Glass fiber sizing and method of making, products and uses thereof

Abstract

The application provides a glass fiber sizing agent, which comprises effective components and water, and the solid content of the sizing agent is 6.0%-15.0%; the effective components comprise a silane coupling agent, a film forming agent, a lubricant and an anti-hydrolysis agent; the percentage of the solid mass of each effective component of the sizing agent in the total mass of the sizing agent is shown as follows: the silane coupling agent is 5.0%-15.0%; the film forming agent is 55.0%-80.0%; the lubricant is 4.0%-12.0%; and the anti-hydrolysis agent is 10.0%-20.0%; wherein the film forming agent is an epoxy emulsion and a polyurethane emulsion, the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent, the lubricant is a silicone oil lubricant, and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer. The glass fiber chopped strand produced by using the sizing agent has good bundling property and good compatibility with polybutylene terephthalate resin, and the polybutylene terephthalate resin composite prepared by using the glass fiber chopped strand has excellent mechanical properties and wet heat aging resistance.

Description

Technical Field

[0001] This application relates to the field of glass fiber sizing agents, and in particular to a glass fiber sizing agent, its preparation method, product, and application. Background Technology

[0002] In recent years, with the rapid development of the photovoltaic and solar energy industries, glass fiber reinforced polybutylene terephthalate (PBT) composite materials have been increasingly used in photovoltaic module materials. For example, they are used as back-side protective encapsulation materials to enhance the aging and corrosion resistance of photovoltaic modules. This not only extends the service life of photovoltaic modules but also improves their light absorption efficiency by scattering light incident on the module through the white backsheet. Furthermore, when used as a replacement for aluminum frame materials, it can protect the glass edges, strengthen the sealing performance of photovoltaic modules, and improve the overall mechanical strength of the modules, facilitating installation and transportation. Photovoltaic modules are used in open, harsh outdoor environments, constantly exposed to high and low temperatures, wind, rain, and strong sunlight, resulting in rapid aging. Evaluating aging performance is crucial for the safe operation of photovoltaic systems. Therefore, domestic and international thermoplastic companies have conducted increasing research on the application of PBT composite materials in the photovoltaic industry. How to maintain good mechanical properties under long-term heat or harsh natural environments has become one of the key challenges and research hotspots for major composite material companies.

[0003] Conventional glass fiber reinforced PBT composites are prone to decomposition in water at high temperatures, which is largely related to the resin's properties. PBT resin itself has numerous ester bonds, making it susceptible to degradation upon contact with water. From the perspective of glass fiber materials, glass fiber itself exhibits excellent aging resistance and can maintain its performance for extended periods under humid and hot environments. Furthermore, the surface of glass fiber is typically coated with a chemical mixture (known in the industry as a sizing agent) to ensure smooth production, excellent performance in use, and improved interfacial bonding with the matrix resin. Therefore, developing corresponding sizing agents to improve the compatibility between glass fiber and PBT resin, and to enhance the composite material's resistance to humid and hot aging, is of great significance.

[0004] Therefore, it is necessary to develop a novel wetting agent to improve the performance of glass fiber reinforced PBT composites. Summary of the Invention

[0005] This application aims to provide a glass fiber sizing agent, and particularly relates to a glass fiber sizing agent and its preparation method, product and application. Glass fibers coated with this sizing agent have good bundle properties, fewer fuzz during production, good compatibility with polybutylene terephthalate resin, and uniform dispersion in polybutylene terephthalate resin, so that the prepared polybutylene terephthalate resin composite material has excellent mechanical properties and resistance to damp heat aging.

[0006] According to a first aspect of this application, a glass fiber impregnating agent is provided, the impregnating agent comprising an effective component and water, the solid content of the impregnating agent being 6.0% to 15.0%; the effective component comprising a silane coupling agent, a film-forming agent, a lubricant, and an anti-hydrolysis agent; the percentage of the solid mass of each effective component of the impregnating agent to the total solid mass of the impregnating agent is expressed as follows:

[0007]

[0008] The film-forming agent is an epoxy emulsion and a polyurethane emulsion, the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent, the lubricant is a silicone oil lubricant, and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer.

[0009] Preferably, the solid content of the wetting agent is 7.0% to 14.0%; the percentage of the solid mass of each effective component of the wetting agent to the total solid mass of the wetting agent is expressed as follows:

[0010]

[0011] The film-forming agent is an epoxy emulsion and a polyurethane emulsion, the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent, the lubricant is a silicone oil lubricant, and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer.

[0012] Preferably, the amino-based silane coupling agent includes one or more of 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane;

[0013] The epoxy silane coupling agent includes one or both of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidyl etherpropyltrimethoxysilane.

[0014] Preferably, the epoxy emulsion is a bisphenol S type epoxy emulsion and / or a fluorinated epoxy emulsion, and the polyurethane emulsion is a polyether type polyurethane emulsion and / or a polyolefin type polyurethane emulsion.

[0015] Preferably, the lubricant is one or both of phenylethyl silicone oil lubricant and phenolic methyl silicone oil lubricant.

[0016] Preferably, the anti-hydrolysis agent is a glycidyl ether-based epoxy compound hydrolysis stabilizer.

[0017] Preferably, the glycidyl ether-based epoxy compound hydrolysis stabilizer includes one or more of phenyl glycidyl ether, triglycidyl isocyanate, bisphenol A bisglycidyl ether, tetra(phenylglycidyl)ethane, and trimethoxy[3-(glycidyl)propyl]silane.

[0018] Preferably, the mass ratio C1 of the amino-based silane coupling agent and the epoxy-based silane coupling agent is 2:3 to 4:1.

[0019] Preferably, the solid mass ratio C2 of the epoxy emulsion to the polyurethane emulsion is 1:3 to 3:1.

[0020] According to a second aspect of this application, a method for preparing the aforementioned glass fiber impregnating agent is provided, comprising the following steps:

[0021] Hydrolysis of coupling agent: Add silane coupling agent to water to hydrolyze the silane coupling agent, stir until the solution is clear, and obtain silane coupling agent solution;

[0022] Dilution of film-forming agents, lubricants, and anti-hydrolysis agents: Dilute the film-forming agents, lubricants, and anti-hydrolysis agents separately with water;

[0023] The diluted film-forming agent, lubricant, and anti-hydrolysis agent are added to the silane coupling agent solution, and the remaining water is added. The mixture is stirred evenly to obtain the glass fiber impregnating agent.

[0024] According to a third aspect of this application, a glass fiber product produced by coating with the aforementioned glass fiber sizing agent is provided.

[0025] According to the fourth aspect of this application, the above-mentioned glass fiber product is provided for use in reinforced polybutylene terephthalate resin composites.

[0026] The glass fiber produced using the impregnating agent of this application has good bundle properties, low fuzz during production and use, good compatibility with PBT resin, excellent mechanical properties after PBT reinforcement, and significantly improved resistance to damp heat aging. Detailed Implementation

[0027] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with specific embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. It should be noted that, unless otherwise specified, the embodiments and features in the embodiments of this application can be arbitrarily combined with each other.

[0028] In some optional embodiments, a glass fiber impregnating agent is provided, comprising an active ingredient and water, wherein the solid content of the impregnating agent is 6.0% to 15.0%; the active ingredient comprises a silane coupling agent, a film-forming agent, a lubricant, and an anti-hydrolysis agent; the percentage of the solid mass of each active ingredient in the impregnating agent relative to the total solid mass of the impregnating agent is expressed as follows:

[0029]

[0030] The film-forming agent is an epoxy emulsion and a polyurethane emulsion; the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent; the lubricant is a silicone oil lubricant; and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer.

[0031] In some optional embodiments, a glass fiber sizing agent is provided, comprising an effective component and water, wherein the solid content of the sizing agent is 7.0% to 14.0%; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:

[0032]

[0033] The film-forming agent is an epoxy emulsion and a polyurethane emulsion; the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent; the lubricant is a silicone oil lubricant; and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer.

[0034] In some optional embodiments, a glass fiber sizing agent is provided, comprising an effective component and water, wherein the solid content of the sizing agent is 8.0% to 13.0%; the percentage of the solid mass of each effective component of the sizing agent to the total solid mass of the sizing agent is expressed as follows:

[0035]

[0036] The film-forming agent is an epoxy emulsion and a polyurethane emulsion; the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent; the lubricant is a silicone oil lubricant; and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer.

[0037] In this application, silane coupling agents enable coupling between glass fibers and the matrix resin. This not only repairs microcracks in the glass fibers during production but also affects the compatibility and interfacial bonding between the glass fibers and the matrix resin, thus influencing the mechanical properties of the composite material. The silane coupling agents in this application include both amino-based and epoxy-based agents, which can synergistically work with film-forming agents, lubricants, and anti-hydrolysis agents in the glass fiber impregnating agent to effectively improve the compatibility between the glass fibers and PBT resin. Simultaneously, the dosage of the silane coupling agent must be controlled within an appropriate range. Excessive dosage will result in a yellowish color in the product, poor dispersion of the glass fibers in the resin, and unnecessary waste; insufficient dosage will prevent the mechanical properties of the composite material from meeting design requirements. Therefore, in this application, the percentage of the solid mass of the silane coupling agent to the total solid mass of the wetting agent is 5.0% to 15.0%, preferably 6.0% to 13.0%, and more preferably 7.5% to 12.0%.

[0038] Film-forming agents are one of the most important components in glass fiber sizing agents, determining the performance of glass fiber production, processing, and the resin composites reinforced with it. Film-forming agents protect glass fibers from abrasion during fiber drawing, maintain yarn bundle structure, improve the compatibility between glass fibers and matrix resins during resin reinforcement, and, with special modifications, impart more functional characteristics to the final composite material. Therefore, selecting a suitable film-forming agent ensures yarn bundle structure and smoothness in subsequent use, as well as uniform mixing of glass fibers and matrix resins and sufficient and complete interfacial bonding, thereby improving the mechanical properties of the composite material and the finished product, and giving the composite material superior water resistance. The film-forming agent in this application is a combination of epoxy emulsion and polyurethane emulsion. Epoxy resin and PBT resin have excellent compatibility, resulting in superior mechanical properties in the final product. The selected epoxy emulsion improves the bonding between glass fiber and PBT resin and imparts better stability to the composite material under high humidity and high heat. Simultaneously, the selected polyurethane emulsion exhibits excellent film-forming properties, and the polyurethane-coated glass fiber has better processability, contributing to improved moisture and heat resistance of the composite material. Furthermore, the film-forming agent used in this application needs to be controlled within a certain range. Excessive use of the film-forming agent will lead to excessively strong glass fiber aggregation, making dispersion difficult and reducing the mechanical properties of the composite material. Insufficient use of the film-forming agent will result in poor surface abrasion resistance of the glass fiber, increased fuzzing, affecting production smoothness and easily leading to fiber floating. Therefore, this application controls the percentage of the solid mass of the film-forming agent to the total solid mass of the sizing agent to be 55.0%–80.0%, preferably 60.0%–70.0%, and more preferably 65.0%–70.0%.

[0039] Choosing a suitable anti-hydrolysis agent can provide glass fibers with better temperature resistance and improve the anti-aging properties of the impregnating agent, thereby improving the color of the composite product and enhancing its anti-aging performance. The anti-hydrolysis agent used in this application is an epoxy compound hydrolysis stabilizer. The hydrolysis stabilization mechanism of the epoxy compound hydrolysis stabilizer is as follows: the epoxy group reacts with the carboxyl group produced by hydrolysis to generate a hydroxyl group, thus inhibiting the catalytic effect of the carboxyl group on hydrolysis; the epoxy group also reacts with the hydroxyl group, causing the broken chains generated by hydrolysis to reconnect. The amount of anti-hydrolysis agent is a crucial factor affecting the damp heat resistance of glass fibers in PBT resin. Excessive use of the anti-hydrolysis agent will result in poor product bundle structure, leading to excessive hairiness and decreased performance during extrusion; insufficient use will not improve temperature and damp heat resistance. Therefore, this application controls the percentage of the solid mass of the anti-hydrolysis agent to the total solid mass of the wetting agent to be 10.0% to 20.0%, preferably 12.0% to 19.0%, and more preferably 13.0% to 16.0%.

[0040] The use of silicone oil-based lubricants in this application provides sufficient lubrication during glass fiber production to ensure smooth operation. However, the amount of lubricant used must be controlled within a certain range. Excessive lubricant will affect the bonding strength between the glass fiber and the resin; insufficient lubricant will not provide adequate lubrication, making the glass fiber prone to fuzzing. In this application, the percentage of the solid mass of the lubricant to the total solid mass of the impregnating agent is controlled to be 4.0% to 12.0%, preferably 5.0% to 10.0%, and more preferably 6.0% to 9.0%.

[0041] It should be noted that the solid mass of each effective component in this application refers to the mass of the non-aqueous component of the corresponding effective component.

[0042] In this application, water is the dispersed phase of each effective component in the glass fiber wetting agent, wherein the water is preferably deionized water.

[0043] In some optional embodiments, the amino-based silane coupling agent includes one or more of 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane. In some optional embodiments, the epoxy-based silane coupling agent includes one or two of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidyl etherpropyltrimethoxysilane. The use of such amino-based and epoxy-based silane coupling agents in this application can further enhance the synergy with the film-forming agent, lubricant, and anti-hydrolysis agent in the glass fiber impregnating agent, thereby further improving the compatibility between the glass fiber and PBT resin.

[0044] In some optional embodiments, the epoxy emulsion is a bisphenol S-type epoxy emulsion and / or a fluorinated epoxy emulsion. In some optional embodiments, the polyurethane emulsion is a polyether-type polyurethane emulsion and / or a polyolefin-type polyurethane emulsion. The bisphenol S-type epoxy emulsion or fluorinated epoxy resin itself is modified; the bisphenol S-type epoxy resin uses a strongly polar sulfone group to replace the isopropyl group of the bisphenol A-type epoxy resin, which enhances its heat resistance and reactivity. The fluorinated epoxy resin has good hydrophobicity, and its moisture resistance and thermal stability are superior to those of conventional bisphenol A-type epoxy resin emulsions. The fluorinated epoxy resin or the bisphenol S-type epoxy resin has fluorine atoms or -SO atoms introduced, respectively. 2- This process densifies the molecular structure and enhances reactivity, resulting in superior corrosion resistance, heat resistance, and hydrophobicity. It effectively improves the reaction between the epoxy compound hydrolysate and the carboxyl groups generated during the hydrolysis of PBT resin, producing hydroxyl groups and thus inhibiting the catalytic effect of carboxyl groups on hydrolysis. Simultaneously, the epoxy groups react with the hydroxyl groups generated during the hydrolysis of fluorinated epoxy resin or bisphenol S-type epoxy resin, causing the broken chains resulting from hydrolysis to reconnect. Therefore, the high-temperature aging resistance of glass fibers coated with this sizing agent is significantly improved.

[0045] In some optional embodiments, the epoxy emulsion is anionic and / or nonionic. In some optional embodiments, the polyurethane emulsion is anionic and / or nonionic.

[0046] In some optional embodiments, the lubricant is one or both of phenylethyl silicone oil lubricant and phenolic methyl silicone oil lubricant.

[0047] In some optional embodiments, the anti-hydrolysis agent is a glycidyl ether epoxy compound hydrolysis stabilizer.

[0048] In some optional embodiments, the glycidyl ether-based epoxy compound hydrolysis stabilizer includes one or more of phenyl glycidyl ether, triglycidyl isocyanate, bisphenol A bisglycidyl ether, tetra(phenylglycidyl)ethane, and trimethoxy[3-(glycidyl)propyl]silane.

[0049] In some optional embodiments, the mass ratio (C1) of amino-based silane coupling agent to epoxy-based silane coupling agent is 2:3 to 4:1. Amino-based silane coupling agents are highly reactive; a predominantly amino-based formulation can better improve the interfacial bonding between the glass fiber surface and the resin. Better interfacial bonding helps to mitigate high-temperature and humid heat damage. Simultaneously, the addition of epoxy-based silane coupling agents, which have excellent high-temperature resistance, helps to improve the temperature resistance of the composite material. Therefore, the combined use of amino-based and epoxy-based silane coupling agents, with adjustments to their mass ratio, can simultaneously improve both the interfacial bonding and temperature resistance of the composite material.

[0050] For example, the mass ratio of amino-based silane coupling agents to epoxy-based silane coupling agents is 2:3, 1:1, 2:1, 3:1, 3.5:1, or 4:1.

[0051] In some optional embodiments, the solid mass ratio (C2) of the epoxy emulsion to the polyurethane emulsion is 1:3 to 3:1. Conventional formulations use a mixture of epoxy and polyurethane emulsions to balance mechanical and performance characteristics. Specifically, in the mixture, a higher proportion of epoxy emulsion results in better bonding between the composite material and PBT resin; conversely, a higher proportion of polyurethane emulsion leads to better binding properties, less fuzz, and better performance. The solid mass ratio of the epoxy and polyurethane emulsions can be adjusted according to actual needs, which will not be elaborated upon here.

[0052] For example, the solid mass ratio of epoxy emulsion to polyurethane emulsion is 1:3, 2:3, 1:1, 2:1, 2.5:1, or 3:1.

[0053] In some optional embodiments, a method for preparing the aforementioned glass fiber impregnating agent is provided, comprising the following steps:

[0054] S1: Hydrolysis of silane coupling agent: Add the silane coupling agent to water to hydrolyze the silane coupling agent, stir until the solution is clear, and obtain the silane coupling agent solution;

[0055] S2: Dilution of film-forming agent, lubricant and anti-hydrolysis agent: Dilute the film-forming agent, lubricant and anti-hydrolysis agent separately with water;

[0056] S3: Add the diluted film-forming agent, lubricant and anti-hydrolysis agent to the silane coupling agent solution, add the remaining water, and stir evenly to obtain the glass fiber impregnating agent.

[0057] In some optional embodiments, step S1 includes: adding water at a weight of 20 to 40 times that of the silane coupling agent to a first container, adding the silane coupling agent to the first container, hydrolyzing the silane coupling agent, stirring while adding, and stirring until the solution is clear and there are no oil droplets on the surface, thus obtaining a silane coupling agent solution.

[0058] In some optional embodiments, step S2 includes: adding water at 60-90°C to a second container at a weight of 10-15 times the weight of the film-forming agent, then slowly adding the film-forming agent, stirring to dissolve, and obtaining a film-forming agent diluted with water;

[0059] Add water at 60-90°C to the third container at a weight of 15-25 times that of the lubricant, then slowly add the lubricant and stir to dissolve it, thus obtaining a lubricant diluted with water.

[0060] Add water at 60-90°C to the fourth container at a weight of 15-25 times that of the anti-hydrolysis agent, then slowly add the anti-hydrolysis agent and stir to dissolve, thus obtaining the anti-hydrolysis agent diluted with water.

[0061] 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 the film-forming agent, lubricant and anti-hydrolysis agent with water can also be adjusted according to actual needs, which will not be elaborated here.

[0062] In some alternative embodiments, a glass fiber product produced by the aforementioned glass fiber sizing agent coating is provided.

[0063] In some optional embodiments, the chopped length of the glass fiber product is 2 to 9 mm, preferably 2.5 to 7.5 mm, and more preferably 3 to 6 mm.

[0064] In some alternative embodiments, the use of the aforementioned glass fiber impregnating agent in reinforced polybutylene terephthalate resin composites is provided.

[0065] To more clearly explain the technical solution of this application, some specific embodiments of the glass fiber impregnating agent of this application (Examples 1 to 18) are listed below. The specific formulations of the glass fiber impregnating agent of Examples 1 to 18 of this application are shown in Table 1. The amount of each effective component in Table 1 is the percentage of the solid mass of the corresponding effective component to the total solid mass of the impregnating agent.

[0066] 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.

[0067] Table 1. Wetting agent formulations for Examples 1-18

[0068]

[0069]

[0070] Table 1 (continued) Wetting agent formulations for Examples 1-18

[0071]

[0072] Table 1 (continued) Wetting agent formulations for Examples 1-18

[0073]

[0074] The preparation method of the glass fiber impregnating agent in Examples 1-18 specifically includes the following steps:

[0075] Hydrolysis of silane coupling agent: Add the silane coupling agent to water to hydrolyze the silane coupling agent, stir until the solution is clear, and obtain a silane coupling agent solution;

[0076] Dilution of film-forming agents, lubricants, and anti-hydrolysis agents: Dilute the film-forming agents, lubricants, and anti-hydrolysis agents separately with water;

[0077] The diluted film-forming agent, lubricant, and anti-hydrolysis agent are added to the silane coupling agent solution, and the remaining water is added. The mixture is stirred evenly to obtain the glass fiber impregnating agent.

[0078] In addition, to further illustrate the beneficial effects of this application, the following sizing agent formulations (Comparative Examples 1 to 3) are selected as comparative examples, wherein Comparative Example 3 is a commonly used sizing agent for glass fibers that reinforces polybutylene terephthalate resin, which facilitates the explanation of the technical solution of this application.

[0079] Comparative Example 1

[0080] The wetting agent contains active ingredients and water, with a solid content of 9.0%. The percentage of the solid mass of each active ingredient to the total solid mass of the wetting agent is expressed as follows:

[0081] Coupling agent (aminosilane coupling agent): 15%

[0082] Film-forming agent (bisphenol A epoxy resin): 60%

[0083] Anti-hydrolysis agent (polymeric aliphatic carbodiimide emulsion): 15%

[0084] Lubricant (silicone oil-based lubricant): 10%.

[0085] Comparative Example 2

[0086] The wetting agent contains active ingredients and water, with a solid content of 8.5%. The percentage of the solid mass of each active ingredient to the total solid mass of the wetting agent is expressed as follows:

[0087] Coupling agent (aminosilane coupling agent): 10%

[0088] Film-forming agent (alicyclic epoxy emulsion): 60%

[0089] Anti-hydrolysis agent (isocyanate-based anti-hydrolysis agent): 20%

[0090] Lubricant (polyether lubricant): 10%.

[0091] Comparative Example 3

[0092] The wetting agent contains active ingredients and water, with a solid content of 8.0%. The percentage of the solid mass of each active ingredient to the total solid mass of the wetting agent is expressed as follows:

[0093] Coupling agent (γ-aminopropyltriethoxysilane): 10%;

[0094] Film-forming agent (mixture of bisphenol A type epoxy and polyurethane-urea emulsion): 76%;

[0095] Lubricant (polyethylene glycol lubricant): 14%.

[0096] The preparation method of the sizing agent for glass fibers in Comparative Examples 1-3 specifically includes the following steps:

[0097] Hydrolysis of coupling agent: Add the coupling agent to water to hydrolyze the coupling agent, stir until the solution is clear, and obtain the coupling agent solution;

[0098] Dilution of film-forming agents, lubricants, and anti-hydrolysis agents: Dilute the film-forming agents, lubricants, and anti-hydrolysis agents separately with water;

[0099] The diluted film-forming agent, lubricant, and anti-hydrolysis agent are added to the coupling agent solution, and the remaining water is added. The mixture is stirred evenly to obtain a glass fiber impregnating agent.

[0100] Performance testing:

[0101] This application compares the performance of Examples 1-18 and Comparative Examples 1-3, and the test methods are as follows:

[0102] The sizing agents of Examples 1-18 and Comparative Examples 1-3 were respectively coated for the production of glass fibers, and the corresponding glass fibers were baked and chopped to finally produce chopped filament products with a chopped length of 3 mm.

[0103] Then, the corresponding chopped glass fibers were melt-blended with polybutylene terephthalate resin, extruded and granulated to finally obtain glass fiber reinforced polybutylene terephthalate resin composite material (glass fiber content of 30%). A portion of the composite material was placed in 100% pure water and kept at 121℃ for 100 hours before being taken out and its performance was retested. The performance test results are shown in Table 2.

[0104] Table 2 Performance test results of the examples and comparative examples

[0105]

[0106] Table 2 (continued) Performance test results of examples and comparative examples

[0107]

[0108] Table 2 (continued) Performance test results of examples and comparative examples

[0109]

[0110]

[0111] As can be seen from the test results in Table 2, compared with the sizing agents of Comparative Examples 1-3, the glass fibers prepared with the sizing agent of this application (Examples 1-18) exhibit higher mechanical properties when reinforcing polybutylene terephthalate (30% glass fiber content). The performance degradation after high-temperature boiling is significantly reduced, and the retention rate of tensile strength is greatly improved. Therefore, the glass fiber sizing agent formulation of this application is scientifically sound and can effectively improve the compatibility between glass fibers and resin when used in the production of polybutylene terephthalate resin composites, thus enhancing interfacial bonding performance and improving the hydrolysis resistance of the composite material.

[0112] In summary, the chopped glass fibers produced using the sizing agent of this application have good compatibility with polybutylene terephthalate (PET) resin, and the glass fibers can be uniformly dispersed in PET resin. The resulting products have excellent mechanical properties and can effectively solve the problem that traditional chopped glass fibers are not resistant to high temperature and high humidity when reinforcing PET. Glass fibers treated with the sizing agent provided in this application can meet the current market requirements for the mechanical properties and aging resistance of composite materials in complex environments.

[0113] 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. Unless otherwise specified, 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 that element.

[0114] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit it. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A glass fiber impregnating agent, characterized in that, The wetting agent comprises an effective component and water, and the solid content of the wetting agent is 6.0% to 15.0%; the effective component comprises a silane coupling agent, a film-forming agent, a lubricant, and an anti-hydrolysis agent; the percentage of the solid mass of each effective component of the wetting agent to the total solid mass of the wetting agent is expressed as follows: Silane coupling agent 5.0%–15.0% Film-forming agent 55.0%~80.0% Lubricant 4.0%~12.0% Anti-hydrolysis agent 10.0%–20.0%; The film-forming agent is an epoxy emulsion and a polyurethane emulsion, and the solid mass ratio (C2) of the epoxy emulsion to the polyurethane emulsion is 2:3 to 2.5:1; the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent; the lubricant is a silicone oil lubricant; and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer. The epoxy emulsion is a bisphenol S type epoxy emulsion and / or a fluorinated epoxy emulsion; the polyurethane emulsion is a polyether type polyurethane emulsion and / or a polyolefin type polyurethane emulsion.

2. The glass fiber impregnating agent according to claim 1, characterized in that, The solid content of the wetting agent is 7.0% to 14.0%; the percentage of the solid mass of each effective component of the wetting agent to the total solid mass of the wetting agent is expressed as follows: Silane coupling agent 6.0%–13.0% Film-forming agent 60.0%–70.0% Lubricant 5.0%~10.0% Anti-hydrolysis agent 12.0%~19.0%; The film-forming agent is an epoxy emulsion and a polyurethane emulsion, the silane coupling agent is an amino silane coupling agent and an epoxy silane coupling agent, the lubricant is a silicone oil lubricant, and the anti-hydrolysis agent is an epoxy compound hydrolysis stabilizer.

3. The glass fiber impregnating agent according to claim 1 or 2, characterized in that, The amino-based silane coupling agent includes one or more of 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane; The epoxy silane coupling agent includes one or both of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane and γ-glycidyl etherpropyltrimethoxysilane.

4. The glass fiber impregnating agent according to claim 1 or 2, characterized in that, The lubricant is one or both of phenylethyl silicone oil lubricant and phenolic methyl silicone oil lubricant.

5. The glass fiber impregnating agent according to claim 1 or 2, characterized in that, The anti-hydrolysis agent is a glycidyl ether-based epoxy compound hydrolysis stabilizer.

6. The glass fiber impregnating agent according to claim 5, characterized in that, The glycidyl ether-based epoxy compound hydrolysis stabilizers include one or more of phenyl glycidyl ether, triglycidyl isocyanate, bisphenol A bisglycidyl ether, tetra(phenylglycidyl)ethane, and trimethoxy[3-(glycidyl)propyl]silane.

7. The glass fiber impregnating agent according to claim 1 or 2, characterized in that, The mass ratio of the amino-based silane coupling agent to the epoxy-based silane coupling agent C1 is 2:3 to 4:

1.

8. A method for preparing a glass fiber impregnating agent as described in any one of claims 1 to 7, characterized in that, Includes the following steps: Hydrolysis of silane coupling agent: Add the silane coupling agent to water to hydrolyze the silane coupling agent, stir until the solution is clear, and obtain a silane coupling agent solution; Dilution of film-forming agents, lubricants, and anti-hydrolysis agents: Dilute the film-forming agents, lubricants, and anti-hydrolysis agents separately with water; The diluted film-forming agent, lubricant, and anti-hydrolysis agent are added to the silane coupling agent solution, and the remaining water is added. The mixture is stirred evenly to obtain the glass fiber impregnating agent.

9. A glass fiber product produced by coating with the glass fiber sizing agent according to any one of claims 1 to 7.

10. The use of the glass fiber product according to claim 9 in reinforced polybutylene terephthalate resin composites.

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