Glass fiber impregnating compound composition, glass fiber impregnating compound, glass fiber direct yarn product and application

Abstract

The invention provides a glass fiber impregnating compound composition, a glass fiber impregnating compound, a glass fiber direct yarn product and application. The glass fiber impregnating compound composition comprises effective components and water, and the effective components comprise a silane coupling agent, a film-forming agent A, a film-forming agent B, a lubricant, a flexibilizer, a wetting agent and a pH value regulator; the film-forming agent A is a water-based bisphenol A epoxy resin emulsion, and the film-forming agent B is a water-based polyether polyurethane modified aliphatic epoxy emulsion; the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent, the first silane coupling agent is an epoxy silane coupling agent, the second silane coupling agent is an amino-containing silane coupling agent, and the mass ratio of the film-forming agent A to the film-forming agent B is (2-4.5): 1. The problems that in the prior art, when glass fibers are applied to winding gas cylinders, abrasion resistance is insufficient, fuzzing is prone to occurring in the winding process, and due to incomplete resin permeation, the winding gas cylinders are prone to layering, cracking and other defects in the high-pressure environment are solved.

Description

Technical Field

[0001] This invention relates to the field of glass fiber technology, and more specifically, to a glass fiber sizing agent composition, a glass fiber sizing agent, glass fiber direct yarn products, and applications. Background Technology

[0002] In recent years, with the rapid development of the new energy industry, glass fiber reinforced composite materials have been widely used in the manufacture of energy storage cylinders. Their excellent mechanical properties, lightweight characteristics, and corrosion resistance make them an ideal material choice. However, due to the special winding method used in the processing of energy storage cylinders, the performance of the sizing agent used in the glass fiber direct yarn as the reinforcing material directly affects the mechanical properties, durability, and service life of the cylinder. This requires the fibers to possess excellent wear resistance, flexibility, rapid and complete resin impregnation, and high compressive strength and fatigue resistance in the finished product.

[0003] The current application of glass fiber in wound gas cylinders remains relatively limited, suffering from insufficient abrasion resistance, fuzzing during the winding process, and incomplete resin impregnation. This leads to defects such as delamination and cracking under high pressure. Currently, glass fiber is primarily used for outer shell reinforcement and protection, constituting only a small portion of the overall cylinder composition. To meet the diverse performance requirements of glass fiber winding for energy storage cylinders, providing excellent resin impregnation, good abrasion resistance, and bundling properties while ensuring superior pressure resistance and fatigue resistance, developing a suitable glass fiber yarn and impregnating agent for high-tensile winding of energy storage cylinders would offer significant economic benefits in increasing the application of glass fiber in energy storage cylinders and promoting the development of the energy storage industry. Summary of the Invention

[0004] The main objective of this invention is to provide a glass fiber impregnating agent composition, glass fiber impregnating agent, glass fiber direct yarn products and applications, in order to solve the problems of insufficient wear resistance, easy fuzzing during the winding process, and incomplete resin penetration when glass fiber is used to wind gas cylinders in the prior art, which leads to defects such as delamination and cracking of the wind-wound gas cylinders under high pressure.

[0005] To achieve the above objectives, according to one aspect of the present invention, a glass fiber impregnating composition is provided, comprising an active ingredient and water, wherein the active ingredient comprises, by weight percentage: 9.0%–18.0% of a silane coupling agent, 34.0%–55.0% of a film-forming agent A, 12.0%–20.0% of a film-forming agent B, 14.0%–24.0% of a lubricant, 3.0%–6.0% of a toughening agent, 0.5%–1.5% of a wetting agent, and 1.0%… The composition contains 5% to 2.5% pH adjuster; the solid content of the glass fiber impregnating agent composition is 5% to 9%, wherein film-forming agent A is an aqueous bisphenol A epoxy resin emulsion, film-forming agent B is an aqueous polyether-type polyurethane modified aliphatic epoxy emulsion; the silane coupling agent includes a first silane coupling agent and a second silane coupling agent, the first silane coupling agent is an epoxy-based silane coupling agent, the second silane coupling agent is an amino-containing silane coupling agent, and the mass ratio of film-forming agent A to film-forming agent B is (2 to 4.5):1.

[0006] Further, by mass percentage, the above-mentioned effective components include: 10.0%–16.0% silane coupling agent, 36.0%–52.0% film-forming agent A, 14.0%–20.0% film-forming agent B, 15.0%–22.0% lubricant, 3.0%–5.0% toughening agent, 0.5%–1.0% wetting agent, and 1.0%–2.0% pH adjuster; wherein the solid content of the glass fiber impregnating agent composition is 5.5%–8.5%, and the mass ratio of film-forming agent A to film-forming agent B is (2.5–4):1; preferably, the effective components include: 12.0%–16.0% silane coupling agent, 40.0%–50.0% film-forming agent A, 14.0%–18.0% film-forming agent B, and 16.0%–21.0% lubricant. The composition comprises 3.0%–4.5% toughening agent, 0.5%–1.0% wetting agent, and 1.0%–1.5% pH adjuster; wherein the solid content of the glass fiber impregnating agent composition is 6–8%; the mass ratio of film-forming agent A to film-forming agent B is (3–4):1; further, the preferred effective components include: 13.0%–16.0% silane coupling agent, 43.0%–48.0% film-forming agent A, 14.0%–16.0% film-forming agent B, 16.0%–20.0% lubricant, 3.0%–4.0% toughening agent, 0.5%–1.0% wetting agent, and 1.0%–1.5% pH adjuster; wherein the solid content of the glass fiber impregnating agent composition is 6–8%; and the mass ratio of film-forming agent A to film-forming agent B is (3–3.5):1.

[0007] Furthermore, the total solid mass of the film-forming agent A and film-forming agent B accounts for 50-72% of the total solid mass of the glass fiber impregnating agent composition, preferably 55-70%, more preferably 58-63%; and / or the molecular weight of film-forming agent A is 500-800, and the molecular weight of film-forming agent B is 2000-3500.

[0008] Further, the mass ratio of the first silane coupling agent and the second silane coupling agent is (2.5-4):1, preferably (2.5-3.5):1, and more preferably (2.5-3):1; wherein the first silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane; and / or the second silane coupling agent is selected from any one or more of γ-aminoethylaminopropyltrimethoxysilane and amino-based silane coupling agent oligomers.

[0009] Furthermore, the above-mentioned lubricant is a nonionic lubricant and / or an organosilicon lubricant, preferably selected from any one or more of fatty acid amide lubricants, alkyl-modified polyoxyethylene ether lubricants and polyether-modified organosilicon lubricants; and / or the pH adjuster is an acid, preferably citric acid.

[0010] Furthermore, the toughening agent mentioned above is a waterborne polyether-type polyurethane elastomer modified epoxy emulsion.

[0011] Furthermore, the aforementioned wetting agent is an acetylenic diol wetting agent and / or an aqueous organosilicone wetting agent.

[0012] According to another aspect of the present invention, a glass fiber sizing agent is provided, which is obtained by mixing a glass fiber sizing agent composition, wherein the glass fiber sizing agent composition is the glass fiber sizing agent composition described above.

[0013] According to another aspect of the present invention, a glass fiber direct yarn product produced by coating the glass fiber with the above-mentioned glass fiber sizing agent is provided.

[0014] According to another aspect of the present invention, the application of the above-described glass fiber direct yarn product in the winding of energy storage cylinders is provided.

[0015] By applying the technical solution of the present invention, through the synergistic effect of the above components, the glass fiber direct yarn produced by coating the glass fiber with the glass fiber impregnating agent composition has very good flexibility, is not easy to fuzz during use, has good smoothness, especially in epoxy resin system, it impregnates quickly and has strong penetration, has high bonding strength with resin, and excellent fatigue resistance, making it particularly suitable for winding and molding of energy storage gas cylinders. Detailed Implementation

[0016] It should be noted that, unless otherwise specified, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0017] As analyzed in the background section of this application, existing technologies used in winding gas cylinders suffer from problems such as insufficient wear resistance, easy fuzzing during the winding process, and incomplete resin penetration. These problems lead to defects such as delamination and cracking in gas cylinders under high pressure. To solve these problems, this application provides a glass fiber sizing agent composition, a glass fiber sizing agent, a glass fiber direct yarn product, and its application.

[0018] In a typical embodiment of this application, a glass fiber impregnating agent composition is provided, comprising an active ingredient and water. The active ingredient, by mass percentage, comprises: 9.0%–18.0% of a silane coupling agent, 34.0%–55.0% of a film-forming agent A, 12.0%–20.0% of a film-forming agent B, 14.0%–24.0% of a lubricant, 3.0%–6.0% of a toughening agent, 0.5%–1.5% of a wetting agent, and 1.0%–2% of a water. 0.5% pH adjuster; wherein, the solid content of the glass fiber impregnating agent composition is 5-9%, wherein film-forming agent A is a water-based bisphenol A epoxy resin emulsion, and film-forming agent B is a water-based polyether-type polyurethane modified aliphatic epoxy emulsion; the silane coupling agent includes a first silane coupling agent and a second silane coupling agent, the first silane coupling agent is an epoxy-based silane coupling agent, and the second silane coupling agent is an amino-containing silane coupling agent, and the mass ratio of film-forming agent A to film-forming agent B is (2-4.5):1.

[0019] Film-forming agents are the main components of glass fiber impregnation agents, protecting the glass fiber surface and improving its bundle structure, abrasion resistance, and bending resistance. Furthermore, the film-forming agent is a key factor determining the impregnation effect and bonding strength between the glass fiber and the matrix resin. This application uses a combination of film-forming agents A and B, which have good affinity with epoxy resin, ensuring full bonding between the glass fiber and the epoxy matrix resin with high bonding strength. Film-forming agent A is an aqueous epoxy emulsion, and film-forming agent B is an aqueous polyether-type polyurethane-modified aliphatic epoxy emulsion. Compared to traditional epoxy emulsion film-forming agents, the aqueous aliphatic polyurethane-modified epoxy film-forming agent used in this application does not contain benzene rings, possessing not only the elasticity of polyurethane but also the toughness of aliphatic epoxy, protecting the glass fiber from wear during use and exhibiting good flexibility. Film-forming agent A is a water-based bisphenol A type epoxy emulsion, which not only forms a uniform protective film on the glass fiber surface but also improves the compatibility between the fiber and the epoxy matrix resin, promotes rapid impregnation of the glass fiber in the epoxy, and imparts excellent bonding strength between the glass fiber and the matrix resin. Film-forming agent B is a water-based polyether-type polyurethane-modified aliphatic epoxy emulsion. Its molecular chain contains flexible aliphatic segments, providing excellent toughness to the sizing agent film. The polyurethane component helps improve the integrity of the sizing agent film coating on the glass fiber, providing strong protection to the glass fiber surface and effectively improving the yarn's bundleability and abrasion resistance. Both film-forming agents A and B contain epoxy segments, which help improve the compatibility between the sizing agent and the epoxy matrix resin, reducing interfacial bonding defects between the fiber and the matrix resin in glass fiber reinforced composite products. The combination of film-forming agent A and film-forming agent B not only enables the yarn to be quickly impregnated in epoxy resin, but also helps the sizing agent form a uniform and flexible protective film on the fiber surface, improving the yarn's bundle properties, abrasion resistance, and smoothness of use in high-tension winding molding.

[0020] Furthermore, this application requires control over the dosage relationship between film-forming agent A and film-forming agent B. Studies have found that an excessively high proportion of film-forming agent A can easily lead to insufficient toughness of the sizing agent during drying and a decrease in fiber bundle cohesion; an excessively high proportion of film-forming agent B can easily lead to excessive fiber stiffness and poor fiber impregnation in epoxy resin. Therefore, this application controls the mass ratio of film-forming agent A to film-forming agent B within the range of (2–4.5):1, thereby ensuring that the prepared glass fiber not only has good bundle cohesion and high wear resistance, but also penetrates quickly in epoxy resin, meeting various performance requirements for glass fiber. For example, the mass ratio of film-forming agent A to film-forming agent B is 2.5:1, 2.7:1, 3:1, 3.2:1, 3.5:1, 4:1, or 4.5:1.

[0021] This application uses a silane coupling agent, which acts as a bridge between the glass fiber surface and the sizing agent coating film. On one hand, the silanol groups generated by the hydrolysis of the silane coupling agent react with the hydroxyl groups on the glass fiber surface, filling microcracks and reducing brittle fracture of the glass fiber. On the other hand, the coupling agent's molecular structure contains epoxy and amino functional groups, which can react with the film-forming agent in the sizing agent and the matrix resin, thus becoming key to the strong bonding between the glass fiber, the sizing agent film, and the epoxy resin. Specifically, epoxy silane coupling agents have a small molecular weight and contain epoxy groups, exhibiting good compatibility with epoxy film-forming agents and facilitating uniform coating of the sizing agent on the glass fiber surface. Amino silane coupling agents can improve the mechanical strength and fatigue resistance of fiber-reinforced composites. Therefore, the coupling agent used in this application is a combination of epoxy silane coupling agents and amino silane coupling agents, possessing high reactivity and being crucial for improving the interfacial compatibility and interfacial bonding force between the glass fiber material and the epoxy resin. The amount of silane coupling agent must also be controlled within a suitable range. If the silane coupling agent content is too low, it will not be able to fully coat the glass fiber surface, and residual microcracks on the fiber surface will cause brittle fracture of the fiber, reducing the toughness of the composite. If the silane coupling agent content is too high, it will lead to excess silane coupling agent. Due to the high reactivity of the coupling agent, self-polymerization will occur during the film formation process of the sizing agent on the glass fiber surface, which will reduce the film uniformity of the sizing agent on the glass fiber surface, resulting in insufficient bonding between the glass fiber and the matrix resin, causing local defects in the composite material. Therefore, this application controls the silane coupling agent content within the above range.

[0022] Lubricants impart softness and smoothness to glass fibers, serving as crucial auxiliary materials to protect them from damage during production and post-processing. Excessive lubricant content results in a softer sizing film, insufficient bonding strength between the sizing agent and the glass fibers, reduced fiber bundle cohesion, and increased fraying and fuzzing during use. Conversely, insufficient lubricant content leads to inadequate smoothness, reduced abrasion resistance, and hinders fiber winding applications. Therefore, this application controls the lubricant content within the aforementioned range.

[0023] One of the key aspects of this application is the introduction of a toughening agent. Toughening agents are crucial raw materials for improving the bonding toughness between glass fibers and the matrix resin, effectively enhancing the tensile strength and fatigue resistance of composite materials. The amount of toughening agent used must be controlled within a suitable range. Excessive use will result in a larger molecular weight, reducing the uniformity of the wetting agent coating on the fiber surface and hindering the complete encapsulation of the glass fiber by the film-forming agent. Insufficient use will lead to a lower toughening effect, resulting in insufficient compressive strength and fatigue resistance in the finished product. Therefore, this application controls the toughening agent content within the aforementioned range.

[0024] Another key aspect of this application is the addition of an appropriate amount of wetting agent. The main function of the wetting agent is to significantly reduce surface tension. Adding an appropriate amount of wetting agent to the impregnating agent can improve the film uniformity of the impregnating agent, improve the impregnation speed and effect of glass fiber in the matrix resin, enhance the interfacial bonding integrity between glass fiber and resin, reduce local defects caused by insufficient impregnation, and ultimately improve the mechanical strength of the composite material.

[0025] In addition, this application also adds a certain amount of pH adjuster to regulate the pH value of the glass fiber impregnating agent composition.

[0026] In summary, through the synergistic effect of the above components, the glass fiber direct yarn produced by coating the glass fiber with the sizing agent obtained by this glass fiber sizing agent composition has very good flexibility, is not easy to fuzz during use, has good smoothness, and is especially fast and has strong penetration in epoxy resin system. It has high bonding strength with resin and excellent fatigue resistance, making it particularly suitable for winding and molding of energy storage gas cylinders.

[0027] To further enhance the synergistic effect of the effective components in the glass fiber sizing agent composition and enable each component to exert better performance, the effective components, by mass percentage, include: 10.0%–16.0% silane coupling agent, 36.0%–52.0% film-forming agent A, 14.0%–20.0% film-forming agent B, 15.0%–22.0% lubricant, 3.0%–5.0% toughening agent, 0.5%–1.0% wetting agent, and 1.0%–2.0% pH adjuster; wherein the solid content of the glass fiber sizing agent composition is 5.5%–8.5%, and the mass ratio of film-forming agent A to film-forming agent B is (2.5–4):1; preferably, the effective components include: 12.0%–16.0% silane coupling agent, 40.0%–50.0% film-forming agent A, and 14.0%–18.0% film-forming agent B. The composition comprises: agent B, 16.0%–21.0% lubricant, 3.0%–4.5% toughening agent, 0.5%–1.0% wetting agent, and 1.0%–1.5% pH adjuster; wherein the solid content of the glass fiber impregnating agent composition is 6–8%; the mass ratio of film-forming agent A to film-forming agent B is (3–4):1; further, preferably, the effective components include: 13.0%–16.0% silane coupling agent; 43.0%–48.0% film-forming agent A; 14.0%–16.0% film-forming agent B, 16.0%–20.0% lubricant, 3.0%–4.0% toughening agent, 0.5%–1.0% wetting agent, and 1.0%–1.5% pH adjuster; wherein the solid content of the glass fiber impregnating agent composition is 6–8%; the mass ratio of film-forming agent A to film-forming agent B is (3–3.5):1.

[0028] In one embodiment of this application, the total solid mass of the film-forming agent A and film-forming agent B accounts for 50-72% of the total solid mass of the glass fiber impregnating agent composition, preferably 55-70%, more preferably 58-63%; and / or the molecular weight of film-forming agent A is 500-800, and the molecular weight of film-forming agent B is 2000-3500.

[0029] The amount of film-forming agent needs to be controlled within a suitable range. If the amount of film-forming agent is too small, the integrity of the coating of the sizing agent on the glass fiber surface will decrease, resulting in low film strength and problems such as insufficient fiber bundles, low wear resistance, and poor bending resistance. If the amount of film-forming agent is too large, it will lead to insufficient smoothness of the glass fiber, reduced drawing smoothness, easy fuzzing of the glass fiber during use, and low high-speed shear resistance of the yarn.

[0030] Experiments revealed that if the molecular weight of the film-forming agent is too low, the sizing agent's bonding and protective force on the yarn is insufficient, reducing the fiber bundle structure. Conversely, if the molecular weight of the film-forming agent is too high, the uniformity of the sizing agent's film formation decreases, and the wetting rate with the resin slows down, resulting in insufficient bonding strength between the fiber and the resin, failing to meet the high tensile and compressive strength requirements of the product. Therefore, this application limits the molecular weight of film-forming agent A to 500–800, for example, 500, 550, 600, 650, 700, 750, or 800; and the molecular weight of film-forming agent B to 2000–3500, for example, 2000, 2200, 2500, 2700, 3000, 3200, or 3500. This application uses a combination of two film-forming agents, which allows the glass fiber to simultaneously possess excellent flexibility and abrasion resistance, good compatibility with epoxy resin, rapid impregnation, and strong bonding force. The glass fibers obtained by subsequent sizing agent coating not only have high smoothness of use, but also can be quickly and completely impregnated in the matrix resin. This allows the glass fibers to meet the high-tension winding process requirements of energy storage cylinders and provide the composite material with excellent tensile strength and fatigue resistance. For example, the total solid mass of film-forming agent A and film-forming agent B accounts for 50%, 52%, 55%, 58%, 60%, 63%, 65%, 70%, or 72% of the total solid mass of the glass fiber sizing agent composition.

[0031] In one embodiment of this application, the mass ratio of the first silane coupling agent and the second silane coupling agent is (2.5-4):1, preferably (2.5-3.5):1, and further preferably (2.5-3):1; wherein the first silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane; and / or the second silane coupling agent is selected from any one or more of γ-aminoethylaminopropyltrimethoxysilane and amino-based silane coupling agent oligomers.

[0032] Epoxy-based silane coupling agents possess epoxy reactivity and can form chemical bonds with the epoxy resin matrix, enabling the fiber to bond tightly with the matrix resin and enhancing mechanical strength. Amino-based silane coupling agents not only exhibit strong reactivity and good adhesion to the glass fiber surface, but also react with the matrix epoxy resin, improving the interfacial stability between the fiber and matrix materials and further enhancing the fatigue resistance of the fiber composite material. Specifically, the first coupling agent is preferably 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and the second coupling agent is an amino-based silane coupling agent oligomer. More preferably, the first coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane, and the second coupling agent is an amide-based silane coupling agent oligomer. When using coupling agents of the above types, especially the first and second coupling agents, it is necessary to control their dosage ratio. If the proportion of the first silane coupling agent is too high, it can easily lead to insufficient bonding toughness between the fiber and the matrix resin, resulting in low fatigue resistance. Conversely, if the proportion of the second silane coupling agent is too high, the number of reactive sites in the coupling agent will be relatively small, easily causing insufficient reaction between the coupling agent and the glass fiber surface, thus reducing the bonding strength between the fiber and the epoxy matrix resin. Therefore, this application controls the mass ratio of the first and second silane coupling agents to the range described above. For example, the mass ratio of the first and second silane coupling agents is 2.5:1, 2.7:1, 3:1, 3.2:1, 3.5:1, or 4:1.

[0033] In one embodiment of this application, the lubricant is a nonionic lubricant and / or an organosilicon lubricant, preferably selected from any one or more of fatty acid amide lubricants, alkyl-modified polyoxyethylene ether lubricants, and polyether-modified organosilicon lubricants; and / or the pH adjuster is an acid, preferably citric acid.

[0034] The above-mentioned types of lubricants (such as polyethylene glycol oleate lubricants) have good water dispersibility and excellent lubrication effect, which can significantly improve the wear of glass fibers during the drawing and forming process. At the same time, polyether-modified silicone lubricants, because they contain low surface energy polymer silicones, can effectively reduce the coefficient of friction, reduce fiber damage during use, ensure good smoothness of yarn during use, prevent pilling, and ensure good flowability.

[0035] In one embodiment of this application, the toughening agent is a waterborne polyether-type polyurethane elastomer modified epoxy emulsion.

[0036] The toughening agents described above contain long-chain flexible polyurethane segments and epoxy segments, which have good compatibility with film-forming agents and strong affinity with glass fiber surfaces, thus helping to improve the flexibility of glass fibers.

[0037] In this application, water is the dispersed phase of each effective component in the glass fiber wetting agent, and deionized water is selected.

[0038] It should be noted that, in this application, the solid mass of the effective component in emulsion form refers to the mass of the emulsion after it has been dried by heat under certain conditions.

[0039] In one embodiment of this application, the wetting agent is an acetylenic diol wetting agent and / or an aqueous organosilicone wetting agent.

[0040] The wetting agent used in this application is preferably one of the above types, which has strong penetrability and helps to reduce the surface tension of the wetting agent after film formation, thereby promoting the rapid impregnation of glass fiber in the matrix resin.

[0041] In another typical embodiment of this application, a glass fiber impregnating agent is provided, which is obtained by mixing a glass fiber impregnating agent composition, wherein the glass fiber impregnating agent composition is the glass fiber impregnating agent composition described above.

[0042] The sizing agent obtained by using the glass fiber impregnating agent composition described above in this application enables the prepared glass fibers to not only have good bundle properties and high wear resistance, but also to penetrate quickly in epoxy resin, thus meeting various performance requirements of glass fibers.

[0043] In another typical embodiment of this application, a glass fiber direct yarn product produced by coating the glass fiber with the above-mentioned glass fiber sizing agent is provided.

[0044] Glass fiber direct yarn produced by coating with the sizing agent obtained by the above-mentioned glass fiber sizing agent composition of this application has very good flexibility, is not easy to fuzz during use, has good smoothness, especially in epoxy resin system, it has fast impregnation and strong penetration, high bonding strength with resin, and excellent fatigue resistance, making it particularly suitable for winding molding of energy storage gas cylinders.

[0045] In another typical embodiment of this application, the application of the above-mentioned glass fiber direct yarn product in winding energy storage cylinders is provided.

[0046] The glass fiber direct yarn of this application has excellent flexibility, is not prone to fuzzing during use, has good smoothness, and is especially fast and has strong penetration in epoxy resin systems. It has high bonding strength with resin and excellent fatigue resistance, making it particularly suitable for winding molding of energy storage gas cylinders.

[0047] In some optional embodiments, a method for preparing the aforementioned glass fiber impregnating agent is provided, comprising the following steps:

[0048] 1S: Add water at 40 times the amount of coupling agent to the container, then add pH adjuster and silane coupling agent in sequence, stir for more than 30 minutes until the solution is clear, and obtain coupling agent dispersion;

[0049] 2S: Dissolve and disperse the lubricant in water at a temperature of 45-50°C at 3-5 times its volume to obtain a lubricant dilution. Add the lubricant dilution to the container of 1S and stir evenly to obtain a coupling agent-lubricant dispersion.

[0050] 3S: Toughening agent, wetting agent, film-forming agent A and film-forming agent B are diluted with 3 to 5 times their own weight of water, then added to the container of 1S, stirred evenly, and then the remaining water is added to obtain glass fiber impregnation agent.

[0051] It should be noted that the terms "1S" and "2S" in this document are only used to more clearly explain the technical solution of this application, and are not intended to limit this application; in the preparation process, the order of steps 1S and 2S can be adjusted according to the actual situation. Moreover, the dilution of toughening agent, wetting agent, film-forming agent A and film-forming agent B with water can also be adjusted according to actual needs, which will not be elaborated here.

[0052] The beneficial effects of this application will be further illustrated below with reference to the embodiments.

[0053] Example 1

[0054] 1S: Add water at 40 times the amount of coupling agent to the container, then add pH adjuster and silane coupling agent in sequence, stir for more than 30 minutes until the solution is clear, and obtain coupling agent dispersion;

[0055] 2S: Dissolve and disperse the lubricant in water at 50°C at 4 times its volume to obtain a lubricant dilution. Add the lubricant dilution to the container in 1S and stir evenly to obtain a coupling agent-lubricant dispersion.

[0056] 3S: Toughening agent, wetting agent, film-forming agent A and film-forming agent B are diluted with 5 times their own weight of water in sequence, and then added to the container of 1S. Stir well, and then add the remaining water to obtain glass fiber impregnation agent.

[0057] To more clearly explain the technical solution of this application, the following are examples and comparative examples of the glass fiber impregnating agent composition of this application. The specific formulations of Examples 1 to 14 and Comparative Examples 1 to 2 are shown in Table 1. The preparation methods of Examples 2 to 14 and Comparative Examples 1 to 2 are similar to those of Example 1, except that the proportions of each raw material are shown in Table 1. In Table 1, the amount of each effective component is the percentage of the solid mass of the corresponding effective component to the total solid mass of the impregnating agent.

[0058] 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.

[0059] Table 1 Formulations of glass fiber impregnating agents in examples and comparative cases.

[0060]

[0061] Table 1 Formulations of glass fiber impregnating agents in examples and comparative cases (continued)

[0062]

[0063]

[0064] It should be noted that the proportion of the sizing agent on the glass fiber to the total mass of the glass fiber is generally controlled between 0.2% and 1%. Based on actual application requirements and test comparisons, it can be seen that the combustible content is preferably between 0.5% and 0.6% to obtain the required mechanical properties and bundle properties of the product.

[0065] To further illustrate the beneficial effects of this application, two commonly used direct yarn sizing agent formulations for winding processes were selected as Comparative Examples 3 and 4. Both Comparative Examples 3 and 4 contain active ingredients and water. The percentage of the solid mass of each active ingredient to the total solid mass of the direct yarn sizing agent is expressed as follows:

[0066] Comparative Example 3

[0067]

[0068]

[0069] Among them, coupling agent 1 is γ-methacryloxypropyltrimethoxysilane; coupling agent 2 is 3-(2,3-epoxypropoxy)propyltrimethoxysilane; film-forming agent 1 is acrylic acid modified epoxy resin emulsion; film-forming agent 2 is aqueous epoxy resin emulsion; surfactant is dodecylbenzyldimethylammonium chloride; lubricant is PEG1000; pH adjuster is acetic acid.

[0070] Comparative Example 4

[0071]

[0072] Among them, the coupling agent is an amide silane coupling agent; film-forming agent 1 is an aqueous epoxy emulsion; film-forming agent 2 is an aqueous polyurethane modified epoxy emulsion; lubricant 1 is a cationic quaternary ammonium salt emulsion; lubricant 2 is a modified organosilicon lubricant; anti-aging agent is an ammonium salt; and pH adjuster is acetic acid.

[0073] Comparative Example 5

[0074] The difference from Example 1 is that the waterborne bisphenol A epoxy emulsion is 36% and the waterborne polyether-type polyurethane modified aliphatic epoxy emulsion is 36%, ultimately yielding a glass fiber impregnating agent.

[0075] Comparative Example 6

[0076] The difference from Example 1 is that the waterborne bisphenol A epoxy emulsion is 60% and the waterborne polyether-type polyurethane modified aliphatic epoxy emulsion is 12%, ultimately yielding a glass fiber impregnating agent.

[0077] Performance testing:

[0078] Based on the sizing agent formulations of Examples 1-14 and Comparative Examples 1-6 above, the sizing agents of the corresponding examples and comparative examples were used in the production process of glass fiber direct yarn, and the product performance of the glass fibers was tested. Table 2 records the test results of the glass fiber performance of the examples and comparative examples.

[0079] The glass fiber is drawn using a 4000H platinum spindle, with a linear density of 2400 tex and a single fiber diameter of 17 micrometers.

[0080] The tensile strength of glass fiber is tested according to GB / T 1458, and the unit is MPa.

[0081] The tensile strength of glass fiber was tested according to GB / T7690.3, and the unit is N / tex.

[0082] The fiber fuzz test was performed using a self-made fiber fuzz tester.

[0083] The impregnation time of the glass fiber was determined using a self-made one-way plate test method.

[0084] Table 2. Test results of glass fibers produced by direct impregnation and coating of glass fiber yarn.

[0085]

[0086] Table 2. Test results of glass fibers produced by direct impregnation with sizing agent (continued)

[0087]

[0088]

[0089] Table 2. Test results of glass fibers produced by direct impregnation with sizing agent (continued)

[0090]

[0091] The following explanations are provided for some of the terms and indicators in Table 2 above:

[0092] "Average," "Good," and "Very Good" indicate the degree to which the bundle properties of the raw silk gradually improve.

[0093] "Easily pills, slightly pills, average, good, very good" indicates the degree to which the smoothness of the winding pipe gradually improves;

[0094] "Slight white streaks, average, good, very good" indicates a gradual improvement in the degree of wrapping and penetration.

[0095] The test data of the above embodiments were obtained according to the general testing method for glass fibers. From the test results of the above formulation test examples, it can be seen that the performance of the embodiments of this application is superior to that of Comparative Examples 1-6, especially Examples 7-9, which have better overall performance. Examples 7-9 not only have less yarn fuzz and excellent abrasion resistance, but also high tensile strength, rapid and complete impregnation in epoxy resin, and excellent fatigue resistance. They can meet the comprehensive performance requirements of energy storage gas cylinder winding molding for yarn abrasion resistance, high mechanical properties and fatigue resistance, and excellent epoxy impregnation.

[0096] In summary, the glass fiber direct yarn produced using the glass fiber impregnating agent of this application not only has less fuzz, better wear resistance, and better bundle properties, but is also less prone to fuzzing or yarn breakage during use. At the same time, it can also endow the composite material with excellent mechanical strength and fatigue resistance.

[0097] Finally, it should be noted that in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0098] As can be seen from the above description, the embodiments of the present invention achieve the following technical effects:

[0099] Through the synergistic effect of the above components, the glass fiber direct yarn produced by coating the glass fiber with the sizing agent obtained by the glass fiber sizing agent composition has very good flexibility, is not easy to fuzz during use, has good smoothness, and is especially fast and has strong penetration in epoxy resin system. It has high bonding strength with resin and excellent fatigue resistance, making it particularly suitable for winding and molding of energy storage gas cylinders.

[0100] The above are merely embodiments of the present invention and are not intended to limit the invention. Those skilled in the art will recognize that the present invention can have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A glass fiber impregnating agent composition comprising an active ingredient and water, characterized in that, The active ingredient comprises, by weight percentage: 9.0%–18.0% silane coupling agent; Film-forming agent A: 34.0%–55.0%; Film-forming agent B: 12.0%–20.0%; 14.0%–24.0% lubricant; 3.0% to 6.0% toughening agent; 0.5% to 1.5% wetting agent; 1.0%–2.5% pH adjuster; The glass fiber impregnating agent composition has a solid content of 5-9%, wherein the film-forming agent A is an aqueous bisphenol A epoxy resin emulsion, and the film-forming agent B is an aqueous polyether-type polyurethane modified aliphatic epoxy emulsion; the silane coupling agent comprises a first silane coupling agent and a second silane coupling agent, wherein the first silane coupling agent is an epoxy-based silane coupling agent, and the second silane coupling agent is an amino-containing silane coupling agent, and the mass ratio of the film-forming agent A to the film-forming agent B is (2-4.5):

1.

2. The glass fiber impregnating agent composition according to claim 1, characterized in that, The active ingredient comprises, by weight percentage: 10.0% to 16.0% of the silane coupling agent; 36.0% to 52.0% of the film-forming agent A; 14.0% to 20.0% of the film-forming agent B; The lubricant, comprising 15.0% to 22.0% of its content; 3.0% to 5.0% of the toughening agent; 0.5% to 1.0% of the aforementioned wetting agent; 1.0% to 2.0% of the pH adjuster; The glass fiber impregnating agent composition has a solid content of 5.5-8.5%, and the mass ratio of film-forming agent A to film-forming agent B is (2.5-4):

1. Preferably, the effective components include: 12.0% to 16.0% of the silane coupling agent; 40.0% to 50.0% of the film-forming agent A; 14.0% to 18.0% of the film-forming agent B; The lubricant, comprising 16.0% to 21.0% of its content; 3.0% to 4.5% of the toughening agent; 0.5% to 1.0% of the aforementioned wetting agent; 1.0% to 1.5% of the pH adjuster; The solid content of the glass fiber sizing agent composition is 6-8%; the mass ratio of film-forming agent A to film-forming agent B is (3-4):

1. Further, the preferred effective component comprises: 13.0% to 16.0% of the silane coupling agent; 43.0% to 48.0% of the film-forming agent A; 14.0% to 16.0% of the film-forming agent B; The lubricant, in the form of 16.0% to 20.0%; 3.0% to 4.0% of the toughening agent; 0.5% to 1.0% of the aforementioned wetting agent; 1.0% to 1.5% of the pH adjuster; The solid content of the glass fiber impregnating agent composition is 6-8%; the mass ratio of film-forming agent A to film-forming agent B is (3-3.5):

1.

3. The glass fiber impregnating agent composition according to claim 1 or 2, characterized in that, The total solid mass of film-forming agent A and film-forming agent B accounts for 50-72% of the total solid mass of the glass fiber impregnating agent composition, preferably 55-70%, more preferably 58-63%; and / or the molecular weight of film-forming agent A is 500-800, and the molecular weight of film-forming agent B is 2000-3500.

4. The glass fiber impregnating agent composition according to any one of claims 1 to 3, characterized in that, The mass ratio of the first silane coupling agent to the second silane coupling agent is (2.5-4):1, preferably (2.5-3.5):1, and more preferably (2.5-3):1; Wherein, the first silane coupling agent is 3-(2,3-epoxypropoxy)propyltrimethoxysilane; and / or the second silane coupling agent is selected from any one or more of γ-aminoethylaminopropyltrimethoxysilane and amino silane coupling agent oligomers.

5. The glass fiber impregnating agent composition according to any one of claims 1 to 4, characterized in that, The lubricant is a nonionic lubricant and / or an organosilicon lubricant, preferably selected from any one or more of fatty acid amide lubricants, alkyl-modified polyoxyethylene ether lubricants, and polyether-modified organosilicon lubricants; and / or the pH adjuster is an acid, preferably citric acid.

6. The glass fiber impregnating agent composition according to any one of claims 1 to 5, characterized in that, The toughening agent is a waterborne polyether-type polyurethane elastomer modified epoxy emulsion.

7. The glass fiber impregnating agent composition according to any one of claims 1 to 6, characterized in that, The wetting agent is an acetylenic diol wetting agent and / or an aqueous organosilicone wetting agent.

8. A glass fiber impregnating agent, obtained by mixing a glass fiber impregnating agent composition, characterized in that, The glass fiber sizing agent composition is the glass fiber sizing agent composition according to any one of claims 1 to 7.

9. A glass fiber direct yarn product produced by coating with the glass fiber sizing agent according to claim 8.

10. The application of the glass fiber direct yarn product of claim 9 in the winding of energy storage cylinders.

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