a silane coupling agent can form a denser cross-linking point with the epoxy and unsealed isocyanate in the first bath to form a stronger three-dimensional network structure, which can significantly improve the durability of the adhesive force and the water resistance. At the same time, it is combined with the fumed silica in the second bath to strengthen the bonding force with the second bath. The addition of more heat-resistant inorganic fumed silica in the second bath improves the heat resistance of the second bath impregnation layer and reacts with the coupling agent in the first bath to improve the adhesion between the first and second baths. Through the synergistic effect between the first and second baths, the overall adhesion force and heat resistance are ultimately improved. The main advantage is that it maintains high adhesion under sulfur conditions. The most obvious advantage of such high-performance tires is that they have better resistance to heat buildup. Since tires tend to heat up during driving, especially when the sun shines on asphalt roads in summer, prolonged overheating is the main cause of tire failure. These tires using the impregnation formula of this invention will not burst due to overheating, thus making driving safer.

[0030] (2) The high-temperature and over-vulcanization resistant impregnation solution provided by the present invention has good compatibility with traditional impregnation solution preparation and use in terms of equipment and process, which is conducive to the factory to organize production and switch between different categories. Compared with the traditional RFL impregnation system, it significantly improves the bonding performance between the fiber and the rubber matrix, especially under over-vulcanization conditions, and has excellent bonding performance. The excellent performance of the rubber matrix and the skeleton material is not lost, which solves the technical problem of low bonding performance of fiber / rubber composite materials under harsh conditions, resulting in loss and damage, and increases the safety and stability of fiber / rubber composite materials. Detailed Implementation

[0031] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] In this embodiment of the invention, there is no special limitation on the source of the blocked isocyanate. Commercially available blocked isocyanates well known to those skilled in the art can be used, such as caprolactam-terminated isocyanate IL-6 (EMS Chemical Group).

[0033] The present invention does not have any special limitation on the source of the epoxy resin, and commercially available products well known in the art can be used, such as G1701 (EMS Chemical Group), EX614B (NAGASE), or EX512 (NAGASE), etc.

[0034] In this embodiment of the invention, there is no special limitation on the source of the fumed silica. Commercially available fumed silica known to those skilled in the art can be used, such as fumed silica WV33 (Nourion).

[0035] Example 1

[0036] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0037] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 20 min, then add 100 g of acetylacetonate diol surfactant ZY-1104 and 100 g of silane coupling agent MP-200, stir for 15 min, and the first bath impregnation solution is obtained.

[0038] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 3 h, then add 12 kg of butadiene-pyridine (VP) latex to the reaction vessel, stir evenly, let stand at 25 °C for 25 h, then add 300 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0039] Example 2

[0040] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0041] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 0.5 h, then add 300 g of isocyanate IL-6, stir for 10 min, then add 150 g of acetylacetonate diol surfactant ZY-1104 and 150 g of silane coupling agent MP-200, stir for 10 min, and the first bath impregnation solution is obtained.

[0042] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 20 °C for 4 h, then add 12 kg of butadiene-pyridine (VP) latex to the reaction vessel, stir evenly, let stand at 30 °C for 20 h, then add 400 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0043] Example 3

[0044] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0045] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 1.5 h, then add 300 g of isocyanate IL-6, stir for 30 min, then add 200 g of low foaming wetting and penetrating agent HY-1000 and 200 g of silane coupling agent MP-200, stir for 20 min, and the first bath impregnation solution is obtained.

[0046] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 30 °C for 3 h, then add 12 kg of butadiene-pyridine (VP) latex to the reaction vessel, stir evenly, let stand at 25 °C for 30 h, then add 500 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0047] Example 4

[0048] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0049] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 50 g of epoxy resin EX-614B, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 15 min, then add 100 g of wetting and dispersing agent BYK-163 and 100 g of silane coupling agent MP-200, stir for 15 min, and the first bath impregnation solution is obtained.

[0050] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 3 h, then add 12 kg of butadiene-pyridine (VP) latex to the reaction vessel, stir evenly, let stand at 25 °C for 24 h, then add 300 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0051] Example 5

[0052] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0053] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 50 g of epoxy resin EX-614B, stir for 1.5 h, then add 300 g of isocyanate IL-6, stir for 25 min, then add 150 g of acetylacetonate diol surfactant ZY-1104 and 150 g of silane coupling agent MP-200, stir for 15 min, and the first bath impregnation solution is obtained.

[0054] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 4 h, then add 12 kg of butadiene-pyridine (VP) latex to the reaction vessel, stir evenly, let stand at 30 °C for 25 h, then add 400 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0055] Example 6

[0056] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0057] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 50 g of epoxy resin EX-614B, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 25 min, then add 200 g of acetylacetonate diol surfactant ZY-1104 and 200 g of silane coupling agent MP-200, stir for 10-20 min to obtain the first bath impregnation solution;

[0058] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 30 °C for 3 h, then add 12 kg of butadiene-pyridine (VP) latex to the reaction vessel, stir evenly, let stand at 25 °C for 30 h, then add 500 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0059] Example 7

[0060] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0061] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 15 min, then add 100 g of wetting and dispersing agent BYK-163 and 100 g of silane coupling agent MP-200, stir for 15 min, and the first bath impregnation solution is obtained.

[0062] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 4 h, then add 5 kg of PVC latex, 2 kg of styrene-butadiene latex, 1 kg of natural latex and 2 kg of PVC latex to the reaction vessel, stir evenly, let stand at 25 °C for 28 h, then add 300 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0063] Example 8

[0064] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0065] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 1.5 h, then add 300 g of isocyanate IL-6, stir for 25 min, then add 150 g of acetylacetonate diol surfactant ZY-1104 and 150 g of silane coupling agent MP-200, stir for 15 min, and the first bath impregnation solution is obtained.

[0066] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 4 h, then add 5 kg of PVC latex, 2 kg of styrene-butadiene latex, 1 kg of natural latex and 2 kg of PVC latex to the reaction vessel, stir evenly, let stand at 25 °C for 30 h, then add 400 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0067] Example 9

[0068] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0069] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 30 min, then add 200 g of acetylacetonate diol surfactant ZY-1104 and 200 g of silane coupling agent MP-200, stir for 15 min, and the first bath impregnation solution is obtained.

[0070] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 3 h, then add 5 kg of PVC latex, 2 kg of styrene-butadiene latex, 1 kg of natural latex and 2 kg of PVC latex to the reaction vessel, stir evenly, let stand at 25 °C for 25 h, then add 500 g of fumed silica wv33, stir evenly to obtain the second bath impregnation solution.

[0071] Comparative Example 1

[0072] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0073] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 20 min, and the first bath impregnation solution is obtained.

[0074] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 3 h, then add 12 kg of butyl pyridine (VP) latex to the reaction vessel, stir evenly, and let stand at 25 °C for 25 h to obtain the second bath impregnation solution.

[0075] Comparative Example 2

[0076] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0077] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 50 g of epoxy resin EX-614B, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 15 min to obtain the first bath impregnation solution.

[0078] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 3 h, then add 12 kg of butyl pyridine (VP) latex to the reaction vessel, stir evenly, and let stand at 25 °C for 24 h to obtain the second bath impregnation solution.

[0079] Comparative Example 3

[0080] A high-temperature and over-vulcanization resistant impregnation solution, comprising a first bath impregnation solution and a second bath impregnation solution, is prepared as follows:

[0081] Preparation of the first bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 100 g of epoxy resin G1701, stir for 1 h, then add 300 g of isocyanate IL-6, stir for 15 min, and the first bath impregnation solution is obtained.

[0082] Preparation of the second bath impregnation solution: Add 10 kg of deionized water to the reaction vessel, then add 17 g of sodium hydroxide and 580 g of resorcinol, stir until the solid dissolves, then add 850 g of formaldehyde, stir at 25 °C for 4 h, then add 5 kg of PVC latex, 2 kg of styrene-butadiene latex, 1 kg of natural latex and 2 kg of PVC latex to the reaction vessel, stir evenly, and let stand at 25 °C for 28 h to obtain the second bath impregnation solution.

[0083] This invention uses a 1500D / 2 polyester cord fabric as an example. The polyester cord fabric was impregnated in the high-temperature and over-vulcanization resistant impregnation solutions of Examples 1-9 and Comparative Examples 1-3 using a two-bath impregnation process. The conditions for the first-bath impregnation were: drying temperature 165℃, tension 800 daN, stretching temperature 235℃, tension 2000 daN, and speed 75 m / min. The conditions for the second-bath impregnation were: drying temperature 160℃, tension 1200 daN, setting temperature 240℃, tension 800 daN, and speed 75 m / min. The polyester cord fabric after impregnation was tested, and the test results are shown in Table 1 below.

[0084] Table 1 Comparison of physical property data

[0085]

[0086] The polyester cords treated with resin in Examples 1-9 and Comparative Examples 1-3 were subjected to CRA testing. Standard resin (provided by Bridgestone) was completely coated onto the resin-coated cords to prepare CRA patterns. These patterns were then vulcanized on a flat vulcanizing machine at a vulcanization temperature of 160°C, a vulcanization pressure of 3.5 MPa, and vulcanization times of 20 min, 60 min, 120 min, and 180 min, respectively. Surface grades: A: Surface resin coating range: 96-100%; B: Surface resin coating range: 71-95%; C: Surface resin coating range: 41-70%; D: Surface resin coating range: 11-40%; E: Surface resin coating range: 0-10%. The test results are shown in Table 2 below.

[0087] Table 2 Comparison of CRA Adhesion Strength Data

[0088]

[0089] As can be seen from the data in the table above, the RFL impregnation system of the present invention, although additives are added to the impregnation solution, does not have a significant impact on the physical properties of the cord. Furthermore, the preparation process of the impregnation solution is very simple, which can not only improve its adhesive performance, but also does not affect production efficiency.

[0090] In summary, compared with the traditional RFL impregnation system, this invention significantly improves the adhesion performance between the fiber and the rubber matrix by adding the wetting and penetrating agent and the silane coupling agent in the first bath and adding fumed silica in the second bath. In particular, it exhibits excellent adhesion performance under over-sulfurization conditions, without compromising the superior properties of the rubber matrix and the skeleton material. This solves the technical problem of low adhesion performance of fiber / rubber composites under harsh conditions, which leads to damage and loss, and increases the safety and stability of fiber / rubber composites in use.

[0091] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high temperature and over-sulfurized resistant impregnating solution, said impregnating solution comprising a first bath impregnating solution and a second bath impregnating solution, characterized in that, By weight parts, including the following components: The first bath dipping glue solution: deionized water 100 parts, water-soluble epoxy resin 0.1-9 parts, isocyanate 0.5-50 parts, wetting penetrant 0.5-5 parts, silane coupling agent 0.5-5 parts; The second bath dipping glue solution: deionized water 100 parts, resorcinol 1-10 parts, formaldehyde 1.5-15 parts, sodium hydroxide 0.05-0.4 parts, latex 60-200 parts, fumed silica 1-10 parts; The preparation method of the high-temperature-resistant and over-sulfurized dipping glue solution comprises the following steps: Preparation of the first bath dipping glue solution: deionized water is added to the reaction kettle, then water-soluble epoxy resin is added, stirring for 0.5-1.5h, then isocyanate is added, stirring for 10-30min, wetting penetrant and silane coupling agent are continuously added, stirring for 10-20min, and the first bath dipping glue solution is obtained; Preparation of the second bath dipping glue solution: deionized water is added to the reaction kettle, then sodium hydroxide and resorcinol are added, stirring until the solids are dissolved, then formaldehyde is added, stirring at 20-30℃ for 3-4h, latex is added to the reaction kettle, stirring uniformly, then fumed silica is added after standing, stirring uniformly, and the second bath dipping glue solution is obtained.

2. The high-temperature resistant per-sulfurized impregnating solution according to claim 1, characterized in that, By weight parts, including the following components: The first bath dipping glue solution: deionized water 100 parts, water-soluble epoxy resin 0.5-3 parts, isocyanate 5-30 parts, wetting penetrant 1-3 parts, silane coupling agent 1-3 parts; The second bath dipping glue solution: deionized water 100 parts, resorcinol 3-8 parts, formaldehyde 4.5-12 parts, sodium hydroxide 0.1-0.2 parts, latex 80-180 parts, fumed silica 2-8 parts.

3. The high-temperature resistant and over-sulfurized impregnating solution according to claim 1, characterized in that, By weight parts, including the following components: The first bath dipping glue solution: deionized water 100 parts, water-soluble epoxy resin 1-2 parts, blocked isocyanate 3-10 parts, wetting penetrant 1-2 parts, silane coupling agent 1-2 parts; The second bath dipping glue solution: deionized water 100 parts, resorcinol 4-6 parts, formaldehyde 6-9 parts, sodium hydroxide 0.12-0.2 parts, latex 90-150 parts, fumed silica 3-6 parts.

4. The high temperature resistant and over-sulfurized impregnating solution according to claim 1, characterized in that, The water-soluble epoxy resin is one or several of EX614B, EX512, JF313, JF512, and G1701.

5. The high temperature resistant and over-sulfurized impregnating solution according to claim 1, characterized in that, The latex is one or several of butadiene-acrylonitrile rubber latex, styrene-butadiene rubber latex, and natural rubber latex.

6. The high temperature resistant and over-sulfurized impregnating solution according to claim 1, characterized in that, The wetting penetrant is one or several of acetylenic diol, HY-1000 low-foam wetting penetrant, and BYK wetting dispersant.

7. The high temperature resistant per-sulphidization resistant impregnating solution according to claim 1, characterized in that, The isocyanate is one or several of toluene diisocyanate, diphenylmethane diisocyanate, and 1,6-hexane diisocyanate.

8. A process for the preparation of a high temperature resistant over-sulfurized dip solution according to any one of claims 1 to 7, characterized in that, The preparation method comprises the following steps: Preparation of the first bath dipping glue solution: deionized water is added to the reaction kettle, then water-soluble epoxy resin is added, stirring for 0.5-1.5h, then isocyanate is added, stirring for 10-30min, wetting penetrant and silane coupling agent are continuously added, stirring for 10-20min, and the first bath dipping glue solution is obtained; Preparation of the second bath impregnation glue solution: add deionized water into the reaction tank, then add sodium hydroxide and resorcinol, stir until the solid is dissolved, then add formaldehyde, stir at 20-30°C for 3-4h, then add latex into the reaction tank, stir uniformly, after standing, add fumed silica, stir uniformly to obtain the second bath impregnation glue solution.

9. The production method according to claim 8, characterized by, The standing temperature is 25-30°C, and the standing time is 20-30h.

10. A process for the impregnation of high temperature resistant over-sulphidized impregnating solutions according to any one of claims 1 to 7, characterized in that, The bone frame material is subjected to one-bath impregnation treatment through the first bath impregnation glue solution, and after the treatment is completed, two-bath impregnation treatment is performed through the second bath impregnation glue solution, and then the bone frame material is obtained. The conditions of the one-bath impregnation treatment are as follows: drying temperature 140-170°C, tension 500-2000daN, drawing temperature 230-250°C, tension 1000-4000daN, and speed 65-95m / min; the conditions of the two-bath impregnation treatment are as follows: drying temperature 140-170°C, tension 500-2000daN, setting temperature 230-250°C, tension 300-1000daN, and speed 65-95m / min.

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