A glass fiber surface treatment agent and a preparation method thereof, a glass fiber and application thereof

Abstract

The application provides a glass fiber surface treatment agent and a preparation method thereof, glass fiber and application thereof. The glass fiber surface treatment agent comprises effective components and water, wherein the effective components account for 4.2-12.5% of the weight percentage of the glass fiber surface treatment agent; according to the weight percentage of the effective components, the effective components comprise: coupling agent 11.2-19.7%, antioxidant 0.1-0.5%, lubricant 6.1-11.2%, film forming agent 59.2-79.7%, light stabilizer 0.5-1.6% and auxiliary agent 2.5-7.6%; wherein the film forming agent is a combination of epoxy resin, vinyl resin and polyurethane prepolymer. The glass fiber produced by using the glass fiber surface treatment agent has excellent weather resistance, smoothness in use and mechanical properties of glass steel, and can meet various use requirements of weather-resistant glass steel composite materials.

Description

Technical Field

[0001] This application relates to the field of glass fiber reinforced composite materials technology, and more specifically, to a glass fiber surface treatment agent and its preparation method, glass fiber and its applications. Background Technology

[0002] Fiberglass composites possess excellent impact resistance and corrosion resistance. Due to the presence of interwoven glass fiber reinforcement in their structure, they effectively absorb external impact energy, enhancing the product's impact resistance. Furthermore, fiberglass composites can withstand corrosion from various acids, alkalis, salts, and other chemicals, thus finding wide application in aerospace, wind power generation, construction, transportation, chemical industry, and outdoor sports.

[0003] Although fiberglass and fiberglass composites possess excellent resistance to chemical corrosion, their weather resistance under long-term exposure to ultraviolet light is not particularly outstanding. This is mainly due to the poor weather resistance of fiberglass, the basic raw material of fiberglass composites, and existing technologies have not yet achieved a breakthrough in this area. To enable fiberglass composites to have excellent weather resistance and maintain stable performance under harsh environmental conditions for more than 20 years, current technologies can only treat the surface of fiberglass composites with special coatings to prevent ultraviolet erosion and chemical corrosion, thus maintaining color stability and mechanical property integrity over a long period of time. Examples include wind turbine blades, photovoltaic module frames and supports, and water treatment membrane shells made of fiberglass reinforced polymer (GFRP). However, this technology involves a cumbersome production process with extremely high requirements for the production environment (such as painting), which significantly reduces production efficiency and increases production costs. Furthermore, the surface of the composite material needs to be sanded before painting, generating dust, and the painting process itself is environmentally unfriendly, contradicting the concept of low-carbon and environmentally friendly green development.

[0004] Therefore, improving the UV resistance of glass fiber, the basic raw material for fiberglass composites, to enhance their weather resistance has always been a critical technical challenge for the composite materials industry. In summary, the composite materials industry urgently needs a glass fiber with excellent weather resistance, superior ease of use, and superior mechanical properties, while simultaneously meeting the high-performance requirements of various resin systems reinforcing different composite materials, thus promoting the high-quality development of the glass composite materials industry. With the increasing global awareness of environmental protection and energy conservation, and the continued advancement of green and low-carbon development in my country, its application prospects will be even broader.

[0005] The relevant technical requirements for fiberglass composite materials in the industry are as follows (taking 4800tex as an example, reinforcing unsaturated polyester resin, epoxy resin, and polyurethane resin):

[0006] The performance indicators are as follows:

[0007] Summary of the Invention

[0008] This application aims to provide a glass fiber surface treatment agent and its preparation method, glass fiber and its application, glass fiber with excellent weather resistance, smoothness of use and mechanical properties of fiberglass, and the glass fiber surface treatment agent applied to the glass fiber.

[0009] According to a first aspect of this application, a glass fiber surface treatment agent is provided, comprising an effective component and water, wherein the effective component accounts for 4.2 to 12.5% ​​by weight of the glass fiber surface treatment agent; and the effective component comprises, by weight percentage of the effective component:

[0010] The composition includes: coupling agent 11.2–19.7%, antioxidant 0.1–0.5%, lubricant 6.1–11.2%, film-forming agent 59.2–79.7%, light stabilizer 0.5–1.6%, and additives 2.5–7.6%.

[0011] The film-forming agent is a composition of epoxy resin, vinyl resin and polyurethane prepolymer.

[0012] The effective components, by weight percentage of the effective components, include:

[0013] The composition includes coupling agent 12.3–18.8%, antioxidant 0.13–0.46%, lubricant 6.8–10.1%, film-forming agent 61.6–77.9%, light stabilizer 0.5–1.6%, and additives 2.8–7.2%.

[0014] The epoxy resin is at least one of bisphenol A type epoxy and bisphenol F type epoxy;

[0015] The vinyl resin is at least one of epoxy-modified vinyl resin and toluene diisocyanate-modified vinyl resin;

[0016] The polyurethane prepolymer is at least one of a polyurethane prepolymer containing terminal hydroxyl groups and a polyurethane prepolymer containing blocked groups.

[0017] Wherein, the epoxy resin is a blend of bisphenol A type epoxy and bisphenol F type epoxy; the vinyl resin is an epoxy-modified vinyl resin; and the polyurethane prepolymer is a polyurethane prepolymer containing blocked groups.

[0018] The epoxy value of the epoxy resin is 0.26-0.43; the relative weight-average molecular weight of the vinyl resin is 7000-10000; and the relative weight-average molecular weight of the polyurethane prepolymer is 1700-4800.

[0019] The epoxy resin accounts for 22.2-39.6% of the effective components by weight; the vinyl resin accounts for 18-30% of the effective components by weight; and the polyurethane prepolymer accounts for 10.1-19% of the effective components by weight. The weight ratio of the epoxy resin, the vinyl resin, and the polyurethane prepolymer is (1.17-3.92):(0.95-2.97):1, preferably (1.35-3.68):(1.02-2.76):1.

[0020] The antioxidant is an ester antioxidant, which is at least one of tris[2,4-di-tert-butylphenyl]phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

[0021] The coupling agent is a silane coupling agent, which is at least one of isocyanate-based silane coupling agents, epoxy-based silane coupling agents, and polyamino-based silane coupling agents.

[0022] Preferably, when the silane coupling agent is a combination of isocyanate-based silane coupling agent, epoxy-based silane coupling agent, and polyamino-based silane coupling agent, the isocyanate-based silane coupling agent accounts for 6.1-9.5% by weight of the effective component; the epoxy-based silane coupling agent accounts for 2.8-5.4% by weight of the effective component; and the polyamino-based silane coupling agent accounts for 2.3-4.8% by weight of the effective component.

[0023] Preferably, the weight ratio of the isocyanate-based silane coupling agent, the epoxy silane coupling agent, and the polyamino silane coupling agent is (1.27–4.12):(0.58–2.35):1, more preferably (1.49–3.92):(0.71–2.08):1.

[0024] The lubricant is one or more of the following: polyethylene glycol, polypropylene glycol, fatty acid esters, and silicone oil lubricants.

[0025] The light stabilizer is an ultraviolet absorber;

[0026] The additive is an organic acid.

[0027] The ultraviolet absorber is at least one of benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers;

[0028] The organic acid is at least one of citric acid and acetic acid.

[0029] According to a second aspect of this application, a method for preparing the aforementioned glass fiber surface treatment agent is provided, comprising: mixing an additive, a coupling agent, an antioxidant, a lubricant, a light stabilizer, a film-forming agent, a light stabilizer, and water to obtain the glass fiber surface treatment agent.

[0030] According to a third aspect of this application, glass fibers are provided that are obtained by treating a glass fiber surface treatment agent prepared by the above-described preparation method.

[0031] According to the fourth aspect of this application, the application of the aforementioned glass fiber in fiberglass composites with excellent weather resistance is provided.

[0032] This application provides a glass fiber surface treatment agent comprising a coupling agent, an antioxidant, a lubricant, a film-forming agent, a light stabilizer, additives, and water. The coupling agent and film-forming agent are the main components of this glass fiber surface treatment agent. The coupling agent's main function is to react with the active groups on the surface of the glass fiber reinforcement material, repairing microcracks on the fiber surface and forming an effective and continuous protective layer on the glass fiber surface, improving processability. Simultaneously, the coupling agent can react with the matrix resin, forming a stress-transferring interface layer between the glass fiber reinforcement material and the resin matrix. This not only enhances the adhesion strength between the glass fiber reinforcement material and the matrix resin, improving the performance of the composite material, but also prevents other media from penetrating into the interface, improving the interface state and thus enhancing the aging resistance and stress resistance of fiberglass products. The film-forming agent's main function is to improve the bundle properties and weather resistance of the glass fiber, enhance its compatibility with the reinforcing resin, and improve the physical and mechanical strength of the composite material.

[0033] Compared to other types of film-forming agents, the film-forming agent selected in this application is a combination of epoxy resin, vinyl ester resin and polyurethane prepolymer. The biggest advantage of this combination is that it is compatible with a variety of resin systems, has stronger adhesion to the surface of glass fiber, and is stable and does not decompose at high temperatures, thus enabling the glass fiber to have excellent weather resistance and meet the mechanical performance requirements of fiberglass.

[0034] Experiments have shown that the glass fiber surface treatment agent prepared by combining coupling agent, antioxidant, lubricant, film-forming agent, light stabilizer, additives and water in the proportions specified in this application, when applied to glass fibers, results in glass fibers with significantly better wear resistance, weather resistance and mechanical properties than glass fibers treated with other glass fiber surface treatment agents. Detailed Implementation

[0035] 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 in 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 combined with each other. The present application will be described in detail below with reference to the embodiments.

[0036] To address the problems in the prior art as described above, according to one aspect of this application, a glass fiber surface treatment agent is provided, comprising an effective component and water, wherein the effective component accounts for 4.2 to 12.5% ​​by weight of the glass fiber surface treatment agent; the effective component, by weight percentage, comprises: 11.2 to 19.7% coupling agent, 0.1 to 0.5% antioxidant, 6.1 to 11.2% lubricant, 59.2 to 79.7% film-forming agent, 0.5 to 1.6% light stabilizer, and 2.5 to 7.6% additives; wherein the film-forming agent is a composition of epoxy resin, vinyl ester resin, and polyurethane prepolymer.

[0037] In one alternative embodiment, the weight ratio of epoxy resin, vinyl resin and polyurethane prepolymer is (1.17–3.92):(0.95–2.97):1.

[0038] In some alternative embodiments, a glass fiber surface treatment agent is provided, wherein the effective components, by weight percentage, include: 12.3–18.8% coupling agent, 0.13–0.46% antioxidant, 6.8–10.1% lubricant, 61.6–77.9% film-forming agent, 0.6–1.5% light stabilizer, and 2.8–7.2% additives.

[0039] In one alternative embodiment, the film-forming agent is 64-76% by weight, based on the weight percentage of the effective components.

[0040] In one optional embodiment, the epoxy resin is at least one of bisphenol A type epoxy and bisphenol F type epoxy; preferably, the epoxy resin is a blend of bisphenol A type epoxy and bisphenol F type epoxy; more preferably, the epoxy value of the epoxy resin is 0.26-0.43. If the epoxy value is too high, the epoxy resin has high strength but is also brittle; while if the epoxy value is low, the epoxy resin has poor strength at high temperatures. Therefore, this application selects epoxy resins with a medium epoxy value range (0.26-0.43), which have good strength at both high and low temperatures.

[0041] The preferred bisphenol A and bisphenol F epoxy blends in this application possess excellent heat resistance, water resistance, and electrical properties, and are widely used in casting and potting materials for transformers, semiconductor sealants, and semiconductor conductive adhesives. Applying a glass fiber surface treatment agent containing the aforementioned preferred epoxy resins is more conducive to obtaining glass fibers with excellent heat resistance, water (moisture) resistance, and insulation properties. This significantly improves the processing (operation) and mechanical strength of the fiberglass composite material, enabling it to maintain good mechanical properties even after long-term exposure to high outdoor temperatures.

[0042] In one optional embodiment, the vinyl resin is selected from at least one of epoxy-modified vinyl resin and toluene diisocyanate-modified vinyl resin; preferably, the vinyl resin is epoxy-modified vinyl resin; more preferably, the relative weight-average molecular weight of the vinyl resin is 7000 to 10000.

[0043] Vinyl ester resins, by linking hydrophilic acrylic and methacrylic acids to the epoxy segments, can synthesize waterborne resins without the addition of emulsifiers that adversely affect interfacial bonding. These resins possess characteristics such as moderate viscosity, high relative molecular weight, strong adhesion, high transparency, high reactivity, and a relatively high heat distortion temperature. Therefore, glass fibers treated with surface treatment agents containing the aforementioned preferred epoxy-modified vinyl ester resins exhibit better bundled properties and wettability, simultaneously meeting the requirements of various application processes such as winding, pultrusion, and weaving. Furthermore, after impregnation in the reinforcing resin, they achieve extremely high transparency, further facilitating the production of high-strength, low-defect, and high-temperature-resistant fiberglass composites.

[0044] In one optional embodiment, the polyurethane prepolymer is at least one of a polyurethane prepolymer containing terminal hydroxyl groups and a polyurethane prepolymer containing blocked groups; preferably, the polyurethane prepolymer is a polyurethane prepolymer containing blocked groups; more preferably, the relative weight-average molecular weight of the polyurethane prepolymer is 1700 to 4800.

[0045] By reacting an active hydrogen-containing blocking agent with NCO groups, the free NCO groups in the prepolymer are protected, thus obtaining a blocked polyurethane prepolymer. This blocked polyurethane prepolymer can regenerate NCO groups upon thermal deblocking, and these groups participate in the crosslinking reaction, causing the system to solidify. Therefore, using a glass fiber surface treatment agent containing the aforementioned preferred polyurethane prepolymer is more advantageous for obtaining glass fibers that possess hydrolysis resistance, flexibility, and weather resistance.

[0046] In one optional embodiment, the epoxy resin accounts for 22.2–39.6% of the effective components by weight, the vinyl ester resin accounts for 18–30% of the effective components by weight, and the polyurethane prepolymer accounts for 10.1–19% of the effective components by weight, with the weight ratio of epoxy resin, vinyl ester resin, and polyurethane prepolymer being (1.17–3.92):(0.95–2.97):1. This formulation is more conducive to improving the performance of the glass fiber surface treatment agent. In a preferred embodiment, the weight ratio of epoxy resin, vinyl ester resin, and polyurethane prepolymer is (1.35–3.68):(1.02–2.76):1.

[0047] In one optional embodiment, the antioxidant is an ester-based antioxidant; preferably, the ester-based antioxidant is at least one selected from tris[2,4-di-tert-butylphenyl]phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The use of ester-based antioxidants can effectively prevent redox reactions during long-term storage of the glass fiber surface treatment agent, thereby improving the aging resistance of the glass fiber.

[0048] The aforementioned preferred antioxidants possess characteristics such as very low volatility, poor migration resistance, resistance to extraction, high thermal stability, long-lasting effect, non-coloring, non-polluting, and non-toxic. They not only exhibit excellent compatibility with most polymers, effectively preventing thermal oxidative degradation of polymer materials during long-term aging, but also improve the discoloration resistance of polymer materials under high-temperature processing conditions. The inventors have found that an antioxidant dosage of 0.1–0.5% is most suitable. Insufficient antioxidant dosage results in minimal improvement in the storage resistance of glass fiber; while excessive antioxidant dosage affects the interfacial bonding between glass fiber and reinforcing resin, negatively impacting the performance of fiberglass composites. In a preferred embodiment, the antioxidant dosage is 0.13–0.46% by weight of the effective component.

[0049] In one optional embodiment, the coupling agent is a silane coupling agent; preferably, the silane coupling agent is at least one of isocyanate-based silane coupling agent, epoxy-based silane coupling agent, and polyamino-based silane coupling agent; more preferably, the silane coupling agent is a composition of isocyanate-based silane coupling agent, epoxy-based silane coupling agent, and polyamino-based silane coupling agent, wherein the isocyanate-based silane coupling agent accounts for 6.1 to 9.5% of the effective component by weight; the epoxy-based silane coupling agent accounts for 2.8 to 5.4% of the effective component by weight; and the polyamino-based silane coupling agent accounts for 2.3 to 4.8% of the effective component by weight; more preferably, the weight ratio of the isocyanate-based silane coupling agent, epoxy-based silane coupling agent, and polyamino-based silane coupling agent is (1.27 to 4.12):(0.58 to 2.35):1. The introduction of silane coupling agents can not only further improve the processability of glass fibers, but also enhance the bonding strength between materials and resins, the physical and mechanical strength of composite materials, and the aging resistance and stress resistance of fiberglass products.

[0050] The coupling agent selected in this application exhibits good wettability and high reactivity on the glass fiber surface. It not only reacts fully with the active groups on the surface of the glass fiber reinforcement, repairing microcracks on the fiber surface, but also forms an effective and continuous protective layer on the glass fiber surface, improving processability. Simultaneously, the coupling agent reacts with the matrix resin, forming an interface layer between the reinforcement and the resin matrix. This interface layer can transfer stress, thereby enhancing the adhesion strength between the reinforcement and the resin, improving the performance of the composite material. Furthermore, it prevents other media from penetrating into the interface, improving the interface state and contributing to improved aging resistance and stress resistance properties of fiberglass products.

[0051] Specifically, the isocyanate-based silane coupling agent selected in this application is a highly functional isocyanate-based silane containing two different active groups: isocyanate and ethoxy. The ethoxy group has good adhesion to various inorganic substrates (such as metals and glass), while the isocyanate group can react with active groups such as hydroxyl and amino groups. When used in organic materials, it can play a significant coupling role. It has good compatibility with various thermoplastic and thermosetting resins such as phenolic, polyester, epoxy, PBT, polyamide, and carbonate, and improves the wettability and dispersibility of glass fiber in the reinforcing resin. Thus, it can significantly improve the physical and mechanical properties of the reinforcing material, such as dry and wet flexural strength, compressive strength, and shear strength, as well as its wet electrical properties and anti-aging properties.

[0052] The epoxy-based silane coupling agent selected in this application is a bifunctional silane containing both epoxy organic active groups and methoxy inorganic active groups. The epoxy group has the activity to react with a variety of resins, while the silanol group formed after the hydrolysis of the methoxy group can undergo a condensation reaction with the hydroxyl groups on the surface of inorganic materials (glass), thereby building a "molecular bridge" between the inorganic materials and the resin, playing a coupling role, which can improve the adhesion of the glass fiber surface treatment agent to the glass fiber surface in both wet and dry states, and enhance the mechanical properties of the fiberglass composite material.

[0053] The polyamino silane coupling agent selected in this application has good compatibility with various resins such as unsaturated polyester resin, vinyl ester resin, epoxy resin, and polyurethane resin. Its polyamino structure has stronger polarity, which can provide multiple chemical reaction possibilities at the same time. It can interact with hydroxyl and carboxyl groups on the fiber surface, so that the silane can be better oriented and attached to the fiber surface, thereby producing a better coupling effect or cross-linking effect. This endows the material with excellent corrosion resistance, water resistance, oxidation resistance, and fiberglass mechanical properties, effectively extending the service life of fiberglass composite materials.

[0054] This application preferably uses a combination of isocyanate-based silane coupling agents, epoxy-based silane coupling agents, and polyamino-based silane coupling agents, which can produce a synergistic effect, resulting in high strength of the treated glass fibers. Simultaneously, it offers a long shelf life, good compatibility with various thermosetting resins, and significantly improves the corrosion resistance, oxidation resistance, radiation resistance, high-temperature resistance, electrical properties, and mechanical properties of dry and wet fiberglass composites. However, due to the high reactivity and high degree of cross-linking of polyamino-based silane coupling agents, excessive use can lead to hardening and brittleness of the glass fibers, reducing the wetting rate of the glass fibers in the resin. Conversely, insufficient use will prevent the achievement of the expected synergistic effect. The combination of coupling agents is based on the number of active groups generated after hydrolysis. Practical experience has shown that a weight ratio of (1.27–4.12):(0.58–2.35):1 for the isocyanate-based silane coupling agent, epoxy-based silane coupling agent, and polyamino-based silane coupling agent achieves an excellent synergistic effect. In a preferred embodiment, the weight ratio of isocyanate-based silane coupling agent, epoxy-based silane coupling agent, and polyamino-based silane coupling agent is (1.49–3.92):(0.71–2.08):1.

[0055] In some optional embodiments, the coupling agent is selected from 3-propyltriethoxysilane, 3-glycidyl ether propyltriethoxysilane, and γ-diethylenetriaminopropyltrimethoxysilane. In a preferred embodiment, the content of the coupling agent is 12.3% to 18.8%.

[0056] In one optional embodiment, the lubricant is one or more of polyethylene glycol, polypropylene glycol, fatty acid esters, and silicone oil lubricants. Preferably, the lubricant is one or more of polyethylene glycol, polypropylene glycol, and silicone oil lubricants. The introduction of a lubricant can reduce wear damage to the glass fiber when it comes into contact with process accessories during production, thereby improving the reprocessing performance of the glass fiber and reducing the generation of glass fiber fuzz. The preferred lubricant in this application has few side effects and can effectively reduce the frictional resistance of the friction pair, further improving the reprocessing performance of the glass fiber. In a preferred embodiment, the lubricant content is 6.8% to 10.1%.

[0057] In one optional embodiment, the light stabilizer is an ultraviolet absorber; preferably, the ultraviolet absorber is at least one of benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers. The introduction of an ultraviolet absorber can improve the outdoor aging resistance of glass fiber and its fiberglass products.

[0058] In a preferred embodiment, the light stabilizer is UVP-327, an ultraviolet absorber. Ultraviolet absorbers are substances that absorb the ultraviolet rays from sunlight or fluorescent sources without changing their own structure. Their photostable mechanism involves hydrogen-bonded chelate rings in their molecules. When absorbing ultraviolet light energy, the molecules undergo thermal vibration, the hydrogen bonds break, and the chelate rings open, thus converting harmful ultraviolet light into harmless heat energy, thereby protecting the substance containing the ultraviolet absorber from ultraviolet damage. The preferred ultraviolet absorber of this application has good chemical stability, extremely low volatility, and excellent compatibility with various reinforcing resins such as polyolefins, polyethylene, polypropylene, polyvinyl chloride, polymethyl methacrylate, polyoxymethylene, polyoxymethylene, polyurethane, unsaturated polyester, ABS resin, and epoxy resin. It also exhibits excellent resistance to heat sublimation, washability, resistance to gas fading, and retention of mechanical properties. Furthermore, when used in combination with antioxidants, it produces a significant synergistic effect, improving the thermo-oxidative stability of the product. The appropriate amount of light stabilizer used in combination with antioxidant can improve and enhance the light stability of composite material products, preventing the occurrence of "photo-oxidative aging" in polymer materials. In a preferred embodiment, the amount of light stabilizer is 0.6% to 1.5%.

[0059] In one optional embodiment, the adjuvant is an organic acid; preferably, the organic acid is at least one selected from citric acid and acetic acid. The introduction of organic acid can improve the dispersibility of the coupling agent, while also providing bactericidal and antifungal effects.

[0060] In a preferred embodiment, the additive can be a combination of acetic acid and citric acid. The amount of additive used in this application needs to be strictly controlled. Excessive addition may cause some components of the wetting agent to become ineffective and may also cause acid corrosion to the glass fiber; conversely, insufficient addition will fail to fully achieve the coupling agent dispersion effect and the bactericidal and antifungal effects. In a preferred embodiment, the amount of additive is 2.8% to 7.2%.

[0061] In some optional embodiments, a method for preparing the above-mentioned glass fiber surface treatment agent is provided, comprising: mixing an additive, a coupling agent, an antioxidant, a lubricant, a light stabilizer, a film-forming agent, and water to obtain the glass fiber surface treatment agent. When the glass fiber surface treatment agent obtained by the preparation method of this application is applied to glass fibers, the resulting glass fibers simultaneously possess excellent weather resistance, smoothness of use, and fiberglass mechanical properties, meeting the requirements for the use of fiberglass composite materials with excellent weather resistance.

[0062] In a preferred embodiment, the preparation method of this application can be carried out according to the following steps:

[0063] 1S: Add 30-45% of the total amount of treatment agent to the container with water, then add the auxiliary agent, stir for 1-2 minutes, then add the coupling agent. Add each coupling agent at 15-30 minute intervals, and continue stirring for 45-90 minutes until the coupling agent is evenly dispersed, the aqueous solution is clear, and there are no oil droplets on the surface.

[0064] 2S: Disperse the antioxidant with 15 times its volume of water, stir well, and then add to the container;

[0065] 3S: Disperse the lubricant with 15 times its volume of water, stir well, and then add it to the container;

[0066] 4S: Disperse the light stabilizer with 15 times its volume of water and stir well before adding it to the container;

[0067] 5S: Add the film-forming agent to the container and stir for 1-2 minutes;

[0068] 6S: Add the remaining water to the container and stir well.

[0069] The above preparation methods are merely examples. Without departing from the aforementioned preparation methods provided in this application, those skilled in the art can adjust the order of certain steps or the parameters of specific steps according to actual circumstances to obtain the corresponding glass fiber surface treatment agent.

[0070] In some alternative embodiments, a glass fiber is provided, which is obtained by treating a glass fiber surface treatment agent prepared by the aforementioned preparation method.

[0071] In some alternative embodiments, the use of the above-described glass fiber in a fiberglass composite material with excellent weather resistance is provided.

[0072] The present application will be further described in detail below with reference to specific embodiments, which should not be construed as limiting the scope of protection claimed in the present application.

[0073] Examples 1-12

[0074] The performance test results of the fiberglass composite materials produced by the formulations of Examples 1-6 and their corresponding fiberglass products are shown in Table 1; the performance test results of the fiberglass composite materials produced by the formulations of Examples 7-12 and Comparative Examples 1-2 and their corresponding fiberglass products are shown in Table 2.

[0075] Examples 1-12 show the specific test results of applying glass fiber surface treatment agent to 4800tex direct yarn.

[0076] Unless otherwise specified, in the examples, the isocyanate-based silane coupling agent is 3-propylisocyanatetriethoxysilane; the epoxy silane coupling agent is β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane; and the polyamino silane coupling agent is γ-diethylenetriaminopropyltrimethoxysilane.

[0077] The polyethylene glycol lubricant is PEG1000; the polypropylene glycol lubricant is PPG3000; and the silicone oil lubricant is dimethyl silicone oil.

[0078] The ester antioxidant is tris[2,4-di-tert-butylphenyl]phosphite.

[0079] In the film-forming agent, the epoxy value of the epoxy resin is 0.35±0.3; the relative weight-average molecular weight of the vinyl resin is 8200±500; and the relative weight-average molecular weight of the polyurethane prepolymer is 3900±500.

[0080] The epoxy resin is bis((3,4-epoxycyclohexyl)methyl) adipate; the vinyl resin is epoxy-modified vinyl resin; and the polyurethane prepolymer is a polyurethane prepolymer containing blocked groups.

[0081] The light stabilizer is tris[2,4-di-tert-butylphenyl]phosphite.

[0082] The additives are organic acids, specifically acetic acid and citric acid, with a weight ratio of 3:1.

[0083] Comparative Example 1

[0084] The specific components of the glass fiber surface treatment agent are as follows:

[0085] Coupling agent: a combination of 3-aminopropyltriethoxysilane (5%) and γ-glycidyl ether propyltrimethoxysilane (8%);

[0086] Lubricant: PE1000 (16%);

[0087] Film-forming agent: epoxy-modified vinyl resin (67%);

[0088] Additive: Citric acid (4%).

[0089] Comparative Example 2

[0090] The specific components of the glass fiber surface treatment agent are as follows:

[0091] Coupling agent: γ-methacryloyloxypropyltrimethoxysilane (12%);

[0092] Lubricant: PEGMO (11%);

[0093] Film-forming agent: Bisphenol A type epoxy resin emulsion (71%);

[0094] Additive: glacial acetic acid (6%).

[0095] Table 1

[0096]

[0097]

[0098] Table 2

[0099]

[0100]

[0101] As can be seen from the above formulation test examples, by designing the components and component content of the glass fiber surface treatment agent, a glass fiber surface treatment agent that meets the requirements can be obtained, and all performance data are better than those of the comparative examples; among them, the effects of Examples 6, 8, and 10 are particularly better. It can be seen that when the components in the glass fiber surface treatment agent of this application are matched in the above proportions, the advantages of each component can be fully utilized to achieve better technical effects.

[0102] In summary, the glass fibers produced using the glass fiber surface treatment agent of this application possess excellent weather resistance, smoothness of use, and mechanical properties of fiberglass, which can meet the application requirements of fiberglass composite materials with excellent weather resistance.

[0103] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

[0104] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of this application.

Claims

1. A glass fiber surface treatment agent, characterized in that, The agent comprises an effective component and water, wherein the effective component accounts for 4.2 to 12.5% ​​of the glass fiber surface treatment agent by weight; the effective component comprises, by weight percentage, the following: Coupling agent 11.2~19.7%, antioxidant 0.1~0.5%, lubricant 6.1~11.2%, film-forming agent 59.2~79.7%, light stabilizer 0.5~1.6%, additives 2.5~7.6%; The film-forming agent is a composition of epoxy resin, vinyl resin and polyurethane prepolymer; The epoxy resin is at least one of bisphenol A type epoxy and bisphenol F type epoxy; the vinyl resin is at least one of epoxy modified vinyl resin and toluene diisocyanate modified vinyl resin; the polyurethane prepolymer is at least one of polyurethane prepolymer containing terminal hydroxyl groups and polyurethane prepolymer containing blocked groups. The coupling agent is a silane coupling agent, which is a combination of isocyanate-based silane coupling agents, epoxy-based silane coupling agents, and polyamino-based silane coupling agents.

2. The glass fiber surface treatment agent according to claim 1, characterized in that, The effective component comprises, by weight percentage of the effective component: Coupling agent 12.3~18.8%, antioxidant 0.13~0.46%, lubricant 6.8~10.1%, film-forming agent 61.6~77.9%, light stabilizer 0.6~1.5%, and additives 2.8~7.2%.

3. The glass fiber surface treatment agent according to claim 1, characterized in that, The epoxy resin is a blend of bisphenol A type epoxy and bisphenol F type epoxy; the vinyl resin is an epoxy-modified vinyl resin; and the polyurethane prepolymer is a polyurethane prepolymer containing blocked groups.

4. The glass fiber surface treatment agent according to claim 1, characterized in that, The epoxy value of the epoxy resin is 0.26-0.43; the relative weight-average molecular weight of the vinyl resin is 7000-10000; and the relative weight-average molecular weight of the polyurethane prepolymer is 1700-4800.

5. The glass fiber surface treatment agent according to claim 1 or 2, characterized in that, The epoxy resin accounts for 22.2-39.6% of the effective components by weight; the vinyl resin accounts for 18-30% of the effective components by weight; the polyurethane prepolymer accounts for 10.1-19% of the effective components by weight, and the weight ratio of the epoxy resin, the vinyl resin and the polyurethane prepolymer is (1.17-3.92):(0.95-2.97):

1.

6. The glass fiber surface treatment agent according to claim 1 or 2, characterized in that, The antioxidant is an ester antioxidant, which is at least one of tris[2,4-di-tert-butylphenyl]phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

7. The glass fiber surface treatment agent according to claim 1, characterized in that, The isocyanate-based silane coupling agent accounts for 6.1-9.5% of the effective component by weight; the epoxy-based silane coupling agent accounts for 2.8-5.4% of the effective component by weight; and the polyamino-based silane coupling agent accounts for 2.3-4.8% of the effective component by weight.

8. The glass fiber surface treatment agent according to claim 7, characterized in that, The weight ratio of the isocyanate-based silane coupling agent, the epoxy-based silane coupling agent, and the polyamino silane coupling agent is (1.27~4.12):(0.58~2.35):

1.

9. The glass fiber surface treatment agent according to claim 1 or 2, characterized in that, The lubricant is one or more of the following: polyethylene glycol, polypropylene glycol, fatty acid esters, and silicone oil lubricants; The light stabilizer is an ultraviolet absorber; The additive is an organic acid.

10. The glass fiber surface treatment agent according to claim 9, characterized in that, The ultraviolet absorber is at least one of benzophenone-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers; The organic acid is at least one of citric acid and acetic acid.

11. A method for preparing a glass fiber surface treatment agent as described in any one of claims 1 to 10, characterized in that, include: The glass fiber surface treatment agent is obtained by mixing the additives, coupling agent, antioxidant, lubricant, light stabilizer, film-forming agent, and water.

12. A type of glass fiber, characterized in that, The glass fiber surface treatment agent prepared by the preparation method described in claim 11 is used to treat the glass fiber surface treatment agent.

13. The application of the glass fiber according to claim 12 in a fiberglass composite material with excellent weather resistance.

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