Glass fiber wetting agent, method for producing the same, glass fiber products, and applications

Abstract

The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0%-6.0%, and the active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, an antifoaming agent, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is 6%-26% for the silane coupling agent, 45%-78% for the film-forming agent, 5%-15% for the lubricant, 1%-6% for the surfactant, 1%-5% for the leveling agent, 1%-6% for the interface enhancer, 1%-5% for the wetting agent, 1%-5% for the antifoaming agent, and 1%-7% for the pH adjuster. The glass fiber yarn produced by the wetting agent has high bundling ability, flexibility and high dispersibility after receiving a certain tension, fast penetration speed in epoxy resin, good penetration effect, high interfacial compatibility between glass fiber and resin, and suitable for knitting process. It is particularly suitable for producing thick wind blade fabrics, and composite materials made by vacuum infusing the fabric with epoxy resin have high static mechanics and fatigue resistance.

Description

Technical Field

[0005] ,

[0001] This invention claims the priority of a Chinese patent application filed with the China National Intellectual Property Administration on April 20, 2022, with an application number of 202210415238.5 and an invention title of "Glass Fiber Sizing Agent and Its Manufacturing Method, Glass Fiber Products and Applications", and all its contents are incorporated into this invention by reference.

[0002] Technical field This invention relates to the technical field of glass fiber sizing agents, and particularly to glass fiber sizing agents and their manufacturing methods, glass fiber products and applications.

Background Art

[0003] After wind power generation enters the parity stage, market competition becomes increasingly fierce. Each finished product manufacturer and blade manufacturer must reduce costs and improve efficiency from all aspects to maintain the healthy and stable development of the industry. The mainstream cost reduction measures for wind turbine blades mainly include two paths: the first path is to reduce the costs of raw materials such as resin, glass fiber, and core materials, and the second path is to improve the overall manufacturing efficiency and reduce the unit manufacturing cost.

[0004] In such a background, some finished product manufacturers at the forefront of industry research have proposed a comprehensive solution of thick fabrics. The use of thick fabrics has two advantages: (1) improving the laying efficiency and reducing the laying time significantly by reducing the number of main beams of the same thickness by 1 / 3 to 1 / 2, thereby reducing the costs of labor and mold use; (2) significantly improving the glass fiber content, effectively reducing the resin usage, making the arrangement between the thick fabric fibers denser, and reducing the resin usage after injection by 2 - 3%.

[0005] While thick woven fabrics offer significant cost and efficiency advantages, they require extremely high technical expertise. These requirements primarily concern the glass fiber wetting agent. Firstly, thick woven fabrics have a denser fiber arrangement, which negatively impacts the resin injection rate after laying and reduces the number of injection channels. This leads to problems such as longer injection times and insufficient injection. Therefore, it is necessary to ensure that the glass fiber wetting agent and epoxy resin have higher compatibility, allowing for increased overall injection speed and complete penetration into the main beam without negatively impacting the overall injection time. Secondly, the increased glass fiber content after injection in thick woven fabrics directly negatively impacts the fatigue resistance of the main beam. Generally, within a certain range, the higher the glass fiber content, the lower the fatigue resistance; therefore, it is necessary to redesign the glass fiber wetting agent to ensure the fatigue resistance of the blade.

[0006] Currently, there are no dedicated wetting agents for thick fiberglass fabrics on the market. Downstream customers strongly desire the development of professional solutions for thick wind power fabrics to meet the needs of the industry's development. Therefore, the design of fiberglass suitable for thick wind power fabrics will have a significant improvement and promotional effect on the development of the entire wind power industry, as well as a profound impact and remarkable significance on cutting-edge research in the field of new composite materials. [Overview of the project]

[0007] The object of the present invention is to provide a glass fiber wetting agent. Glass fiber yarns produced by applying this agent have high cohesion, are flexible and highly dispersible after being subjected to a certain tension, exhibit a fast penetration rate of epoxy resin, have good penetration effect, have high interfacial compatibility between glass fibers and resin, and are suitable for knitting processes. It is particularly suitable for the production of thick wind-blown braided fabrics, and the composite material obtained by vacuum-injecting the fabric and epoxy resin has high static mechanical properties and fatigue resistance.

[0008] According to one aspect of the present invention, a glass fiber wetting agent is provided which comprises an active ingredient and water, and has a solid content of 4.0 to 6.0%. The active ingredient comprises a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, an antifoaming agent, and a pH adjuster, and the percentage of the solid content mass of each active ingredient relative to the total solid content mass of the wetting agent is Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%.

[0009] In some examples, the percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 7%~25%, Film-forming agent 50%~75%, Lubricant 7%~14%, Surfactants 1%~5%, Leveling agent 1%~4%, Interface enhancer 1%~5%, Humectant 1%~4%, Defoaming agent 2%~4%, The pH adjuster is present in a concentration of 2% to 6%.

[0010] In some examples, the percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 9%~21%, Film-forming agent 52%~73%, Lubricant 7%~13%, Surfactants 2%~5%, Leveling agent 2%~4%, Interface enhancer 2%~5%, Humectant 2%~4%, Defoaming agent 2%~3%, The pH adjuster is 2% to 6%.

[0011] In some embodiments, the silane coupling agent is a mixture of a first silane coupling agent which is an amino silane coupling agent and a second silane coupling agent which is an epoxy silane coupling agent.

[0012] In some embodiments, the mass ratio C1 of the first silane coupling agent to the second silane coupling agent is 1:5 to 1:3.

[0013] In some embodiments, the first silane coupling agent is aminopropyltriethoxysilane and / or γ-aminopropyltrimethoxysilane.

[0014] In some embodiments, the second silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

[0015] In some embodiments, the film-forming agent is a mixture of a first film-forming agent which is a bisphenol A type epoxy resin and a second film-forming agent which is a polyurethane resin.<000008o>

[0016] In some embodiments, the mass ratio C2 of the first film-forming agent to the second film-forming agent is 1:1 to 2:1.

[0017] In some embodiments, the first film-forming agent is a bisphenol A type epoxy resin with a molecular weight of 2000 to 3000.

[0018] In some embodiments, the second film-forming agent is a polyurethane resin with a molecular weight of 200 to 400.

[0019] In some embodiments, the first film-forming agent is a bisphenol A type epoxy resin with a molecular weight of 2300 to 2700.

[0020] In some embodiments, the second film-forming agent is a polyurethane resin with a molecular weight of 250 to 350.

[0021] In some embodiments, the lubricant is a polyethyleneimine-based lubricant and / or a fatty acid amide and its derivatives.

[0022] In some embodiments, the surfactant is pyrrolidone and its derivatives and / or pyridinium salts and their derivatives.

[0023] In some embodiments, the defoaming agent is an organic silicone composite and / or a polyether-based defoaming agent.

[0024] In some embodiments, the leveling agent is a modified polyacrylate and / or a modified organosiloxane.

[0025] In some embodiments, the interfacial strengthening agent is silica nanoparticles and / or alumina nanoparticles.

[0026] In some embodiments, the wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative.

[0027] In some embodiments, the pH adjuster is glacial acetic acid and / or citric acid.

[0028] In some embodiments, the percentage of the solid content mass of each active ingredient in the total solid content mass of the wetting agent in the wetting agent is silane coupling agent 10% - 16%, film-forming agent 55% - 72%, lubricant 7% - 12%, surfactant 2% - 4%, leveling agent 2% - 4%, interfacial strengthening agent 2% - 4%, wetting agent 2% - 3%, defoaming agent 2% - 3%, pH adjuster 2% - 5%, and Of these, the silane coupling agent is a mixture of a first silane coupling agent using an aminosilane coupling agent and a second silane coupling agent using an epoxysilane coupling agent; the film-forming agent is a mixture of a first film-forming agent using a bisphenol A type epoxy resin and a second film-forming agent using a polyurethane resin; the lubricant is a polyethyleneimine-based lubricant and / or fatty acid amide and its derivatives; the surfactant is pyrrolidone and its derivatives and / or pyridinium salt and its derivatives; the leveling agent is modified polyacrylate and / or modified organosiloxane; the interface enhancer is silica nanoparticles and / or alumina nanoparticles; the wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative; the defoaming agent is an organosilicon composite and / or a polyether-based defoaming agent; and the pH adjuster is citric acid and / or glacial acetic acid.

[0029] In some embodiments, the water in the wetting agent of the present invention is deionized water. The role of water in the wetting agent of the present invention is that of the dispersed phase of each component.

[0030] According to a second aspect of the present invention, The process involves adding 30% to 45% of the total mass of the wetting agent to a container, then sequentially adding the pH adjuster and the silane coupling agent, pre-dispersing the silane coupling agent, stirring until the solution becomes clear, and obtaining a pre-dispersion of the silane coupling agent. A dilution step of film-forming agents, lubricants, surfactants, leveling agents, interface enhancers, wetting agents, and defoaming agents, each of which is diluted with water, The present invention provides a method for producing the aforementioned glass fiber wetting agent, comprising the step of adding the diluted film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, and defoaming agent solution to a silane coupling agent predispersion, then supplementing with the remaining amount of water, and stirring uniformly.

[0031] In some examples, the film-forming agent is diluted with 3 to 4 times its mass of water, the interface enhancer is dispersed with 5 to 8 times its mass of water, and the defoaming agent is diluted with 3 to 5 times its mass of water.

[0032] In some embodiments, the lubricant is diluted with 5 to 6 times its mass of warm water at a temperature of 45 to 60°C, the surfactant is diluted with 4 to 6 times its mass of warm water at a temperature of 45 to 60°C, the interface enhancer is diluted with 4 to 6 times its mass of warm water at a temperature of 45 to 60°C, and the wetting agent is diluted with 5 to 6 times its mass of warm water at a temperature of 45 to 60°C.

[0033] Of these, the pre-dispersion of the silane coupling agent and the dilution of the film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, and defoaming agent can be performed in any order. The silane coupling agent may be pre-dispersed first, or the film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, and defoaming agent may be diluted first, or they may be performed simultaneously.

[0034] According to a third aspect of the present invention, a glass fiber product manufactured by applying the aforementioned glass fiber wetting agent is provided.

[0035] According to a fourth aspect of the present invention, the use of a glass fiber product manufactured by applying the aforementioned glass fiber wetting agent in an epoxy resin composite material is provided.

[0036] A fifth aspect of the present invention provides for the use of the aforementioned epoxy resin composite material in the field of wind power generation. [Modes for carrying out the invention]

[0037] To further clarify the objectives, technical solutions, and advantages of the embodiments of the present invention, the technical solutions of the present invention will be clearly and completely described below by combining embodiments of the present invention. It is clear that the embodiments described are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art without creative work based on the embodiments of the present invention are all within the scope of protection of the present invention. Notwithstanding that, embodiments and features of embodiments of the present invention can be combined with each other as they see fit, as long as they do not contradict each other.

[0038] The glass fiber wetting agents provided in some embodiments of the present invention contain an active ingredient and water, the active ingredient comprising a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, an antifoaming agent, and a pH adjuster, the solid content of the wetting agent being 4.0% to 6.0%, and the percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent being 6% to 26% for the silane coupling agent, 45% to 78% for the film-forming agent, 5% to 15% for the lubricant, 1% to 6% for the surfactant, 1% to 5% for the leveling agent, 1% to 6% for the interface enhancer, 1% to 5% for the wetting agent, 1% to 5% for the antifoaming agent, and 1% to 7% for the pH adjuster.

[0039] Silane coupling agents are among the most reactive raw materials in wetting agent systems. The silicone hydroxyl groups formed after their hydrolysis are highly active and can react with the silicone hydroxyl groups on the glass fiber surface to form Si-O-Si bonds. In glass fiber wetting agent systems, coupling agents primarily play the following roles (1) and (2): (1) During the glass fiber drawing and molding process, the high tensile speed causes microcracks to form on the surface of the glass fiber as it rapidly converts from a liquid to a solid state. The silicone hydroxyl groups of the silane coupling agent react with the silicone hydroxyl groups on the glass fiber surface to effectively compensate for these microcracks, ensuring a normal drawing process for the glass fiber. (2) They act as a "bridge" between the glass fiber and the resin. The R group of the silane coupling agent can react with functional groups on the matrix resin, and the silicone hydroxyl groups can bond with the silicone hydroxyl groups on the glass fiber, making it an important factor in determining the strength of glass steel products. By selecting an appropriate silane coupling agent, it is possible to improve the performance of the glass fiber itself and the mechanical properties of the glass steel products manufactured afterward, as well as reduce the manufacturing cost of the glass fiber. When incorporating a glass fiber wetting agent, it is necessary to control the amount of silane coupling agent used within a certain range. If the amount of silane coupling agent used is too little, the active groups will be insufficient, negatively affecting the glass fiber drawing process and the performance of the composite material. If the amount used is too much, some of the silane coupling agent will be wasted, increasing costs. In some examples, the percentage of the solid content of the silane coupling agent relative to the total solid content of the wetting agent may be 6% to 26%, 7% to 25%, 9% to 21%, or 10% to 16%.

[0040] In some embodiments, the silane coupling agent may be a mixture of a first silane coupling agent, which may be an aminosilane coupling agent, and a second silane coupling agent, which may be an epoxysilane coupling agent. The aminosilane coupling agent contains an amine group and has very high reaction activity. It not only reacts with the film-forming agent during the firing process to ensure the overall convergence of the glass fibers, but also reacts rapidly with the epoxy resin in subsequent processing to form a very stable chemical bond, thereby strengthening the interfacial bond between the glass fibers and the epoxy resin and improving the mechanical properties of the composite material. The R group in the epoxysilane coupling agent is an epoxy group, which ensures that the glass fibers rapidly penetrate the epoxy resin during the subsequent manufacturing process of the composite material based on the principle that "like mixes well." In the present invention, when the first silane coupling agent is an aminosilane coupling agent and the second silane coupling agent is an epoxysilane coupling agent, the proportional relationship between the aminosilane coupling agent and the epoxysilane coupling agent can also affect the performance of the glass fibers. If there is too much aminosilane coupling agent, the glass fibers become too stiff due to excessive bundling, which is unfavorable for penetration. If there is too much epoxysilane coupling agent, it is favorable for the penetration of epoxy resin into the glass fibers. However, if there is too little aminosilane coupling agent, the bundling of the fibers is insufficient, causing the fibers to spread easily, and also negatively affecting the mechanical properties of the composite material. In some examples, the mass ratio C1 of the aminosilane coupling agent to the epoxysilane coupling agent may be controlled to 1:5 to 1:3, or to 1:4.3 to 1:3.7. Specifically, when the mass ratio C1 of the aminosilane coupling agent to the epoxysilane coupling agent is 1:4, the performance of the glass fibers produced with the wetting agent manufactured by compounding with other components can all meet the requirements.

[0041] In some examples, the first silane coupling agent may be aminopropyltriethoxysilane and / or γ-aminopropyltrimethoxysilane. In some examples, the second silane coupling agent may be γ-glycidoxypropyltrimethoxysilane.

[0042] Film-forming agents are the most important and largest component in wetting agents. They not only determine the molding process, bundling properties, flexibility, and abrasion resistance of glass fibers, but also influence the dispersibility and smoothness of subsequent processing. They are also a crucial factor in the interfacial bonding between glass fibers and the matrix resin. In the actual production of glass fibers, it is necessary to control the amount of film-forming agent used within an appropriate range. Studies have shown that if the film-forming agent content is insufficient, problems arise with the application of the wetting agent, preventing the wetting agent from effectively protecting the glass fibers, thereby negatively impacting the processing performance and mechanical properties of the glass fibers. If the film-forming agent content is too high, the fibers become too bundling, making them difficult to spread, resulting in increased fluffiness and unfavorable resin penetration. In some embodiments, the percentage of the film-forming agent's solid content relative to the total solid content of the wetting agent may be controlled to 45% to 78%, 50% to 75%, 52% to 73%, or even 55% to 72%. Within this range, the film-forming agent can not only ensure that the glass fibers have good dispersibility and flexibility, but also ensure the process smoothness of the glass fibers, compatibility with the matrix resin, and the mechanical properties of the composite material.

[0043] In some embodiments, the film-forming agent may be a mixture of a first film-forming agent and a second film-forming agent. The first film-forming agent may be a bisphenol A type epoxy resin, and the second film-forming agent may be a polyurethane resin. In some embodiments, the first film-forming agent may be a bisphenol A type epoxy resin with a high molecular weight, specifically a bisphenol A type epoxy resin with a molecular weight of 2000-3000, or a bisphenol A type epoxy resin with a molecular weight of 2300-2700. High molecular weight epoxy resins can ensure the film-forming properties of the wetting agent. In some embodiments, the second film-forming agent may be a polyurethane resin with a low molecular weight, specifically a polyurethane resin with a molecular weight of 200-400, a polyurethane resin with a molecular weight of 250-400, or a polyurethane resin with a molecular weight of 250-350. Low molecular weight polyurethane resins disperse very easily after the glass fibers are subjected to tension, ensuring permeability and interfacial bonding. At the same time, it is necessary to strictly control the amounts used for the two types of film-forming agents. If too much of the first film-forming agent is used, the filamentation becomes too good, making it difficult for the yarn to penetrate the resin. If too much of the second film-forming agent is used, the yarn becomes too soft, spreading out easily, negatively affecting the subsequent processing characteristics. In some examples, the mass ratio C2 of the first film-forming agent to the second film-forming agent can be controlled to 1:1 to 2:1. When the mass ratio C2 of the first film-forming agent to the second film-forming agent in this invention is 1:1 to 2:1, the performance characteristics of the manufactured glass fibers can all reach an excellent level.

[0044] In some examples, the mass ratio of the silane coupling agent to the film-forming agent is 1:3 to 1:6. This ratio not only ensures film formation and uniform application of the wetting agent, but also provides sufficient reactive activity between the wetting agent and the glass skeleton and matrix resin.

[0045] Lubricants are one of the main components of glass fiber wetting agents, primarily to improve the wear resistance of glass fibers and ensure smoothness during the drawing and use processes. The lubricant of the present invention may be a polyethyleneimine-based lubricant and / or a fatty acid amide and its derivatives. Such lubricants have excellent dispersibility in water, exhibit remarkable lubrication effects, and can effectively reduce the generation of fuzz. Among these, the fatty acid amide and its derivatives may include one or two of alkoxy-modified fatty acid amides and quaternized fatty acid amides. In the manufacture of glass fibers, it is necessary to strictly control the amount of lubricant used. If the amount of lubricant used is too little, it will negatively affect the smoothness of the drawing and use processes, and is likely to cause problems such as thread breakage during the drawing process and subsequent interruption of the thread. However, if the amount of lubricant is too much, it will not only increase costs, but the excess lubricant will also easily adhere to the surface of the tensioning device during the use of the glass fibers. As the amount of adhesive lubricant increases, the adhesive force increases, causing situations such as thread sticking and thread breakage, thus negatively affecting the processability of using the glass fibers. In some embodiments, the percentage of the solid content of the lubricant relative to the total solid content of the wetting agent may be controlled to 5% to 15%, 7% to 14%, 7% to 13%, or even 7% to 12%.

[0046] Because surfactants are amphiphilic, they primarily play a role in stabilizing the various components of the wetting agent. The complex composition of wetting agents often leads to problems such as aggregation and precipitation after mixing, negatively impacting the normal demarcation process and the uniformity of the wetting agent application. Adding an appropriate amount of surfactant effectively resolves these issues. The surfactant of this invention may be pyrrolidone and its derivatives and / or pyridinium salts and their derivatives, possessing excellent amphiphilicity and being the most common surfactants in industry, thus ensuring good stability of the wetting agent system. At the same time, if the amount of surfactant used in the wetting agent is too small, the wetting agent will settle, resulting in uneven surface application, ultimately negatively affecting the performance of the glass fibers. If too much is used, after reaching the "saturation concentration," the excess becomes non-functional, indirectly increasing manufacturing costs. Furthermore, many surfactants are electrically charged, but the matrix resin is not charged, and excessive charge concentration negatively impacts the penetration of the resin into the glass fibers; therefore, there is a specific requirement for the amount of surfactant used. In some embodiments, the percentage of the solid content of the surfactant relative to the total solid content of the wetting agent may be controlled to 1% to 6%, 1% to 5%, 2% to 5%, or even 2% to 4%.

[0047] The leveling agent effectively reduces surface tension and improves the overall penetration of the wetting agent, thereby increasing the rate at which the epoxy resin penetrates the glass fibers. Furthermore, by improving the coverage of the wetting agent, the leveling agent can form a flat, smooth, and uniform coating during the film formation process by the wetting agent, thereby indirectly enhancing the interfacial bonding between the glass fibers and the epoxy resin. The leveling agent selected in this invention may be a polyacrylate and / or organosiloxane leveling agent. These two types of leveling agents not only promote the flow and leveling of the coating film but also do not adversely affect the interlayer adhesion of the coating film and have a partial defoaming effect. The polyacrylate may include one or two of epoxy-modified polyacrylate and amino-modified polyacrylate, and the organosiloxane leveling agent may include one or two of epoxy- and polyether-modified copolymers and epoxy- and polyester-modified copolymers. At the same time, the amount of leveling agent used must be strictly controlled, as too much or too little leveling agent will have adverse effects. If too much leveling agent is used and the concentration exceeds the saturation level, the cost of the wetting agent will increase, and if too little leveling agent is used, the surface tension cannot be effectively reduced, the uniformity of the wetting agent coating cannot be guaranteed, and the penetration of glass fibers will be fundamentally negatively affected. In some examples, the percentage of the solid content of the leveling agent relative to the total solid content of the wetting agent may be controlled to 1% to 5%, 1% to 4%, or even 2% to 4%.

[0048] In this invention, the use of an interfacial enhancer is also an important technical point. Thick fabrics often have a high glass fiber content after injection, which significantly reduces the fatigue resistance of the composite material. Therefore, it is necessary to introduce an additive that improves interfacial bonding to improve fatigue resistance, and an interfacial enhancer can perform a similar function. In this invention, the interfacial enhancer can be selected from silica nanoparticles and / or alumina nanoparticles. Specifically, the interfacial enhancer in this invention is nanoscale silica particles, and the silica surface has a very large number of silicone hydroxyl groups that can react with glass fibers and silicone hydroxyl groups in the silane coupling agent, as well as participate in the reaction between the epoxy resin and the amine curing agent, thus performing a very good bonding action. Furthermore, the attachment of nanoscale silica increases the specific surface area of ​​the glass fibers, increases the bonding sites between the glass fibers and the epoxy resin, and can improve the interfacial bonding action and the mechanical properties and fatigue resistance of the final composite material. Because of its small size, nanoscale silica has very good dispersibility in water and does not require additional treatment. The amount of silica interface enhancer used must be controlled within a certain range. If the amount used is too small, the increase in specific surface area and bonding sites is small, and the enhancement of the interfacial bonding between the reinforced glass fiber and the resin is not significant. If the amount used is too large, there will be too many "protrusions" on the surface of the glass fiber, which will negatively affect the wear resistance of the glass fiber, and the drawing process will not be smooth, leading to problems such as increased fluffing. In some examples, the percentage of the solid content mass of the interface enhancer relative to the total mass of the solid components of the wetting agent may be controlled to 1% to 6%, 1% to 5%, 2% to 5%, or even 2% to 4%.

[0049] Another key point of the present invention is the use of a wetting agent. The wetting agent significantly reduces the surface tension of the wetting agent, increases the penetration rate of the epoxy resin into the glass fibers, enhances the effect, and strengthens the interfacial bond between the glass fibers and the matrix resin, thereby improving the mechanical properties of the composite material. The wetting agent of the present invention may be an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative. Specifically, the wetting agent of the present invention is an acetylene glycol-based wetting agent. Acetylene glycol-based wetting agents have very good dispersibility, can reduce surface tension and enhance adhesion between glass fibers and epoxy resin, and have low-foaming / defoaming properties, effectively ensuring the penetration state of glass fibers into the epoxy resin. At the same time, it is necessary to control the amount of wetting agent used. If too much wetting agent is used, the wetting effect will saturate, leading to high costs and increased costs for the wetting agent. If too little is used, it will negatively affect the wetting effect, thereby negatively affecting the penetration rate and effect of glass fibers into the epoxy resin. In some embodiments, the percentage of the solid content of the wetting agent relative to the total mass of the solid components of the wetting agent may be controlled to 1% to 5%, 1% to 4%, 2% to 4%, or even 2% to 3%.

[0050] Defoaming agents are primarily used to remove bubbles generated during the preparation and circulation processes of glass fiber wetting agents. During the preparation and circulation of glass fiber wetting agents, the presence of emulsifiers and surfactants generates a large amount of bubbles, which negatively affect the distribution of the wetting agent on the oil application roller, and further negatively impact application uniformity and the normal manufacturing process. Defoaming agents can effectively prevent bubble generation and ensure the normal manufacturing of glass fibers. The defoaming agent of the present invention may be an organic silicone composite and / or a polyether-based defoaming agent; specifically, the defoaming agent is an organic silicone composite. Furthermore, the amount of defoaming agent used must be controlled within a certain range. If too much is used, the defoaming effect saturates, and the excess increases costs. If too little is used, the defoaming effect is not significant, negatively impacting the penetration effect of the glass fiber and epoxy resin. In some embodiments, the percentage of the solid content of the antifoaming agent relative to the total mass of the solid components of the wetting agent may be controlled to 1% to 5%, 2% to 4%, or even 2% to 3%.

[0051] Through experiments, the inventors discovered that glass fiber yarn products manufactured by blending the film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoamer, and silane coupling agent of the present invention in appropriate blending ratios exhibit high cohesion, flexibility and high dispersibility after being subjected to a certain tension, rapid penetration rate and good penetration effect with epoxy resin, high interfacial compatibility between glass fiber and resin, suitability for weaving processes, and particularly suitability for the manufacture of thick wind-blown braided fabrics. Furthermore, they found that composite materials obtained by vacuum-injecting such fabrics with epoxy resin exhibit high static mechanical properties and fatigue resistance.

[0052] The pH adjusting agent of the present invention is mainly used for hydrolysis of the silane coupling agent and adjustment of the pH value of the wetting agent to control the pH value of the wetting agent within the range of 6 to 7. The pH adjusting agent in the present invention may be glacial acetic acid and / or citric acid, and specifically glacial acetic acid. In some examples, the percentage of the solid content mass of the pH adjusting agent relative to the total mass of the solid components of the wetting agent may be controlled to 1% to 7%, to 2% to 6%, or even to 2% to 5%.

[0053] In some examples, the percentage of the solid content of each active ingredient in the wetting agent relative to the total solid content of the wetting agent was as follows: silane coupling agent 7%-25%, film-forming agent 50%-75%, lubricant 7%-14%, surfactant 1%-5%, leveling agent 1%-4%, interface enhancer 1%-5%, wetting agent 1%-4%, defoaming agent 2%-4%, and pH adjuster 2%-6%.

[0054] In some examples, the percentage of the solid content of each active ingredient in the wetting agent relative to the total solid content of the wetting agent was as follows: silane coupling agent 9%-21%, film-forming agent 52%-73%, lubricant 7%-13%, surfactant 2%-5%, leveling agent 2%-4%, interface enhancer 2%-5%, wetting agent 2%-4%, defoaming agent 2%-3%, and pH adjuster 2%-6%.

[0055] In some examples, the percentage of the solid content of each active ingredient in the wetting agent relative to the total solid content of the wetting agent was as follows: silane coupling agent 10%~16%, film-forming agent 55%~72%, lubricant 7%~12%, surfactant 2%~4%, leveling agent 2%~4%, interface enhancer 2%~4%, wetting agent 2%~3%, defoaming agent 2%~3%, and pH adjuster 2%~5%.

[0056] The beneficial effects of selecting the above-mentioned ranges for the content of each component in the glass fiber wetting agent provided by the present invention will be explained by showing specific experimental data with reference to examples.

[0057] The following are examples of preferred value ranges for each component contained in the glass fiber wetting agent according to the present invention. [Examples]

[0058] Preferred example 1 The glass fiber wetting agent contains active ingredients and water, with a solid content of 4.0% to 6.0%. The active ingredients include a silane coupling agent, film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoaming agent, and pH adjuster. The percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%. Among these, the silane coupling agent is characterized by being a mixture of a first silane coupling agent, which is an aminosilane coupling agent, and a second silane coupling agent, which is an epoxysilane coupling agent.

[0059] Preferred example 2 The glass fiber wetting agent contains active ingredients and water, with a solid content of 4.0% to 6.0%. The active ingredients include a silane coupling agent, film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoaming agent, and pH adjuster. The percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%. The film-forming agent is characterized by being a mixture of a first film-forming agent, which is a bisphenol A type epoxy resin, and a second film-forming agent, which is a polyurethane resin.

[0060] Preferred example 3 The glass fiber wetting agent contains active ingredients and water, with a solid content of 4.0% to 6.0%. The active ingredients include a silane coupling agent, film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoaming agent, and pH adjuster. The percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%. The silane coupling agent is a mixture of a first silane coupling agent, which is an aminosilane coupling agent, and a second silane coupling agent, which is an epoxysilane coupling agent, and the film-forming agent is a mixture of a first film-forming agent, which is a bisphenol A type epoxy resin, and a second film-forming agent, which is a polyurethane resin.

[0061] Preferred example 4 The glass fiber wetting agent contains active ingredients and water, with a solid content of 4.0% to 6.0%. The active ingredients include a silane coupling agent, film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoaming agent, and pH adjuster. The percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%. The lubricant is a polyethyleneimine-based lubricant, the surfactant is a polypyrrolidone-based surfactant, the leveling agent is a modified polyacrylate, the interface enhancer is silica nanoparticles, the wetting agent is an acetylene glycol-based wetting agent, the defoaming agent is an organosilicone composite, and the pH adjuster is acetic acid and / or citric acid.

[0062] Preferred example 5 The glass fiber wetting agent contains active ingredients and water, with a solid content of 4.0% to 6.0%. The active ingredients include a silane coupling agent, film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoaming agent, and pH adjuster. The percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%. The silane coupling agent is a mixture of a first silane coupling agent, which is an aminosilane coupling agent, and a second silane coupling agent, which is an epoxysilane coupling agent; the film-forming agent is a mixture of a first film-forming agent, which is a bisphenol A type epoxy resin, and a second film-forming agent, which is a polyurethane resin; the lubricant is a polyethyleneimine-based lubricant and / or fatty acid amide and its derivatives; the surfactant is pyrrolidone and its derivatives and / or pyridinium salt and its derivatives; the leveling agent is a modified polyacrylate and / or modified organosiloxane; the interface enhancer is silica nanoparticles and / or alumina nanoparticles; the wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative; the defoaming agent is an organosilicon composite and / or a polyether-based defoaming agent; and the pH adjuster is citric acid and / or glacial acetic acid.

[0063] Preferred example 6 The glass fiber wetting agent contains active ingredients and water, with a solid content of 4.0% to 6.0%. The active ingredients include a silane coupling agent, film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoaming agent, and pH adjuster. The percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%. The silane coupling agent is a mixture of a first silane coupling agent, which is an aminosilane coupling agent, and a second silane coupling agent, which is an epoxysilane coupling agent. The film-forming agent is a mixture of a first film-forming agent, which is a bisphenol A type epoxy resin, and a second film-forming agent, which is a polyurethane resin. The mass ratio C1 of the first silane coupling agent to the second silane coupling agent is 1:5 to 1:3, and the mass ratio C2 of the first film-forming agent to the second film-forming agent is 1:1 to 2:1.

[0064] Preferred example 7 The glass fiber wetting agent contains active ingredients and water, with a solid content of 4.0% to 6.0%. The active ingredients include a silane coupling agent, film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, defoaming agent, and pH adjuster. The percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactants 1%~6%, Leveling agent 1%~5%, Interface enhancer 1%~6%, Humectant 1%~5%, Defoaming agent 1%~5%, The pH adjuster is present in a concentration of 1% to 7%. Of these, the silane coupling agent is a mixture of a first silane coupling agent, which is an aminosilane coupling agent, and a second silane coupling agent, which is an epoxysilane coupling agent; the film-forming agent is a mixture of a first film-forming agent, which is a bisphenol A type epoxy resin, and a second film-forming agent, which is a polyurethane resin; the mass ratio C1 of the first silane coupling agent to the second silane coupling agent is 1:5 to 1:3; the mass ratio C2 of the first film-forming agent to the second film-forming agent is 1:1 to 2:1; and the lubricant is polyethyleneimine. The invention is characterized by using a lubricant and / or fatty acid amide and its derivatives as a surfactant, pyrrolidone and its derivatives and / or pyridinium salt and its derivatives as a leveling agent, modified polyacrylate and / or modified organosiloxane as a leveling agent, silica nanoparticles and / or alumina nanoparticles as an interface enhancer, acetylene glycol-based wetting agent and / or modified polyoxyethylene derivative as a wetting agent, organosilicon composite and / or polyether-based defoaming agent as an antifoaming agent, and citric acid and / or glacial acetic acid as a pH adjuster.

[0065] The methods for producing the glass fiber wetting agents of Preferred Examples 1 to 7 are as follows: Step 1S involves adding 30% to 45% of the total mass of the wetting agent to a container with water, then sequentially adding the pH adjuster and the silane coupling agent, pre-dispersing the silane coupling agent, and stirring until the solution becomes clear to obtain a pre-dispersion of the silane coupling agent. Step 2S involves diluting the film-forming agent with 3 to 4 times its mass of water, diluting the lubricant with 5 to 6 times its mass of water at 55°C, diluting the surfactant with 4 to 6 times its mass of warm water at 55°C, stirring and diluting the leveling agent with 4 to 6 times its mass of warm water at 55°C, diluting the interface enhancer with 5 to 8 times its mass of water, diluting the wetting agent with 5 to 6 times its mass of water at 55°C, and diluting the defoaming agent with 3 to 5 times its mass of water. Step 3S includes mixing a silane coupling agent pre-dispersion with diluted film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, and defoaming agent, replenishing the remaining water in the container, and stirring uniformly.

[0066] The specific blending ratios for some examples of the glass fiber wetting agent of the present invention are shown in Table 1. The solid content of Examples 1 to 4 is 5.0%, the solid content of Examples 5 to 8 is 4.0%, the solid content of Examples 9 to 12 is 6.0%, the solid content of Example 13 is 4.5%, and the solid content of Example 14 is 5.5%. The values ​​in Table 1 represent the percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent, and the C1 and C2 values ​​are the ratio values ​​of the solid content percentages of the corresponding active ingredients.

[0067] [Table 1-1]

[0068] [Table 1-2]

[0069] [Table 1-3]

[0070] Furthermore, this specification provides for the purpose of illustrating the technical solution of the present invention, including a comparative example.

[0071] Comparative Example 1 The solid content of the wetting agent is 5.5%. The percentage of the mass of each solid component relative to the total mass of the solid components is: Amidosilane coupling agent 15.0%, Film-forming agent (epoxy resin) 60.0%, Lubricant (fatty acid amide lubricant) 8.0%, Surfactant (quaternary ammonium salt-based surfactant) 3.0%, Antifoaming agent (organic silicone composite) 6.0%, The pH adjuster (citric acid) is 8.0%.

[0072] The manufacturing method for Comparative Example 1 is: Step (1) involves adding 30% to 45% of the total volume of water to a container with a variable-speed mixer, then sequentially adding the pH adjuster and the amidosilane coupling agent, and stirring until the solution becomes clear. Step (2) involves diluting the film-forming agent with 3 to 5 times its mass of water and then placing it in a container. Step (3) involves diluting the lubricant with 4 to 6 times its mass in 55°C water and then placing it in a container. Step (4) involves diluting the surfactant with 4 to 5 times its mass of water and then placing it in a container. Step (5) involves diluting the defoaming agent with 3 to 5 times its mass in water and then placing it in a container. Finally, the process includes step (6) of refilling the container with the remaining water, stirring it uniformly, and obtaining the product.

[0073] Table 2 records the performance test results of the glass fiber wetting agents of Examples 1-18 and Comparative Example 1 of the present invention.

[0074] [Table 2-1]

[0075] [Table 2-2]

[0076] [Table 2-3]

[0077] As can be seen from the above examples, by selecting the type and designing the content of each component of the wetting agent, a wetting agent blending ratio that satisfies the requirements can be obtained. Compared to Comparative Example 1, the glass fibers produced in Examples 1-18 of the present invention have good performance, with less fuzz on the glass fibers, less fraying after the yarn is subjected to tension, flexible yarn quality, fast penetration rate in epoxy resin, good interfacial bonding effect, and the produced composite material has excellent mechanical properties and fatigue resistance.

[0078] As can be seen from the above, the glass fiber yarn produced by applying the wetting agent is flexible, disperses very well after being subjected to a certain tension, penetrates quickly and completely with epoxy resin, has very high interfacial compatibility, is suitable for knitting processes, is particularly suitable for the production of thick wind blade base materials, and can effectively solve the problem that resin penetration of thick fabrics is slow and fatigue resistance is reduced. The composite material obtained by vacuum-injecting a fabric produced using the wetting agent with epoxy resin has very high mechanical properties and fatigue resistance.

[0079] In this invention, the solid content mass of each active ingredient refers to the mass of non-water substances in each active ingredient, and is not limited to solid components.

[0080] Finally, it should be noted that in this specification, the terms “include,” “contain,” or any other variation thereof are intended to cover non-exclusive inclusion, thereby including not only those elements but also other elements not explicitly listed, or elements specific to such process, method, article, or equipment. Unless otherwise limited, an element limited by the phrase “includes one of…” does not preclude the presence of other identical elements in a process, method, article, or equipment containing the described element.

[0081] The above embodiments are merely for illustrating the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art may modify the technical solutions described in the above embodiments or make equivalent substitutions for some of the technical features therein, but they should understand that such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of each embodiment of this application.

[0082] Industrial applicability The present invention provides a glass fiber wetting agent. Glass fiber yarn produced using the wetting agent of the present invention exhibits good bundling properties, becomes flexible and highly dispersible after being subjected to a certain tension, has a very fast penetration rate with epoxy resin, exhibits good penetration effect, has high interfacial compatibility between glass fiber and resin, is suitable for knitting processes, and is particularly suitable for the production of thick wind-blown braided fabrics. The composite material obtained by vacuum-injecting the fabric with epoxy resin exhibits high static mechanical properties and fatigue resistance.

Claims

1. The wetting agent contains an active ingredient and water, with a solid content of 4.0% to 6.0%, and the active ingredient includes a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, an antifoaming agent, and a pH adjuster, and the percentage of the solid content of each active ingredient relative to the total solid content of the wetting agent is: Silane coupling agent 6% to 26%, Film-forming agent 45% to 78%, Lubricant 5% to 15%, Surfactants 1% to 6%, Leveling agent 1% to 5%, Interface enhancer 1% to 6%, Humectant 1% to 5%, Antifoaming agent 1% to 5%, pH adjuster 1% to 7% And, The film-forming agent is a mixture of a first film-forming agent and a second film-forming agent, wherein the first film-forming agent is a bisphenol A type epoxy resin with a molecular weight of 2000 to 3000, and the second film-forming agent is a polyurethane resin with a molecular weight of 200 to 400. The wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative. A glass fiber wetting agent characterized by the following features.

2. The percentage of the solid content mass of each active ingredient relative to the total solid content mass of the wetter in the aforementioned wetter is: Silane coupling agent 7% to 25%, Film-forming agent 50% to 75%, Lubricant 7% to 14%, Surfactants 1% to 5%, Leveling agent 1% to 4%, Interface enhancer 1% to 5%, Humectant 1% to 4%, Antifoaming agent 2% to 4%, pH adjuster 2% to 6%, The glass fiber wetting agent according to claim 1, characterized in that it is the same as described above.

3. The glass fiber wetting agent according to claim 1, characterized in that the silane coupling agent is a mixture of a first silane coupling agent which is an aminosilane coupling agent and a second silane coupling agent which is an epoxysilane coupling agent.

4. The glass fiber wetting agent according to claim 3, characterized in that the mass ratio C1 of the first silane coupling agent and the second silane coupling agent is 1:5 to 1:

3.

5. The glass fiber wetting agent according to claim 3, characterized in that the first silane coupling agent is aminopropyltriethoxysilane and / or γ-aminopropyltrimethoxysilane, and the second silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

6. The glass fiber wetting agent according to claim 1, characterized in that the mass ratio C2 of the first film-forming agent and the second film-forming agent is 1:1 to 2:

1.

7. The glass fiber wetting agent according to claim 1, characterized in that the lubricant is a polyethyleneimine-based lubricant and / or a fatty acid amide derivative, and the surfactant is a pyrrolidone derivative and / or a pyridinium salt derivative.

8. The glass fiber wetting agent according to claim 1, characterized in that the defoaming agent is an organic silicone composite and / or a polyether-based defoaming agent, and the leveling agent is a modified polyacrylate and / or a modified organosiloxane.

9. The glass fiber wetting agent according to claim 1, characterized in that the interface enhancing agent is silica nanoparticles and / or alumina nanoparticles.

10. A method for producing a glass fiber wetting agent according to any one of claims 1 to 9, Add 30% to 45% of the total mass of the wetting agent to a container with water, then add the pH adjuster and the silane coupling agent in order, pre-disperse the silane coupling agent, stir until the solution becomes clear, and obtain a pre-dispersion of the silane coupling agent. A dilution step of film-forming agents, lubricants, surfactants, leveling agents, interface enhancers, wetting agents, and defoaming agents, each of which is diluted with water, The steps include adding the diluted film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent, and defoaming agent to the silane coupling agent predispersion, replenishing the remaining water, and stirring uniformly to obtain a glass fiber wetting agent, A manufacturing method characterized by including the following.

11. A glass fiber product having a coating film formed by a glass fiber wetting agent according to any one of claims 1 to 9.

12. An epoxy resin composite material comprising the glass fiber product according to claim 11.

13. Use of the epoxy resin composite material according to claim 12 in the field of wind power generation.

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