A glass fiber direct yarn sizing agent, its preparation method, product and application

Abstract

The application discloses a glass fiber direct yarn sizing agent and a preparation method thereof. The sizing agent comprises effective components and water, wherein the effective components comprise a silane coupling agent, a film forming agent, a lubricant, a hydrolysis inhibitor and a surfactant; the solid content of the sizing agent is 6.6-13.5 %, and the solid mass percentage of each effective component in the total mass of the sizing agent is as follows: the silane coupling agent is 0.3-1.2 %, the lubricant is 0.7-1.4 %, the hydrolysis inhibitor is 0.4-1.6 %, the film forming agent is 5-8.2 %, and the surfactant is 0.2-1.1 %; wherein the silane coupling agent is an amino silane coupling agent or / and an epoxy silane coupling agent; and the hydrolysis inhibitor is a polymeric carbodiimide or / and an isocyanate. The sizing agent can meet the requirements of good bundling of alkali-free glass fibers and PET filaments during forming, can ensure that the direct yarn material for thermoplastic fibers has less hairiness under high tension, and has excellent mechanical properties and high-temperature and high-humidity resistance, thereby meeting the production and market demands.

Description

Technical Field

[0001] This application relates to the field of fiber production and manufacturing technology, specifically to a glass fiber direct yarn impregnating agent, which is particularly suitable for the production of thermoplastic composite fibers for pultrusion. Background Technology

[0002] With increasing environmental awareness and growing pressure on resources and the environment, green manufacturing technology is no longer just a concept; it has become an effective means to improve enterprise energy efficiency, save costs, and reduce pollution. In recent years, continuous glass fiber reinforced thermoplastic composites have been the fastest-growing type of glass fiber reinforced thermoplastic composite. Compared to thermoplastic composites reinforced with short or long glass fibers, continuous glass fiber reinforced thermoplastic composites retain the macroscopic integrity of the glass fibers, improving the mechanical properties of the composite material several times over. This makes them suitable for applications requiring high load-bearing capacity, thus becoming a hot topic in composite material research.

[0003] PET is a transparent, amorphous copolyester, officially named polyethylene terephthalate-1,4-cyclohexanediethanol ester. It is produced by the transesterification polymerization of three monomers: terephthalic acid (TPA), ethylene glycol (EG), and 1,4-cyclohexanediethanol (CHDM). PET possesses broad chemical resistance, resisting corrosion from greases, acids, and detergents. Most importantly, PET exhibits excellent low-temperature resistance, functioning normally at -30°C, with a minimum resistance down to -60°C, making it ideal for extremely cold regions. PET can impart these superior properties to composite materials. Although a small number of short and long glass fiber reinforced PET composites have appeared on the market, these materials still cannot meet the increasingly demanding application requirements. To further improve the performance of PET composites and expand their application range, the development of continuous glass fiber reinforced PET composites is essential.

[0004] PET-GF composite fiber is a novel thermoplastic fiber formed by the continuous composite direct yarn created during the drawing process of continuous alkali-free glass fiber (EGF) and modified polyethylene terephthalate (PET) filaments, resulting in PET filaments distributed around each glass filament. This composite fiber can be used to prepare pipes and profiles via pultrusion, is easy to form and process, and meets environmental protection requirements. The resulting profiles exhibit excellent mechanical properties, particularly high impact resistance. The products are also lightweight, highly wear-resistant, weather-resistant, corrosion-resistant, and recyclable. As a raw material for high-performance, environmentally friendly composite materials, it is widely used in the construction and municipal engineering fields, such as pultruded doors and windows, and protective dikes, replacing traditional materials such as aluminum, steel, or concrete.

[0005] Thermoplastic fiber direct yarn used in pultrusion processes undergoes a sizing agent coating treatment before lamination. The use and selection of the sizing agent are crucial to the molding and performance of the thermoplastic fiber direct yarn. It must ensure good bundle properties during the lamination of the two fibers (EGF and PET filaments), as well as smoothness during subsequent processing, compatibility of the two materials, and the mechanical properties of the finished product. Otherwise, when using thermoplastic fiber direct yarn to produce doors, windows, or protective dikes, problems such as excessive fuzz under high tension, poor interfacial bonding between the two materials, and low mechanical strength may occur. Furthermore, under high temperature, high humidity, and exposure to sunlight and rain, the composite material is prone to chain-splitting reactions, leading to material degradation, decreased mechanical properties, and a significantly reduced service life. This also limits its application under high temperature, high humidity, and exposure to sunlight and rain conditions. Simultaneously, with the rapid development of thermoplastic materials, high-end customers have increasingly stringent requirements for thermoplastic fiber direct yarn.

[0006] Taking thermoplastic fiber direct yarn as an example (70% glass fiber content, linear density of 2690 tex), its relevant performance indicators are as follows:

[0007] Test Project Tensile strength Hairiness Strength retention rate Reference Standard ASTM D3039 \ 360 hours of constant temperature and humidity at 50℃ and 98% humidity. standard ≥800MPa ≤200mg / kg ≥70％ Summary of the Invention

[0008] To address the problems existing in the background technology, this application provides a glass fiber direct yarn impregnating agent that can satisfy the requirements of good production smoothness and bundling of alkali-free glass fiber and modified polyethylene terephthalate filament during composite molding, and can also ensure that the direct yarn material for thermoplastic fiber has less hair under high tension, good temperature and moisture resistance and excellent mechanical properties, thus meeting the needs of production and the market.

[0009] According to one aspect of this application, a glass fiber direct yarn impregnating agent is provided, comprising an effective component and water, wherein the effective component comprises a silane coupling agent, a film-forming agent, a lubricant, an anti-hydrolysis agent, and a surfactant; the solid content of the impregnating agent is 6.6-13.5%; the percentage of the solid mass of each effective component to the total mass of the impregnating agent is expressed as follows:

[0010]

[0011] Wherein, the silane coupling agent is an aminosilane coupling agent or / and an epoxysilane coupling agent;

[0012] The anti-hydrolysis agent is a polymeric carbodiimide and / or isocyanate.

[0013] Preferably, the percentage of the solid mass of each effective component in the wetting agent to the total mass of the wetting agent is expressed as follows:

[0014]

[0015] Preferably, the film-forming agent comprises a first film-forming agent and a second film-forming agent; the first film-forming agent is an epoxy resin with a molecular weight of 500 to 1000; and the second film-forming agent is a water-soluble epoxy resin with a molecular weight of 7000 to 10000.

[0016] Preferably, the anti-hydrolysis agent is at least one of 2,6-diisopropylbenzene carbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

[0017] Preferably, the aminosilane coupling agent is at least one of γ-aminopropyltrimethoxysilane coupling agent, γ-aminopropyltriethoxysilane coupling agent, and N-β(aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent; the epoxysilane coupling agent is at least one of γ-glycidyl etheroxymethylsilane and 3-glycidyl etheroxypropyltriethoxysilane.

[0018] Preferably, the surfactant is at least one of the following: triethanolamine salt of higher fatty acids, sulfonated castor oil ester salt, alkyl alcohol amide sugars, and ether nonionic surfactants.

[0019] Preferably, the lubricant is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax.

[0020] Preferably, the polyether-modified silicone oil is at least one of polyether-modified polydimethylsiloxane and 3-[hydroxy(polyvinyloxy)propyl]heptamethyltrisiloxane; the PEG-based lubricant is at least one of polyethylene glycol 400 distearate and polyethylene glycol 600 distearate; and the polyethylene wax is at least one of low molecular weight polyethylene homopolymer and low molecular weight polyethylene copolymer.

[0021] The wetting agent of this application comprises an effective component and water, wherein the water includes water contained in the raw material and added water; the effective component comprises a silane coupling agent, a film-forming agent, a lubricant, an anti-hydrolysis agent, and a surfactant; the solid content of the wetting agent is 6.6-13.5%.

[0022] The functions and contents of each component in the glass fiber direct yarn impregnating agent are explained below.

[0023] The use of silane coupling agents in impregnation agents serves two purposes: firstly, it imparts good lubricity to the glass fibers, protecting them from damage during the drawing process; secondly, it enhances the inherent strength of the glass fiber monofilaments. The silane on the glass fiber surface can repair and fill micro-cracks generated during the drawing process. The coupling agent alters the interfacial energy between inorganic materials and polymers, forming chemical or physical "molecular bridges" at the interface, thus firmly bonding the inorganic glass fibers to the organic polymers. In this application, aminosilane coupling agents and / or epoxysilane coupling agents are used, which can improve the mechanical properties, aging resistance, and water resistance of glass fiber reinforced composites. In this application, the aminosilane coupling agent can be at least one of γ-aminopropyltrimethoxysilane coupling agent, γ-aminopropyltriethoxysilane coupling agent, and N-β(aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent; the epoxysilane coupling agent is at least one of γ-glycidyl etheroxymethylsilane and 3-glycidyl etheroxypropyltriethoxysilane. All of the above coupling agents can improve the mechanical properties and other properties of glass fiber reinforced composite materials. Considering factors such as cost and production, the preferred aminosilane coupling agent is γ-aminopropyltrimethylsilane coupling agent, and the preferred epoxysilane coupling agent is γ-glycidyl etheroxymethylsilane. In this application, the amount of silane coupling agent should be reasonably controlled. Excessive dosage will saturate the corresponding active components, resulting in waste and increased production costs, and will also cause poor impregnation and yellow spots on the product's appearance. Insufficient dosage will result in insufficient "molecular bridging" effect, affecting the interfacial bonding between the glass fiber and the resin matrix, thus leading to insufficient mechanical properties of the composite material. Therefore, in this application, the percentage of the solid mass of the silane coupling agent to the total mass of the impregnating agent is controlled to be 0.3% to 1.2%, preferably 0.4% to 1.05%.

[0024] In the impregnating agent, the use of an anti-hydrolysis agent can react with the terminal carboxyl groups, terminal amine groups, and terminal hydroxyl groups generated during polymer hydrolysis to produce stable and harmless products, effectively preventing further degradation and chain scission, and improving the service life of the composite material, especially its anti-hydrolysis and hydrolysis-resistant stability under harsh operating conditions such as high temperature, high humidity, and acid / alkali environments, thereby preventing the rapid decline of the material's mechanical properties. In this application, the anti-hydrolysis agent is a polymeric carbodiimide and / or isocyanate. Polymeric carbodiimide is preferred. The modified polyethylene terephthalate described in this application is a polyester, which is a product of the reaction between an acid and a diol, with water as a byproduct. Therefore, at the melting temperature, the reaction is reversible. The anti-hydrolysis agent can react with the terminal carboxyl groups, terminal amine groups, and terminal hydroxyl groups generated during polymer hydrolysis to produce stable and harmless products, effectively preventing further degradation and chain scission, thereby improving the service life of the composite material. It exhibits particularly stable anti-hydrolysis and hydrolysis-resistant properties under harsh operating conditions such as high temperature, high humidity, and acid / alkali environments. Studies have shown that polymeric carbodiimide has good compatibility with polyester fibers and can provide long-term stability. Furthermore, the anti-hydrolysis agent can be at least one of 2,6-diisopropylphenylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride. In this application, the amount of anti-hydrolysis agent must be controlled within a suitable range. Excessive dosage will cause the product to harden and affect its performance and mechanical properties. Insufficient dosage will result in the product's hydrolysis resistance failing to meet the requirements. In this application, the percentage of the solid mass of the anti-hydrolysis agent to the total mass of the wetting agent is controlled to be 0.4% to 1.6%, preferably 0.5% to 1.45%.

[0025] In this application, the use of surfactants can reduce the surface tension of the sizing agent system, making it easier for the sizing agent to wet the glass fiber surface and achieve uniform coating. The surfactant used in this application is at least one of higher fatty acid triethanolamine salts, sulfonated castor oil ester salts, alkyl alcohol amide sugars, and ether-based nonionic surfactants. Studies have shown that higher fatty acid triethanolamine salts, sulfonated castor oil ester salts, alkyl alcohol amide sugars, and ether-based nonionic surfactants all exhibit good adhesion to polyester fibers, can improve intermolecular forces within the fibers, meet the requirements for fiber bundle cohesion, and prevent increased fuzz caused by fiber bundle disorder. In this application, ether-based nonionic surfactants are preferred, as they can reduce the surface tension of the sizing agent system, making it easier for the sizing agent to wet the glass fiber surface and achieve uniform coating. In this application, the ether-based nonionic surfactant can be rosin amine polyoxyethylene ether. In this application, the amount of surfactant used should be reasonably controlled. If the proportion is too high, it will cause the HLB value to shift towards the aqueous phase, reducing the dispersion and solubilizing power of the oil phase and causing the wetting agent emulsion to break down; if the proportion is too low, it will not play a fiber bundling role. Therefore, in this application, the percentage of the solid mass of the surfactant to the total mass of the wetting agent is controlled to be 0.2% to 1.1%, preferably 0.45% to 0.9%.

[0026] The lubricant used in this application is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax. Polyethylene wax is preferred as the lubricant. The polyethylene wax exists in the form of microcrystals in the sizing agent, is coated onto the fiber surface, dried at high temperature, and migrates to the coating surface during solvent evaporation. Upon cooling to room temperature, it precipitates, ultimately forming a "waxed" surface layer on the fiber. Studies have found that polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax not only have good wet lubrication properties but also good dry lubrication properties. This satisfies the requirements for smoothness of composite fibers during drawing, post-processing, and use, while also ensuring minimal fuzzing of the thermoplastic fiber direct yarn during use. In this application, the polyether-modified silicone oil can be at least one of polyether-modified polydimethylsiloxane and 3-[hydroxy(polyvinyloxy)propyl]heptamethyltrisiloxane; the PEG-based lubricant can be at least one of polyethylene glycol 400 distearate and polyethylene glycol 600 distearate; and the polyethylene wax can be at least one of low molecular weight polyethylene homopolymer and low molecular weight polyethylene copolymer. In this application, the amount of lubricant used needs to be controlled within a suitable range. If the lubricant content is too low, fuzzing is likely to occur during fiber drawing and use, affecting product quality and production efficiency. If the content is too high, the bundled properties of the composite fibers will deteriorate, and the mechanical properties of the composite material will also be affected. Therefore, this application controls the percentage of solid mass of the lubricant to the total mass of the wetting agent to be 0.7% to 1.4%; preferably 0.75% to 1.2%.

[0027] As a major component of the sizing agent, the film-forming agent's performance directly determines the sizing agent's application effect. Its main function is to aggregate glass fiber monofilaments into a bundle, protecting the monofilaments from breakage and mechanical wear. This ensures both the bundled nature of the yarn and its smoothness in subsequent applications, while also increasing the impregnation speed of the glass fiber in the matrix resin, thus having a decisive impact on the processing performance of the final glass fiber product. The film-forming agent in this application can be epoxy resin, which dissolves in water to form an epoxy emulsion used to prepare the sizing agent. In this application, the amount of film-forming agent must be controlled within a suitable range. Excessive use of the film-forming agent can easily lead to poor dispersion, resulting in poor impregnation and decreased mechanical properties, among other quality problems. Conversely, too low a content of the film-forming agent is detrimental to product protection. Therefore, in this application, the percentage of the solid mass of the film-forming agent to the total mass of the sizing agent is controlled to be 5-8.2%, preferably 6.5-7.8%.

[0028] The film-forming agent in this application may include a first film-forming agent and a second film-forming agent. The first film-forming agent may be an epoxy resin with a molecular weight of 500-1000, and the second film-forming agent may be a water-soluble epoxy resin with a molecular weight of 7000-10000. Studies have found that using a small-molecule epoxy emulsion with a molecular weight of 500-1000 can improve the impregnation of the matrix resin in glass fibers and provides a certain degree of temperature resistance. When used in combination with an anti-hydrolysis agent, it can further improve the water resistance of the product. A large-molecule water-soluble epoxy emulsion with a molecular weight of 7000-10000 can improve the yarn's bundle strength and abrasion resistance. In this application, the mass ratio of the first film-forming agent to the second film-forming agent can be 1:(2-2.5); specifically, when the mass ratio of the first film-forming agent to the second film-forming agent is 1:(2.05-2.2), the prepared PET-GF composite fiber achieves optimal performance in all aspects.

[0029] This application uses water as the dispersed phase for each component of the wetting agent. Compared to the solvent dispersed phase, water is more environmentally friendly and safer. Deionized water is preferred.

[0030] The solid content of the wetting agent described in this application is 6.6-13.5%, preferably 8.9-10.8%.

[0031] The impregnating agent in this application is a compound of appropriate amounts of silane coupling agent, film-forming agent, anti-hydrolysis agent, lubricant, and surfactant. This ensures that the direct yarn material of PET-GF thermoplastic composite fiber exhibits minimal fuzz under high tension, while also possessing excellent tensile strength and resistance to high temperatures and humidity. The film-forming agent is used in combination with the silane coupling agent, which reacts with the functional groups in the epoxy resin to form a cross-linked structure, thereby improving the heat resistance, chemical resistance, and strength of the product. Furthermore, it ensures good bundle adhesion during the composite molding of the two fibers, as well as good compatibility and penetration with the polyester resin. The addition of appropriate amounts of lubricant and surfactant effectively reduces fuzz generated during the production and processing of PET-GF thermoplastic composite fiber. In addition, the addition of an appropriate amount of anti-hydrolysis agent ensures minimal degradation of the mechanical properties of the final product under high temperature and humidity conditions.

[0032] According to a second aspect of this application, a method for preparing the aforementioned glass fiber direct yarn impregnating agent is provided, specifically including the following steps:

[0033] 1S: Add water equal to 30%–45% of the total amount of wetting agent to a container, add silane coupling agent and stir thoroughly until the solution is clear;

[0034] 2S: In the container of step 1S, add the film-forming agent, lubricant, anti-hydrolysis agent and surfactant, which have been diluted with water respectively, and stir until uniform.

[0035] 3S: Add water to the formula and stir well to obtain the finished product.

[0036] Preferably, in step 2S, the film-forming agent is diluted with 1 to 5 times its solid mass of water; the lubricant is diluted with 5 to 10 times its solid mass of water; the anti-hydrolysis agent is diluted with 5 to 10 times its solid mass of water; and the surfactant is diluted with 5 to 10 times its solid mass of water.

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

[0038] According to the fourth aspect of this application, the aforementioned glass fiber product is provided for use in a thermoplastic pultrusion process.

[0039] The glass fiber direct yarn treated with the sizing agent described in this application exhibits less fuzz under high tension, resulting in superior mechanical properties and high strength retention under high temperature and humidity conditions. It is highly suitable for thermoplastic pultrusion processes, significantly promoting the reinforcement and increasing the high temperature and humidity resistance of thermoplastic pultruded doors, windows, and protective dikes. Furthermore, the preparation method of the sizing agent described in this application is convenient, has a short production cycle, and is easily mass-produced, showing promise for industrial application. Detailed Implementation

[0040] 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.

[0041] The glass fiber direct yarn impregnating agent of this application comprises a silane coupling agent, a film-forming agent, a lubricant, an anti-hydrolysis agent, a surfactant, and water; wherein the solid mass of the impregnating agent accounts for 6.6% to 13.5% of the total mass of the impregnating agent; the percentage of the solid mass of each component in the impregnating agent to the total mass of the impregnating agent is expressed as follows: silane coupling agent 0.3% to 1.2%; film-forming agent 5% to 8.2%; lubricant 0.7% to 1.4%; anti-hydrolysis agent 0.4% to 1.6%; surfactant 0.2% to 1.1%. Preferably, the solid mass of the wetting agent accounts for 8.6% to 12.4% of the total mass of the wetting agent, and the percentage of the solid mass of each component in the wetting agent to the total mass of the wetting agent is expressed as follows: silane coupling agent 0.4% to 1.05%; film-forming agent 6.5% to 7.8%; lubricant 0.75% to 1.2%; anti-hydrolysis agent 0.5% to 1.45%; surfactant 0.45% to 0.9%.

[0042] The beneficial effects of selecting the above-mentioned ranges of component content in the glass fiber direct yarn impregnating agent of this application will be illustrated by specific experimental data provided through examples.

[0043] Below are examples of preferred value ranges for the components included in the glass fiber direct yarn impregnator according to this application.

[0044] Preferred Example 1

[0045] The glass fiber direct yarn impregnating agent according to this application comprises an effective component and water, and the solid content of the impregnating agent is 6.6% to 13.5%; the percentage of the solid mass of each effective component to the total mass of the impregnating agent is expressed as follows:

[0046]

[0047] Among them, the silane coupling agent is an aminosilane coupling agent and / or an epoxysilane coupling agent;

[0048] The anti-hydrolysis agent is a polymeric carbodiimide and / or isocyanate.

[0049] The first film-forming agent is an epoxy resin with a molecular weight of 500 to 1000, and the second film-forming agent is a water-soluble epoxy resin with a molecular weight of 7000 to 10000.

[0050] The surfactant is at least one of the following: triethanolamine salt of higher fatty acids, sulfonated castor oil ester salt, alkyl alcohol amide sugar, or ether nonionic surfactant.

[0051] The lubricant is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax.

[0052] Preferred Example 2

[0053] The glass fiber direct yarn impregnating agent according to this application comprises an effective component and water, and the solid content of the impregnating agent is 6.95% to 13.25%; the percentage of the solid mass of each effective component to the total mass of the impregnating agent is expressed as follows:

[0054]

[0055] Among them, the silane coupling agent is an aminosilane coupling agent and / or an epoxysilane coupling agent;

[0056] The anti-hydrolysis agent is a polymeric carbodiimide and / or isocyanate.

[0057] The first film-forming agent is an epoxy resin with a molecular weight of 500 to 1000, and the second film-forming agent is a water-soluble epoxy resin with a molecular weight of 7000 to 10000.

[0058] The surfactant is at least one of the following: triethanolamine salt of higher fatty acids, sulfonated castor oil ester salt, alkyl alcohol amide sugar, or ether nonionic surfactant.

[0059] The lubricant is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax.

[0060] Preferred Example 3

[0061] The glass fiber direct yarn impregnating agent according to this application comprises an effective component and water, and the solid content of the impregnating agent is 7.23% to 12.82%; the percentage of the solid mass of each effective component to the total mass of the impregnating agent is expressed as follows:

[0062]

[0063] Among them, the silane coupling agent is an aminosilane coupling agent and / or an epoxysilane coupling agent;

[0064] The anti-hydrolysis agent is at least one of 2,6-diisopropylbenzene carbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

[0065] The surfactant is at least one of the following: triethanolamine salt of higher fatty acids, sulfonated castor oil ester salt, alkyl alcohol amide sugar, or ether nonionic surfactant.

[0066] The lubricant is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax.

[0067] Preferred Example 4

[0068] The glass fiber direct yarn impregnating agent according to this application comprises an effective component and water, and the solid content of the impregnating agent is 7.69% to 12.55%; the percentage of the solid mass of each effective component to the total mass of the impregnating agent is expressed as follows:

[0069]

[0070] Wherein, the silane coupling agent is an aminosilane coupling agent and / or an epoxysilane coupling agent; the aminosilane coupling agent is at least one of γ-aminopropyltrimethoxysilane coupling agent, γ-aminopropyltriethoxysilane coupling agent, and N-β(aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent; the epoxysilane coupling agent is at least one of γ-glycidyl etheroxymethylsilane and 3-glycidyl etheroxypropyltriethoxysilane;

[0071] The hydrolysis resistant agent is at least one of 2,6-diisopropylbenzylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

[0072] The film-forming agent comprises a first film-forming agent and a second film-forming agent; the first film-forming agent is an epoxy resin with a molecular weight of 500 to 1000; the second film-forming agent is a water-soluble epoxy resin with a molecular weight of 7000 to 10000.

[0073] The surfactant is at least one of the following: triethanolamine salt of higher fatty acids, sulfonated castor oil ester salt, alkyl alcohol amide sugar or ether nonionic surfactant;

[0074] The lubricant is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax; the polyether-modified silicone oil is at least one of polyether-modified polydimethylsiloxane and 3-[hydroxy(polyvinyloxy)propyl]heptamethyltrisiloxane; the PEG-based lubricant is at least one of polyethylene glycol 400 distearate and polyethylene glycol 600 distearate; and the polyethylene wax is at least one of low molecular weight polyethylene homopolymer and low molecular weight polyethylene copolymer.

[0075] Preferred Example 5

[0076] The glass fiber direct yarn impregnating agent according to this application comprises an effective component and water, and the solid content of the impregnating agent is 8.27% to 12%; the percentage of the solid mass of each effective component to the total mass of the impregnating agent is expressed as follows:

[0077]

[0078] The silane coupling agent is an aminosilane coupling agent and / or an epoxysilane coupling agent; the aminosilane coupling agent is at least one of γ-aminopropyltrimethoxysilane coupling agent, γ-aminopropyltriethoxysilane coupling agent, and N-β(aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent; the epoxysilane coupling agent is at least one of γ-glycidyl etheroxymethylsilane and 3-glycidyl etheroxypropyltriethoxysilane.

[0079] The hydrolysis resistant agent is at least one of 2,6-diisopropylbenzylcarbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

[0080] The film-forming agent comprises a first film-forming agent and a second film-forming agent; the first film-forming agent is an epoxy resin with a molecular weight of 500 to 1000; the second film-forming agent is a water-soluble epoxy resin with a molecular weight of 7000 to 10000.

[0081] The surfactant is at least one of the following: triethanolamine salt of higher fatty acids, sulfonated castor oil ester salt, alkyl alcohol amide sugar or ether nonionic surfactant;

[0082] The lubricant is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax; the polyether-modified silicone oil is at least one of polyether-modified polydimethylsiloxane and 3-[hydroxy(polyvinyloxy)propyl]heptamethyltrisiloxane; the PEG-based lubricant is at least one of polyethylene glycol 400 distearate and polyethylene glycol 600 distearate; the polyethylene wax is at least one of low molecular weight polyethylene homopolymer and low molecular weight polyethylene copolymer.

[0083] Preferred Example Six

[0084] The glass fiber direct yarn impregnating agent according to this application comprises an effective component and water, and the solid content of the impregnating agent is 8.48% to 11.62%. The percentage of the solid mass of each effective component to the total mass of the impregnating agent is expressed as follows:

[0085]

[0086] The aminosilane coupling agent is γ-aminopropyltrimethylsilane coupling agent, and the epoxysilane coupling agent is γ-glycidyl etheroxymethylsilane; the anti-hydrolysis agent is 2,6-diisopropylbenzene carbodiimide; the film-forming agent includes a first film-forming agent and a second film-forming agent, the first film-forming agent being an epoxy resin with a molecular weight of 500-1000, and the second film-forming agent being a water-soluble epoxy resin with a molecular weight of 7000-10000; the surfactant is rosin amine polyoxyethylene ether; and the lubricant is low molecular weight polyethylene homopolymer.

[0087] The methods for preparing the glass fiber direct yarn impregnating agent according to preferred examples one to six specifically include the following steps:

[0088] 1S: Add water equal to 30%–45% of the total amount of wetting agent to a container, add silane coupling agent and stir thoroughly until the solution is clear;

[0089] 2S: In the container of step 1S, add the film-forming agent, lubricant, anti-hydrolysis agent and surfactant, which have been diluted with water respectively, and stir until uniform.

[0090] 3S: Add water to the formula and stir well to obtain the finished product;

[0091] In step 2S, the film-forming agent is diluted with 1 to 5 times its solid mass of water; the lubricant is diluted with 5 to 10 times its solid mass of water; the anti-hydrolysis agent is diluted with 5 to 10 times its solid mass of water; and the surfactant is diluted with 5 to 10 times its solid mass of water.

[0092] To more clearly explain the technical solution of this application, some specific embodiments of the glass fiber direct yarn impregnation agent of this application (Examples 1 to 16) are listed below. The specific formulations of each component of the glass fiber direct yarn impregnation agent of Examples 1 to 16 of this application are shown in Table 1.

[0093] 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.

[0094] Table 1 shows the formulations of the wetting agents used in the embodiments.

[0095]

[0096] Table 1 (continued) Formulation of the wetting agent in the examples

[0097]

[0098] In Table 1, the first film-forming agent is an epoxy resin with a molecular weight of 500 to 1000; the second film-forming agent is a water-soluble epoxy resin with a molecular weight of 7000 to 10000.

[0099] To further illustrate the beneficial effects of this application, two commonly used glass fiber direct yarn sizing agents were selected as comparative examples, namely Comparative Examples 1 and 2. The formulations of Comparative Examples 1 and 2 are shown below, wherein the amount of the effective component is the percentage of the solid mass of the effective component to the total mass of the sizing agent.

[0100] Comparative Example 1:

[0101] Silane coupling agent: Vinyltriethoxysilane; 0.2%

[0102] First film-forming agent: Maleic anhydride modified polyethylene emulsion; 1.2%

[0103] Second film-forming agent: Maleic anhydride modified polypropylene emulsion; 3.2%

[0104] Lubricant: PEG400MS; 0.8%

[0105] Anti-hydrolysis agent: dimethyl oxazoline; 0.3%

[0106] Surfactant: Quaternary ammonium salt; 0.1%

[0107] Comparative Example 2:

[0108] Coupling agent: Propyl dioleoyl oxytitanate; 0.5%

[0109] First film-forming agent: polyurethane emulsion; 0.8%

[0110] Second film-forming agent: PP wax emulsion; 3.6%

[0111] Lubricant: Fatty acid amide; 0.55%

[0112] Anti-hydrolysis agent: dimethyl oxazoline; 0.38%

[0113] Surfactant: Imidazole ring; 1.2%

[0114] The prepared sizing agents (Examples 1-16 and Comparative Examples 1-4) were applied in specific glass fiber and PET fiber production processes, and the performance of the produced 2690tex thermoplastic direct yarn was tested. The specific test results are shown in Table 2. The linear density and breaking strength of the yarn were tested according to GB / T 7690.1-2013 and GB / T 7690.3-2013, respectively. The tensile strength and strength retention rate under high temperature and high humidity conditions provided in Table 2 were obtained by producing sheets with a thickness of 1 mm and a width of 10 mm using a direct yarn pultrusion process for thermoplastic fibers, and finally preparing samples according to the ASTM D3039 test standard to determine the tensile strength. High temperature and high humidity resistance test: A constant temperature and humidity chamber was used. The test process involved maintaining a constant temperature and humidity of 50℃ and 98% humidity for 360 hours to test the tensile strength retention rate under high temperature and high humidity conditions.

[0115] Table 2. Performance test results of the wetting agents in the examples and comparative examples.

[0116]

[0117] Table 2 (continued) Performance test results of the wetting agents in the examples and comparative examples

[0118]

[0119]

[0120] As can be seen from the test results in Table 2, by selecting the types and controlling the content of each component of the sizing agent, we can obtain a sizing agent formulation that meets the requirements. The thermoplastic fiber direct yarn prepared with it has less fuzz, and the resulting composite profile has good tensile strength and high strength retention rate under high temperature and high humidity. In addition, the inventors also used other comparative sizing agents to compare with the sizing agent of this application (Examples 1-16). The anti-hydrolysis agents used in the other comparative examples do not include any one of polymeric carbodiimide or isocyanate. Compared with the sizing agents of the other comparative examples, the thermoplastic fiber direct yarn prepared with the sizing agent of Examples 1-16 of this application has less fuzz, and the resulting composite profile has good tensile strength and high strength retention rate under high temperature and high humidity.

[0121] In summary, the thermoplastic fiber direct fiber yarn produced by the glass fiber direct yarn impregnator involved in this application has good bundle properties and excellent processing performance, making it suitable for pultrusion processes under high tension; the prepared composite material pipe has excellent mechanical properties and excellent temperature and moisture resistance.

[0122] The above-described contents can be implemented individually or in various combinations, and all such variations are within the scope of protection of this application.

[0123] 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 direct yarn impregnating agent, characterized in that: The wetting agent comprises an active ingredient and water. The active ingredient comprises a silane coupling agent, a film-forming agent, a lubricant, an anti-hydrolysis agent, and a surfactant. The solid content of the wetting agent is 6.6%–13.5%. The percentage of the solid mass of each active ingredient to the total mass of the wetting agent is expressed as follows: Silane coupling agent 0.3–1.2% Lubricant 0.7-1.4% Anti-hydrolysis agent 0.4–1.6% Film-forming agent 5-8.2% Surfactant 0.2%–1.1% Wherein, the silane coupling agent is an aminosilane coupling agent or / and an epoxysilane coupling agent; The anti-hydrolysis agent is a polymeric carbodiimide and / or isocyanate; The film-forming agent comprises a first film-forming agent and a second film-forming agent; the first film-forming agent is an epoxy resin with a molecular weight of 500-1000; the second film-forming agent is a water-soluble epoxy resin with a molecular weight of 7000-10000; the mass ratio of the first film-forming agent to the second film-forming agent is 1:(2-2.5); The surfactant is at least one of the following: triethanolamine salt of higher fatty acids, sulfonated castor oil ester salt, alkyl alcohol amide sugars, and ether nonionic surfactants.

2. The glass fiber direct yarn impregnating agent as described in claim 1, characterized in that, The percentage of the solid mass of each effective component in the wetting agent relative to the total mass of the wetting agent is expressed as follows: Silane coupling agent 0.4–1.05% Lubricant 0.75–1.2% Anti-hydrolysis agent 0.5–1.45% Film-forming agent 6.5–7.8% Surfactant 0.45-0.9%.

3. The glass fiber direct yarn impregnation agent as described in claim 1 or 2, characterized in that, The anti-hydrolysis agent is at least one of 2,6-diisopropylbenzene carbodiimide, 1-(3-dimethylaminopropyl)-3-ethyl-carbodiimide hydrochloride, and 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride.

4. The glass fiber direct yarn impregnating agent as described in claim 1 or 2, characterized in that, The aminosilane coupling agent is at least one of γ-aminopropyltrimethoxysilane coupling agent, γ-aminopropyltriethoxysilane coupling agent, and N-β(aminoethyl)-γ-aminopropyltrimethoxysilane coupling agent; the epoxysilane coupling agent is at least one of γ-glycidyl etheroxymethylsilane and 3-glycidyl etheroxypropyltriethoxysilane.

5. The glass fiber direct yarn impregnation agent as described in claim 1 or 2, characterized in that, The lubricant is at least one of polyether-modified silicone oil, PEG-based lubricant, and polyethylene wax; The polyether-modified silicone oil is at least one of polyether-modified polydimethylsiloxane and 3-[hydroxy(polyvinyloxy)propyl]heptamethyltrisiloxane; the PEG-based lubricant is at least one of polyethylene glycol 400 distearate and polyethylene glycol 600 distearate; and the polyethylene wax is at least one of low molecular weight polyethylene homopolymer and low molecular weight polyethylene copolymer.

6. A method for preparing a glass fiber direct yarn impregnating agent as described in any one of claims 1 to 5, characterized in that, Includes the following steps: 1S: Add water equal to 30%–45% of the total amount of wetting agent to a container, add silane coupling agent and stir thoroughly until the solution is clear; 2S: In the container from step 1S, add the film-forming agent, lubricant, anti-hydrolysis agent, and surfactant, which have been diluted with water respectively, and stir until homogeneous; 3S: Add water to the formula and stir well to obtain the finished product.

7. A glass fiber product produced by coating with the glass fiber direct yarn impregnation agent according to any one of claims 1 to 5.

8. The application of the glass fiber product as described in claim 7 in a thermoplastic pultrusion process.

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