A glass fiber sizing for molded grating and its preparation method, product and application

Abstract

The application discloses a glass fiber sizing agent for molded grating, which comprises effective components and water, and the solid content of the sizing agent is 6-9%, and the percentage of the solid mass of the effective components in the total solid mass of the sizing agent is as follows: 5.0-12.0% of silane coupling agent A; 2.0-7.0% of silane coupling agent B; 20.0-45.0% of film forming agent A; 20.0-44.0% of film forming agent B; 10.0-17.0% of film forming agent C; 3.0-8.0% of lubricant; and 1.0-6.0% of pH value regulator; wherein the film forming agent A is a vinyl acetate-vinyl copolymer emulsion, the film forming agent B is a bisphenol F epoxy resin emulsion, and the film forming agent C is a modified polyester resin emulsion. The glass fiber coated by the sizing agent has good yarn smoothness, easy dispersion, good fusing property and flexibility, is not easy to be abraded, has good compatibility with unsaturated polyester resin, has fast penetration speed, has good use smoothness, and meets the process requirements of molded glass steel grating production, and the molded glass steel grating prepared from the sizing agent has excellent shearing resistance.

Description

Technical Field

[0001] This application relates to the field of glass fiber impregnating agent technology, specifically to a glass fiber impregnating agent for molded grids, its preparation method, product, and application. Background Technology

[0002] Molded fiberglass grating has been widely used in recent years in industries such as petroleum, chemical, electronics, power, paper, printing and dyeing, electroplating, marine exploration, and wastewater treatment for work platforms, equipment platforms, drilling platforms, and walkways. It is a common product in corrosive environments and is also used in civil construction facilities. This product is a fiberglass sheet with many regularly distributed rectangular or square openings, manufactured using a molding process. Molded fiberglass grating has a wide range of applications, comes in various types, boasts vibrant colors, and can be flexibly customized in size, making it a commonly used building material.

[0003] Traditional molded fiberglass grating is made of general-purpose fiberglass, which has poor yarn conformability, slow impregnation speed, low production efficiency, and poor shear resistance, failing to meet the ever-increasing performance requirements.

[0004] Therefore, it is of great significance to develop an alkali-free glass fiber direct yarn impregnating agent with good yarn conformability, fast impregnation speed, and better shear resistance. Summary of the Invention

[0005] To address the aforementioned technical problems, this application provides a glass fiber impregnating agent for molded fiberglass grating. Glass fibers coated with this impregnating agent exhibit soft yarn, easy dispersion, good conformability, good flexibility, and resistance to wear. They also have good compatibility with unsaturated polyester resin and smooth operation, thus well meeting the process requirements for the production of molded fiberglass grating. Molded fiberglass gratings prepared with this agent exhibit excellent shear resistance.

[0006] To achieve the above objectives, this application employs the following technical solution:

[0007] According to one aspect of this application, a sizing agent for glass fibers is provided, the sizing agent comprising an effective component and water, the solid content of the sizing agent being 6% to 9%, the effective component comprising silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant, and pH adjuster; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:

[0008]

[0009] Wherein, film-forming agent A is vinyl acetate-ethylene copolymer emulsion, film-forming agent B is bisphenol F epoxy resin emulsion, and film-forming agent C is modified polyester resin emulsion.

[0010] The percentage of the solid mass of each effective component of the wetting agent to the total solid mass of the wetting agent is expressed as follows:

[0011]

[0012] Wherein, silane coupling agent A is a silane coupling agent with a methoxy group, and silane coupling agent B is a silane coupling agent with an ethoxy group.

[0013] Wherein, the silane coupling agent A is one of 1,2-bis(trimethoxysilyl)ethane silane coupling agent, 3-acetoxypropyltrimethoxysilane coupling agent and γ-methacryloyloxypropyltrimethoxysilane coupling agent;

[0014] The silane coupling agent B is a 3-methacryloyloxypropyltriethoxysilane coupling agent or a vinyltriethoxysilane coupling agent.

[0015] The film-forming agent A is a vinyl acetate-ethylene copolymer emulsion, and depending on its content, it is one of VAE emulsion CW-705, VAE emulsion CW-143 and VAE emulsion JZ-1;

[0016] The film-forming agent B is one of 2,2'-bisphenol F epoxy resin emulsion, 2,4'-bisphenol F epoxy resin emulsion, 4,4'-bisphenol F epoxy resin emulsion, and mixed bisphenol F epoxy resin emulsion.

[0017] The film-forming agent C is a modified polyester resin emulsion prepared by reacting biphenyl diol with a diacid; wherein the diacid is one of oxalic acid, phthalic acid, and isophthalic acid.

[0018] The lubricant is a cationic hydroxy silicone oil emulsion; the pH adjuster is an acid.

[0019] The lubricant is either octamethylhydroxy silicone oil emulsion or hexamethyldiphenyl silicone oil emulsion.

[0020] The functions and contents of each effective component in the glass fiber impregnating agent are explained below:

[0021] Silane coupling agents can undergo a condensation reaction with the surface of glass fibers, firmly fixing them to the glass fiber surface. This application introduces two silane coupling agents into the glass fiber impregnating agent: silane coupling agent A and silane coupling agent B. Preferably, silane coupling agent A is a silane coupling agent with methoxy groups, whose molecular structure contains hydrolyzable alkoxy groups (methoxy groups). This allows them to improve the bonding, adhesion, and compatibility between glass fibers and unsaturated polyester resin through reaction, thereby improving the mechanical properties of the resin-based composite material. The hydrolysis of silane coupling agent A requires acetic acid as a catalyst. Specifically, the pH of the water is adjusted to approximately 3.5–4.5, and then silane coupling agent A is added and stirred for a period of time (at least 30 minutes) until the silane coupling agent is completely dissolved and the solution is clear and transparent. The alkoxy groups of silane coupling agent A hydrolyze to generate active silanol groups, which then undergo a condensation reaction with the hydroxyl groups on the glass fiber surface to form chemical bonds. The preferred silane coupling agent B in this application is a silane coupling agent with ethoxy groups. The hydrolyzable alkoxy groups (ethoxy groups) will undergo a condensation reaction with the hydroxyl groups on the surface of the glass fiber to form a chemical bond, which can improve and enhance the adhesion between the resin and the glass fiber, thereby effectively improving the mechanical strength of the fiberglass products.

[0022] In this application, the combined use of silane coupling agent A and silane coupling agent B allows the sizing agent to simultaneously possess six hydrolyzable alkoxy groups, resulting in superior performance. This enables the sizing agent to better adhere to the surface of the glass fiber filament, effectively reducing wear during production and providing more effective protection for the glass fiber. The dosage of silane coupling agent A and silane coupling agent B must be controlled within a certain range. If too much silane coupling agent A is used, its hydrolysate concentration will be too high, leading to self-polymerization into silane polymers (silicone) and rendering it ineffective. If too much silane coupling agent B is used, incomplete hydrolysis may occur, and the excess cannot participate in subsequent reactions, resulting in waste. The inventors discovered that controlling the content of silane coupling agent A to 5.0%–12.0% and the content of silane coupling agent B to 2.0%–7.0% results in the best synergistic effect, which can greatly improve the shear performance of molded fiberglass grating. Preferably, the content of silane coupling agent A is 7.0%–11.0% and the content of silane coupling agent B is 3.0%–6.0%. More preferably, the content of silane coupling agent A is 8.5%–9.5% and the content of silane coupling agent B is 4.5%–5.0%. Even more preferably, the ratio of silane coupling agent A to silane coupling agent B can be controlled at 1.8–2.2:1.

[0023] Preferably, the silane coupling agent A in the wetting agent of this application is one of 1,2-bis(trimethoxysilyl)ethane silane coupling agent, 3-acetoxypropyltrimethoxysilane coupling agent, and γ-methacryloyloxypropyltrimethoxysilane coupling agent; and the silane coupling agent B is 3-methacryloyloxypropyltriethoxysilane coupling agent or vinyltriethoxysilane coupling agent.

[0024] Film-forming agents are the main components of sizing agents used in glass fibers. They protect glass fibers, improve their bundle structure and stiffness, and have a decisive influence on the continuous production and application of glass fibers. The glass fiber sizing agent of this application includes film-forming agent A, film-forming agent B, and film-forming agent C. Preferably, the film-forming agent A is a vinyl acetate-ethylene copolymer emulsion, which has excellent adhesion and can form a uniform protective film on the glass fiber surface, which is beneficial for fiber drawing and forming; the film-forming agent B is a bisphenol F epoxy resin emulsion, which contains alcohol hydroxyl and phenol hydroxyl groups, and can react with the silane coupling agent A and the silane coupling agent B hydrolyzed in this application, and has good compatibility with the matrix resin, which can greatly improve the penetration speed in the matrix resin, and at the same time make the molded fiberglass grating have good water resistance and corrosion resistance; the film-forming agent C is a modified polyester resin emulsion. The viscosity of conventional water-based polyester resin emulsion is usually above 1000 mPas, while the modified polyester resin emulsion used in this application has a lower viscosity, and the emulsion stability after water compatibility is better. After standing for 48 hours, there is no obvious sediment, and after being prepared as an impregnating agent, it can be coated more evenly on the glass fiber surface. The appropriate use of modified polyester resin emulsion can improve the flexibility of glass fiber and effectively reduce the wear of glass fiber during production and use.

[0025] Meanwhile, the dosage of each film-forming agent must be controlled within an appropriate range. Experiments have shown that excessive use of film-forming agent A can cause the fiberglass yarn to become sticky and its smoothness to deteriorate; insufficient use will prevent it from fully reacting with the unsaturated functional groups in the coupling agent, ultimately leading to a decrease in the mechanical properties of the molded fiberglass grating. Excessive use of film-forming agent B can cause the yarn to easily unravel, making the molding of the molded fiberglass grating difficult and reducing production efficiency; insufficient use will result in poor yarn dispersion and slower resin impregnation, also affecting production efficiency. Excessive use of film-forming agent C will cause the yarn to gradually harden, increase fuzz, and worsen its conformability; insufficient use will reduce the yarn's flexibility, increasing wear during production and use, thus leading to a decrease in the mechanical properties of the molded fiberglass grating. Therefore, in this application, the solid mass of film-forming agent A accounts for 20.0% to 45.0% of the total solid mass of the sizing agent, preferably 28.0% to 40.0%, more preferably 30.0% to 34.0%; the solid mass of film-forming agent B accounts for 20.0% to 44.0% of the total solid mass of the sizing agent, preferably 25.0% to 36.0%, more preferably 30.0% to 33.0%; and the solid mass of film-forming agent C accounts for 10.0% to 17.0% of the total solid mass of the sizing agent, preferably 11.0% to 15.0%, more preferably 13.0% to 14.0%.

[0026] Preferably, the film-forming agent A can be one of VAE emulsion CW-705, VAE emulsion CW-143, and VAE emulsion JZ-1, depending on the synthesis method and copolymerization ratio; the film-forming agent B is one of 2,2'-bisphenol F epoxy resin emulsion, 2,4'-bisphenol F epoxy resin emulsion, 4,4'-bisphenol F epoxy resin emulsion, and mixed bisphenol F epoxy resin emulsion; the film-forming agent C is a modified polyester resin emulsion prepared by reacting biphenyl diol with a diacid, wherein the diacid is one of oxalic acid, phthalic acid, and isophthalic acid.

[0027] The function of the lubricant is to improve the smoothness and softness of the yarn, while reducing damage to the glass fiber during molding and use. The lubricant used in this application is preferably a cationic hydroxyl silicone oil emulsion. The cationic hydroxyl silicone oil emulsion has reactive hydroxyl groups at both ends, which can react with the silanol groups in silane coupling agents A and B of this application, enhancing the coating effect of the sizing agent. Preferably, the cationic hydroxyl silicone oil emulsion has a pH value of 5.0–7.0, a particle size of 0.01–2 μm, and a non-aqueous component content of 30% ± 2%. Under these performance indicators, the hydrophilic and lipophilic groups in the emulsion can maintain a relatively balanced state, the emulsion is less prone to stratification, and the final sizing agent will be more stable. The cationic hydroxyl silicone oil emulsion can improve the softness and smoothness of the glass fiber, reduce wear during production, and improve the smoothness of use. Compared with PEG-based lubricants, the cationic hydroxyl silicone oil emulsion lubricant used in this application can improve the softness of the glass fiber while also providing sufficient smoothness. Preferably, the cationic hydroxyl silicone oil emulsion lubricant is octamethylhydroxyl silicone oil emulsion or hexamethyldiphenyl silicone oil emulsion. Simultaneously, the amount of lubricant used needs to be controlled within a suitable range. If the amount of lubricant is too small, it will not achieve the desired lubrication effect, while if the amount is too large, it will make the glass fiber too soft and slippery, unable to be properly drawn and formed. Therefore, this application controls the lubricant content to 3.0%–8.0%; preferably 4.0%–7.0%; more preferably 5.0%–6.0%.

[0028] The pH adjuster used in this application is primarily to ensure that the silane coupling agent can be better and more quickly dispersed uniformly in water, while appropriate acidity also allows the functional groups of each component in the wetting agent to maintain sufficient reactivity. Glacial acetic acid is preferred as the pH adjuster in this application. The amount of pH adjuster must also be controlled within a certain range: too little pH adjuster will result in incomplete hydrolysis of the silane coupling agent, while too much will lead to excessive acidity in the wetting agent, reducing the reactivity between the silane coupling agent and the film-forming agent. Glacial acetic acid at a content of 1% to 6% has a very good dispersing effect, allowing the silane coupling agent to disperse better. Therefore, this application controls the percentage of the solid mass of the pH adjuster to the total solid mass of the wetting agent to be 1.0% to 6.0%, preferably 2.0% to 5.0%, and more preferably 3.0% to 4.0%.

[0029] In this application, the optimal pH range of the wetting agent is 3 to 5.

[0030] This application uses water as the dispersed phase for each component of the wetting agent. Compared with the solvent dispersed phase, water is more environmentally friendly and safer. Among them, deionized water is preferred.

[0031] The glass fiber impregnating agent of this application incorporates a compound of silane coupling agent A and silane coupling agent B. Through their synergistic use, the impregnating agent possesses six hydrolyzable alkoxy groups, resulting in superior performance. This allows the impregnating agent to better adhere to the surface of the glass fiber, effectively reducing wear during production and providing more effective protection for the glass fiber. Furthermore, silane coupling agent A and silane coupling agent B can interact with the double bonds in the unsaturated polyester, strengthening the bond between the glass fiber and the unsaturated polyester resin matrix. This results in higher shear strength in the molded fiberglass grating constructed from the glass fiber reinforced composite material. Secondly, three film-forming agents were selected for compound use. By choosing appropriate types of film-forming agents and rationally configuring the content of each agent, the advantages of the three agents were effectively combined. This allows a uniform protective film to be formed on the surface of the glass fiber, which is more conducive to fiber drawing and shaping. It also allows interaction with the double bonds in the unsaturated polyester, resulting in cross-linking of multiple substances and strengthening the bond between the glass fiber and the unsaturated polyester resin matrix. This makes the yarn easier to spread naturally during use and allows for full contact with the matrix resin, increasing the impregnation speed. Simultaneously, it improves the yarn's conformability and flexibility during use, effectively reducing wear on the glass fiber during production and use. Furthermore, it improves the compatibility between the glass fiber and the unsaturated polyester resin, ultimately enhancing the shear resistance of the molded fiberglass grating. Thirdly, a cationic hydroxyl silicone oil emulsion lubricant with multiple hydroxyl groups was selected. This lubricant can react with the silanol groups in silane coupling agents A and B, enhancing the coating effect of the wetting agent. It also improves the softness and smoothness of the glass fiber, reducing wear during production and improving ease of use. Fourth, glacial acetic acid is used as a pH adjuster. The role of glacial acetic acid is to enable the silane coupling agent to disperse better and faster in water evenly. Simultaneously, the appropriate acidity allows the functional groups of each component in the sizing agent to maintain sufficient reactivity. By rationally proportioning silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant, pH adjuster, and water, a glass fiber sizing agent is prepared. Glass fiber products coated with this sizing agent exhibit characteristics such as soft yarn, easy dispersion, good conformability, good flexibility, wear resistance, good compatibility with unsaturated polyester resin, and smooth operation. This effectively meets the process requirements for molded fiberglass grating production. Furthermore, molded fiberglass grating reinforced with glass fiber direct yarn produced using this sizing agent exhibits superior shear resistance compared to conventional products.

[0032] It should be noted that, in this application, the solid mass of the effective component in emulsion form refers to the mass of the remaining part after the emulsion has been dried and the water removed under certain conditions.

[0033] According to a second aspect of this application, a method for preparing the aforementioned glass fiber impregnating agent is provided, comprising the following steps:

[0034] Dilution of film-forming agents and lubricants: Film-forming agents A, B, and C are diluted with 1 to 3 times their weight of water by stirring to obtain diluted film-forming agent A emulsion, film-forming agent B emulsion, and film-forming agent C emulsion, respectively; lubricant is diluted with 8 to 12 times its weight of water by stirring to obtain diluted lubricant aqueous solution, wherein the water temperature is 50 to 60℃;

[0035] Preparation of a mixed solution of silane coupling agent A and silane coupling agent B: Take water with a mass of 30-40% of the total water content of the wetting agent, add a pH adjuster, and stir for 3-5 minutes to obtain an aqueous solution of the pH adjuster; add silane coupling agent A to the aqueous solution of the pH adjuster and stir for 25-30 minutes, then add silane coupling agent B and stir for 25-30 minutes to obtain a mixed solution of silane coupling agent A and silane coupling agent B;

[0036] Preparation of the sizing agent: The diluted film-forming agent A emulsion, film-forming agent B emulsion, film-forming agent C emulsion, and lubricant aqueous solution are added to the mixed solution of silane coupling agent A and silane coupling agent B, and the water in the sizing agent formula is added. The mixture is stirred for 20-30 minutes to obtain the glass fiber sizing agent.

[0037] According to a third aspect of this application, a glass fiber product produced by coating with the aforementioned glass fiber sizing agent is provided.

[0038] According to the fourth aspect of this application, the aforementioned glass fiber products are provided for use in the production of molded fiberglass gratings.

[0039] Compared with the prior art, the beneficial effects of this application are reflected in:

[0040] 1. This application uses silane coupling agent A and silane coupling agent B in combination and studies a suitable content ratio so that the impregnating agent has one acetoxy functional group containing an unsaturated double bond structure, one unsaturated vinyl functional group and six hydrolyzable alkoxy groups, which can react with the film-forming agent. This can effectively protect the glass fiber and strengthen the bonding between the glass fiber and the matrix resin, thereby giving the molded fiberglass grating made of glass fiber reinforced composite material higher shear strength.

[0041] 2. This application investigated the combination of film-forming agents in the impregnation formulation. Film-forming agents A, B, and C were used in a specific ratio. The synergistic use of these three agents can form a uniform protective film on the glass fiber surface, which is more conducive to fiber drawing and shaping. They also interact with the acetoxy functional groups and unsaturated vinyl functional groups of the unsaturated double bond structure in the silane coupling agent, as well as the double bonds in the unsaturated polyester, resulting in cross-linking of multiple substances and strengthening the bond between the glass fiber and the unsaturated polyester resin matrix. This allows the yarn to spread out more easily during use and make full contact with the matrix resin, increasing the impregnation speed. It also improves the yarn's conformability and flexibility, effectively reducing wear on the glass fiber during production and use. Furthermore, it improves the compatibility between the glass fiber and the unsaturated polyester resin, ultimately enhancing the shear resistance of the molded fiberglass grating. Detailed Implementation

[0042] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be arbitrarily combined with each other.

[0043] The glass fiber sizing agent of this application comprises an effective component and water. The solid content of the sizing agent is 6% to 9%. The effective component includes silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant, and pH adjuster. The percentage of the solid mass of each effective component to the total solid mass of the sizing agent is expressed as follows:

[0044]

[0045] Wherein, silane coupling agent A is a silane coupling agent with a methoxy group, preferably one of 1,2-bis(trimethoxysilyl)ethane silane coupling agent, 3-acetoxypropyltrimethoxysilane coupling agent and γ-methacryloyloxypropyltrimethoxysilane coupling agent; silane coupling agent B is preferably a silane coupling agent with an ethoxy group, preferably 3-methacryloyloxypropyltriethoxysilane coupling agent or vinyltriethoxysilane coupling agent.

[0046] Film-forming agent A is a vinyl acetate-ethylene copolymer emulsion, preferably one of VAE emulsion CW-705, VAE emulsion CW-143, and VAE emulsion JZ-1; film-forming agent B is a bisphenol F epoxy resin emulsion, preferably one of 2,2'-bisphenol F epoxy resin emulsion, 2,4'-bisphenol F epoxy resin emulsion, 4,4'-bisphenol F epoxy resin emulsion, and mixed bisphenol F epoxy resin emulsion; film-forming agent C is a modified polyester resin emulsion, preferably a modified polyester resin emulsion obtained by reacting biphenyl diol with a diacid, wherein the diacid is one of oxalic acid, phthalic acid, and isophthalic acid. The modified polyester resin emulsion is prepared using conventional methods of existing technology, usually using organotin compounds as catalysts, with the catalyst dosage being 0.05-0.25% of the total reaction amount, the reaction temperature controlled at 190-220℃, and the reaction time at least 5 hours.

[0047] The lubricant is a cationic hydroxyl silicone oil emulsion, preferably an octamethyl hydroxyl silicone oil emulsion or a hexamethyl diphenyl silicone oil emulsion.

[0048] The pH adjuster is an acid, preferably glacial acetic acid.

[0049] The water is preferably deionized water.

[0050] The method for preparing the glass fiber impregnating agent of this application includes the following steps:

[0051] Dilution of film-forming agents and lubricants: Film-forming agents A, B, and C are diluted with 1 to 3 times their weight of water by stirring to obtain diluted film-forming agent A emulsion, film-forming agent B emulsion, and film-forming agent C emulsion, respectively; lubricant is diluted with 8 to 12 times its weight of water by stirring to obtain diluted lubricant aqueous solution, wherein the water temperature is 50 to 60℃;

[0052] Preparation of a mixed solution of silane coupling agent A and silane coupling agent B: Take water with a mass of 30-40% of the total water content of the wetting agent, add a pH adjuster, and stir for 3-5 minutes to obtain an aqueous solution of the pH adjuster; add coupling agent A to the aqueous solution of the pH adjuster and stir for 25-30 minutes, then add coupling agent B and stir for 25-30 minutes to obtain a mixed solution of coupling agent A and coupling agent B;

[0053] Preparation of the sizing agent: The diluted film-forming agent A emulsion, film-forming agent B emulsion, film-forming agent C emulsion, and lubricant aqueous solution are added to the mixed solution of coupling agent A and coupling agent B, and the water in the sizing agent formula is added. The mixture is stirred for 20-30 minutes to obtain the glass fiber sizing agent.

[0054] The specific formulations of some embodiments of the sizing agent for glass fiber in this application are shown in Table 1. The values ​​in Table 1 are the percentages of the solid mass of the effective component to the total solid mass of the sizing agent.

[0055] It should be noted that the specific types, contents, and combinations of the components selected in Table 1 do not limit the scope of protection of this application. Those skilled in the art can make adaptive adjustments based on the wetting agent formulation and preparation method of this application according to the actual situation.

[0056] In Examples 1-3, silane coupling agent A is a 1,2-bis(trimethoxysilyl)ethane silane coupling agent, and silane coupling agent B is a 3-methacryloxypropyltriethoxysilane coupling agent; in Examples 4-5, silane coupling agent A is a γ-methacryloxypropyltrimethoxysilane coupling agent, and silane coupling agent B is a 3-methacryloxypropyltriethoxysilane coupling agent; in Examples 6-8, silane coupling agent A is a 3-acetoxypropyltrimethoxysilane coupling agent, and silane coupling agent B is a vinyltriethoxysilane coupling agent; in Examples 9-12, silane coupling agent A is a 1,2-bis(trimethoxysilyl)ethane silane coupling agent, and silane coupling agent B is a vinyltriethoxysilane coupling agent.

[0057] In Examples 1-3, film-forming agent A was VAE emulsion CW-143, film-forming agent B was 2,2'-bisphenol F epoxy resin emulsion, and film-forming agent C was a modified polyester resin emulsion prepared by reacting biphenyl glycol with phthalic acid; in Examples 4-5, film-forming agent A was VAE emulsion CW-143, film-forming agent B was 4,4'-bisphenol F epoxy resin emulsion, and film-forming agent C was a modified polyester resin prepared by reacting biphenyl glycol with phthalic acid. Emulsions; In Examples 6-8, film-forming agent A is VAE emulsion CW-705, film-forming agent B is 2,4'-bisphenol F epoxy resin emulsion, and film-forming agent C is a modified polyester resin emulsion prepared by reacting biphenyl diol with oxalic acid; In Examples 9-12, film-forming agent A is VAE emulsion JZ-1, film-forming agent B is mixed bisphenol F epoxy resin emulsion, and film-forming agent C is a modified polyester resin emulsion prepared by reacting biphenyl diol with isophthalic acid.

[0058] In Examples 1-5, the lubricant was hexamethyldiphenyl silicone oil emulsion; in Examples 6-12, the lubricant was octamethylhydroxy silicone oil emulsion.

[0059] Table 1 shows the proportions of each effective component of the wetting agent in the embodiments.

[0060]

[0061] Table 1 (continued) Proportions of each effective component of the wetting agent in the examples

[0062]

[0063]

[0064] Comparative Example

[0065] To further demonstrate the beneficial effects of this application, commonly used geogrid impregnating agent formulations, highly versatile direct yarn impregnating agent formulations, and impregnating agent formulations with different ratios in the prior art were selected as comparative examples (Comparative Examples 1-4) for comparison. The specific comparative example formulations and comparative test results are as follows. In each comparative example formulation, the content represents the percentage of the solid mass of the effective component to the total solid mass of the impregnating agent.

[0066] Comparative Example 1 (Formulation of impregnating agent for geogrid):

[0067] Silane coupling agent A: γ-methacryloyloxypropyltrimethoxysilane, 9.5%;

[0068] Silane coupling agent B: γ-aminopropyltrimethoxysilane, 2%;

[0069] Lubricant: Sodium stearate, 14%;

[0070] Film-forming agent A: Epoxy resin emulsion: 48.5%;

[0071] Film-forming agent B: Polyurethane emulsion: 21%;

[0072] pH adjuster: citric acid, 5%.

[0073] Comparative Example 2 (sizing agent for highly versatile direct yarn):

[0074] Silane coupling agent A: Methacryloxysilane coupling agent, 5.7%;

[0075] Silane coupling agent B: aminosilane coupling agent, 5.7%;

[0076] Silane coupling agent C: epoxy silane coupling agent, 1.4%;

[0077] Film-forming agent A: Nonionic aqueous polyurethane emulsion, 14.3%;

[0078] Film-forming agent B: Aqueous polyester emulsion, 24.3%;

[0079] Film-forming agent C: Water-soluble epoxy resin emulsion, 25.7%;

[0080] Lubricant A: Quaternary ammonium salt cationic lubricant, 8.6%;

[0081] Lubricant B: Polyoxyethylene amine nonionic lubricant, 10.0%;

[0082] pH adjuster A: Acetic acid, 2.9%;

[0083] pH adjuster B: Citric acid, 1.0%;

[0084] pH adjuster C: Boric acid, 0.4%.

[0085] Comparative Example 3:

[0086] Silane coupling agent A: 1,2-bis(trimethoxysilyl)ethane silane coupling agent, 4.5%;

[0087] Silane coupling agent B: 3-methacryloyloxypropyltriethoxysilane coupling agent, 8.7%;

[0088] Film-forming agent A: VAE emulsion CW-705, 19.0%;

[0089] Film-forming agent B: 2,2'-bisphenol F epoxy resin emulsion, 48.8%;

[0090] Film-forming agent C: 9.5% of a modified polyester resin emulsion prepared by reacting biphenyl diol with oxalic acid;

[0091] Lubricant: Octamethylhydroxy silicone oil emulsion, 6.6%;

[0092] pH adjuster A: glacial acetic acid, 2.9%.

[0093] Comparative Example 4:

[0094] Silane coupling agent A: 3-acetoxypropyltrimethoxysilane coupling agent, 13.0%;

[0095] Silane coupling agent B: Vinyltriethoxysilane coupling agent, 1.5%;

[0096] Film-forming agent A: VAE emulsion CW-143, 46.0%;

[0097] Film-forming agent B: 4,4'-bisphenol F epoxy resin emulsion, 12.7%;

[0098] Film-forming agent C: Modified polyester resin emulsion prepared by reacting biphenyl diol with phthalic acid, 17.3%;

[0099] Lubricant: Hexamethyldiphenyl silicone oil emulsion, 5.6%;

[0100] pH adjuster A: glacial acetic acid, 3.9%.

[0101] Test case

[0102] Glass fiber sizing agents were prepared according to the formulations of the above embodiments and comparative examples, and the performance of alkali-free glass fiber direct yarn coated with the above glass fiber sizing agent and the molded fiberglass grating of the composite material reinforced by the alkali-free glass fiber direct yarn were tested. The glass fiber sizing agent was coated onto the glass fiber, and the performance test results of the alkali-free glass fiber direct yarn coated with the above glass fiber sizing agent and the molded fiberglass grating of the composite material reinforced by the alkali-free glass fiber direct yarn are shown in Table 2. All performance parameters were characterized under the same conditions and for the same time.

[0103] Table 2 Performance Tests of Glass Fiber Direct Yarn and its Reinforced Composites

[0104]

[0105] Table 2 (continued) Performance testing of glass fiber direct yarn and its reinforced composites

[0106]

[0107] As can be seen from the above test examples, the alkali-free glass fiber direct yarn produced using the glass fiber impregnator described in this application and according to conventional glass fiber production processes in the art has a combustible content (i.e., the proportion of the amount of glass fiber impregnator coated on the glass fiber to the mass of the glass fiber) between 0.40% and 0.60%, which can ensure the uniformity of the glass fiber impregnator coating on the glass fiber surface and the wetting speed with the matrix resin, thus ensuring good production efficiency; the linear density is between 2328 and 2472 tex, which can ensure that the final molded fiberglass grating has a suitable glass fiber content and further ensure a suitable performance fluctuation range for the molded fiberglass grating. The average hair content of each embodiment was 7.4 mg / kg (Examples 6, 7, and 8 were superior), and the hair content was significantly less than that of Comparative Examples 1-4. In terms of yarn smoothness, each embodiment was smoother than Comparative Examples 1-4, with Examples 6, 7, and 8 exhibiting the best smoothness. Regarding yarn conformity during the preparation of molded fiberglass grating samples, each embodiment was more conformable than Comparative Examples 1-4, meeting production needs. Among them, Examples 6, 7, and 8 showed the best conformity. In terms of impregnation speed, the average impregnation time of each embodiment was 40.1 s, which was less than that of Comparative Examples 1-4. Among them, Examples 6, 7, and 8 had the shortest impregnation time, with an average impregnation time of only 34.3 s. Furthermore, the average shear strength of the molded fiberglass grating using the alkali-free glass fiber direct yarn reinforced composite material is 70.6 MPa (Examples 6, 7, and 8 are superior), which is much higher than the shear strength of each comparative example. This shows that the molded fiberglass grating using the alkali-free glass fiber direct yarn reinforced composite material coated with the glass fiber impregnator of this application has very excellent shear resistance.

[0108] In summary, the glass fiber impregnating agent of this application has the advantages of good yarn softness, good flexibility, good conformability, good compatibility with unsaturated polyester resin, and fast impregnation speed, which can well meet the production process requirements of molded fiberglass grating. Furthermore, the molded fiberglass grating prepared from the direct yarn produced by this impregnating agent has better shear resistance than conventional products.

[0109] The above-described contents can be implemented individually or in various combinations, and these variations are all within the scope of protection of this application.

[0110] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A glass fiber impregnating agent for molded grating, characterized in that, The wetting agent comprises an effective component and water, and the solid content of the wetting agent is 6% to 9%. The effective component comprises silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant, and pH adjuster. The percentage of the solid mass of each effective component of the wetting agent to the total solid mass of the wetting agent is expressed as follows: Silane coupling agent A 5.0%~12.0% Silane coupling agent B 2.0%~7.0% Film-forming agent A: 0.0%~45.0% Film-forming agent B2 0.0%~44.0% Film-forming agent C 10.0%~17.0% Lubricant 3.0%~8.0% pH adjuster 1.0%~6.0%; Wherein, film-forming agent A is vinyl acetate-ethylene copolymer emulsion, film-forming agent B is bisphenol F epoxy resin emulsion, and film-forming agent C is modified polyester resin emulsion; The film-forming agent C is a modified polyester resin emulsion prepared by reacting biphenyl diol with a diacid. The silane coupling agent A is a silane coupling agent with a methoxy group, and the silane coupling agent B is a silane coupling agent with an ethoxy group.

2. The glass fiber impregnating agent according to claim 1, characterized in that, The percentage of the solid mass of each effective component of the wetting agent to the total solid mass of the wetting agent is expressed as follows: Silane coupling agent A 7.0%~11.0% Silane coupling agent B 3.0%~6.0% Film-forming agent A: 28.0%~40.0% Film-forming agent B: 25.0%~36.0% Film-forming agent C 11.0%~15.0% Lubricant 4.0%~7.0% pH adjuster 2.0%~5.0%.

3. The glass fiber impregnating agent according to claim 1, characterized in that, The silane coupling agent A is one of 1,2-bis(trimethoxysilyl)ethane silane coupling agent, 3-acetoxypropyltrimethoxysilane coupling agent, and γ-methacryloyloxypropyltrimethoxysilane coupling agent; The silane coupling agent B is a 3-methacryloyloxypropyltriethoxysilane coupling agent or a vinyltriethoxysilane coupling agent.

4. The glass fiber impregnating agent according to claim 1 or 2, characterized in that, The film-forming agent A is a vinyl acetate-ethylene copolymer emulsion, and depending on its content, it is one of VAE emulsion CW-705, VAE emulsion CW-143 and VAE emulsion JZ-1; The film-forming agent B is one of 2,2'-bisphenol F epoxy resin emulsion, 2,4'-bisphenol F epoxy resin emulsion, 4,4'-bisphenol F epoxy resin emulsion, and mixed bisphenol F epoxy resin emulsion. The dicarboxylic acid is one of oxalic acid, phthalic acid, and isophthalic acid.

5. The glass fiber impregnating agent according to claim 1 or 2, characterized in that, The lubricant is a cationic hydroxy silicone oil emulsion; the pH adjuster is an acid.

6. The glass fiber impregnating agent according to claim 5, characterized in that, The lubricant is an octamethylhydroxy silicone oil emulsion or a hexamethyldiphenyl silicone oil emulsion.

7. A method for preparing a glass fiber impregnating agent for molded grating as described in any one of claims 1 to 6, characterized in that, Includes the following steps: Dilution of film-forming agents and lubricants: Film-forming agents A, B, and C are diluted with 1 to 3 times their weight of water by stirring to obtain diluted film-forming agent A emulsion, film-forming agent B emulsion, and film-forming agent C emulsion, respectively; lubricant is diluted with 8 to 12 times its weight of water by stirring to obtain diluted lubricant aqueous solution, wherein the water temperature is 50 to 60℃; Preparation of a mixed solution of silane coupling agent A and silane coupling agent B: Take water with a mass of 30-40% of the total water content of the wetting agent, add a pH adjuster, and stir for 3-5 minutes to obtain an aqueous solution of the pH adjuster; add silane coupling agent A to the aqueous solution of the pH adjuster and stir for 25-30 minutes, then add silane coupling agent B and stir for 25-30 minutes to obtain a mixed solution of silane coupling agent A and silane coupling agent B; Preparation of the sizing agent: The diluted film-forming agent A emulsion, film-forming agent B emulsion, film-forming agent C emulsion, and lubricant aqueous solution are added to the mixed solution of silane coupling agent A and silane coupling agent B, and the water in the sizing agent formula is replenished. The mixture is stirred for 20-30 minutes to obtain the glass fiber sizing agent.

8. A glass fiber product produced by coating with the glass fiber sizing agent according to any one of claims 1 to 6.

9. An application of the glass fiber product as described in claim 8 in the production of molded fiberglass grating.

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