Glass fiber sizing agent and method for producing the same, glass fiber product

Abstract

The application discloses a glass fiber sizing agent and a preparation method thereof, and a glass fiber product. The glass fiber sizing agent comprises effective components and water, the solid content of the sizing agent is 3-6%, and the solid mass percentage of each effective component in the sizing agent in the total mass of the sizing agent is as follows: 5-12% of a silane coupling agent A, 1-6% of a silane coupling agent B, 20-49% of a film forming agent A, 12-30% of a film forming agent B, 5-20% of a film forming agent C, 5-14% of a lubricant A, 1-7% of a lubricant B, 1-6% of a fluffy softening agent and 1-6% of a pH value regulator; wherein the film forming agent A is an aqueous aliphatic epoxy emulsion; the film forming agent B is a non-ionic aqueous polyurethane modified epoxy emulsion; and the film forming agent C is a water-soluble bisphenol A / F type epoxy emulsion. The glass fiber yarn produced by using the sizing agent has less hairiness, high bulking rate, good interface compatibility with an epoxy resin, rapid and complete penetration, and can be applied to the field of wind power pultrusion plates.

Description

Technical Field

[0001] This application relates to the field of glass fiber impregnating agents, and particularly to a glass fiber impregnating agent and its preparation method, as well as a glass fiber product. The glass fiber impregnating agent is especially suitable for alkali-free glass fiber bulked yarn for epoxy pultruded sheets. Background Technology

[0002] Glass fiber is an inorganic non-metallic material with excellent properties such as high modulus and light weight, and is widely used in reinforcing emulsions to prepare composite materials. Glass fiber bulked yarn is a novel type of yarn. It is produced using an air-jet method, where continuous glass fiber yarn, including twisted or untwisted rovings, is passed through a bulking nozzle. Inside the nozzle, it is subjected to turbulent impact and disturbance created by compressed air, causing the fibers in the yarn to separate and increase in volume, thus becoming bulked yarn. Due to this processing characteristic, bulked yarn combines some advantages of both continuous and fixed-length fibers, such as bulkiness, better hand feel, high coverage, and higher yarn strength and uniformity than fixed-length fibers. It can be produced in various yarn counts to meet the requirements of different fields, giving glass fiber bulked yarn products a huge market prospect.

[0003] In the application of pultruded profiles, bulked yarn can increase the amount of adhesive absorbed by local fibers, ensuring good filling in some complex structures or surfaces of pultruded fiberglass products. It can compensate for structural defects and rough appearance caused by insufficient emulsion flow and insufficient fiber emulsion absorption when using pure untwisted glass fibers. At the same time, the fiber orientation in bulked yarn is uncertain due to twisting and deformation, thus improving the transverse adhesion of pultruded profile products.

[0004] With the continuous development of composite material technology, the application of epoxy pultruded sheets in wind turbine blade spars has become increasingly mature in the wind power field in recent years. Currently, there are no expanded polypropylene yarn products specifically developed for reinforcing epoxy emulsions. Existing expanded polypropylene yarns used as fillers in mufflers on the market are all reinforced with unsaturated polyester resins, which have poor compatibility with epoxy resins, resulting in problems such as poor fiber penetration and insufficient transverse adhesion of the finished product, failing to meet the requirements for wind power pultruded sheets. Therefore, developing an alkali-free glass fiber expanded polypropylene yarn for epoxy-reinforced pultruded sheets is of great significance. Summary of the Invention

[0005] To address the aforementioned technical problems, this application provides a glass fiber sizing agent. Alkali-free glass fiber bulked yarn produced by coating with this sizing agent not only has a high expansion rate but also good compatibility and penetration with the target resin. Furthermore, it can improve the mechanical properties of the product, meeting industry standards and application requirements.

[0006] According to a first aspect of this application, a glass fiber sizing agent is provided, the sizing agent comprising an effective component and water; the solid content of the glass fiber sizing agent is 3% to 6%, and the effective component comprises silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, a fluffing and softening agent, and a pH adjuster, wherein 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:

[0007]

[0008] Wherein, film-forming agent A is an aqueous aliphatic epoxy emulsion; film-forming agent B is a nonionic aqueous polyurethane-modified epoxy emulsion; and film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion.

[0009] Preferably, the mass ratio of film-forming agent A, film-forming agent B and film-forming agent C is (1-10):(1.5-2):1.

[0010] Preferably, the molecular weight of the aqueous aliphatic epoxy emulsion is 350-800.

[0011] Preferably, the molecular weight of the nonionic waterborne polyurethane-modified epoxy emulsion is 1500-3500.

[0012] Preferably, the average molecular weight of the water-soluble bisphenol A / F type epoxy emulsion is 300 to 1000.

[0013] Preferably, the silane coupling agent A is an epoxy silane coupling agent, and the silane coupling agent B is an amino silane coupling agent.

[0014] Preferably, the mass ratio of the epoxy silane coupling agent to the silane amino silane coupling agent is 2:1 to 5:1.

[0015] Preferably, lubricant A is at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant; lubricant B is a hydrophilic organosilicon lubricant.

[0016] Preferably, the lubricant B is water-based dimethyl silicone oil.

[0017] Preferably, the fluffing and softening agent is a hydrophilic silicone oil-based binary copolymer compound.

[0018] According to a second aspect of this application, a method for preparing the above-mentioned glass fiber impregnating agent is provided, comprising:

[0019] After adding the pH adjuster to water and stirring until homogeneous, add silane coupling agent A and silane coupling agent B, stir until homogeneous, and obtain a solution containing silane coupling agent A and silane coupling agent B.

[0020] Film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, and fluffing softener, diluted with water respectively, are mixed with a solution containing silane coupling agent A and silane coupling agent B. The remaining water is added, and the mixture is stirred evenly to obtain the glass fiber impregnating agent.

[0021] Preferably, the film-forming agent A is an aqueous aliphatic epoxy emulsion with a pH value of 6-7 and a particle size of 0.12-1.0 μm.

[0022] Preferably, the film-forming agent B is a nonionic waterborne polyurethane-modified epoxy emulsion, the pH value of the nonionic waterborne polyurethane-modified epoxy emulsion is 5-7, and the particle size of the nonionic waterborne polyurethane-modified epoxy emulsion is 0.2-2.0 μm.

[0023] Preferably, the film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion, the pH value of the water-soluble bisphenol A / F type epoxy emulsion is 5 to 7, and the particle size of the water-soluble bisphenol A / F type epoxy emulsion is 0.15 to 2.0 μm.

[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 a fourth aspect of this application, an application of the aforementioned glass fiber product in the production of epoxy pultruded sheets is provided.

[0026] Compared with the prior art, this application, through the synergistic effect between the components, enables the glass fiber prepared by coating with the glass fiber sizing agent of this application to have excellent performance, thereby meeting the performance requirements of fiberglass for epoxy pultruded sheet production.

[0027] Its beneficial effects are reflected in:

[0028] First, the film-forming agent imparts bundled properties and flexibility to the yarn. This application uses three different types of epoxy emulsion film-forming agents, which, when dissolved in water, form an aqueous aliphatic epoxy emulsion, a nonionic water-soluble polyurethane-modified epoxy emulsion, and a water-soluble bisphenol A / F type epoxy emulsion. The synergistic use of these three film-forming agents improves the bundled properties of the glass fiber yarn, which is beneficial for yarn drawing and shaping, and also facilitates the subsequent expansion process.

[0029] Secondly, with the assistance of the fluffing and softening agent, the glass fiber yarn becomes relatively soft, and the gaps between the fibers are increased, which increases the fullness of the yarn and also provides a certain degree of smoothness. This facilitates the production and processing of fiber products. The yarn is easier to expand during the expansion process and can spread out naturally, which greatly increases the contact area between the yarn and the epoxy emulsion, thereby improving the impregnation speed and impregnation effect. Therefore, it can greatly improve the fiberglass performance of epoxy pultruded sheets. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below in conjunction with the 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.

[0031] In some optional embodiments, a glass fiber sizing agent is provided, comprising an active ingredient and water; the solid content of the sizing agent is 3% to 6%, and the active ingredient comprises silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, a fluffing and softening agent, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the sizing agent is expressed as follows:

[0032]

[0033]

[0034] Among them, film-forming agent A is an aqueous aliphatic epoxy emulsion; film-forming agent B is a nonionic aqueous polyurethane-modified epoxy emulsion; and film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion.

[0035] It should be noted that the mass percentage of each effective component and the mass ratio between effective components in this application are expressed in terms of solid mass; the water-soluble bisphenol A / F type epoxy emulsion in this application refers to a mixture of water-soluble bisphenol A type epoxy emulsion and water-soluble bisphenol F type epoxy emulsion.

[0036] In some optional embodiments, a glass fiber sizing agent is provided, comprising an active ingredient and water; the solid content of the sizing agent is 3% to 6%, and the active ingredient comprises silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, a fluffing and softening agent, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the sizing agent is expressed as follows:

[0037]

[0038] Among them, film-forming agent A is an aqueous aliphatic epoxy emulsion; film-forming agent B is a nonionic aqueous polyurethane-modified epoxy emulsion; and film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion.

[0039] In some optional embodiments, a glass fiber sizing agent is provided, comprising an active ingredient and water; the solid content of the sizing agent is 3% to 6%, and the active ingredient comprises silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, a fluffing and softening agent, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the sizing agent is expressed as follows:

[0040]

[0041] Among them, film-forming agent A is an aqueous aliphatic epoxy emulsion; film-forming agent B is a nonionic aqueous polyurethane-modified epoxy emulsion; and film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion.

[0042] The alkali-free glass fiber expanded yarn sizing agent of this application introduces two silane coupling agents and three epoxy film-forming agents. Through their synergistic use, the glass fiber yarn exhibits relatively good bundle properties and facilitates expansion during the production of expanded yarn, preventing yarn adhesion. It also improves the compatibility between glass fiber and epoxy emulsion, thereby enhancing the fiberglass performance of epoxy pultruded sheets to a certain extent. By introducing a fluffing and softening agent as an auxiliary agent, the yarn becomes fuller and possesses a certain degree of smoothness, making it easier to expand. The sizing agent is prepared through the interaction of substances such as silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, fluffing and softening agent, pH adjuster, and water. Glass fiber yarn coated with this sizing agent exhibits characteristics such as easy dispersion and good compatibility with epoxy emulsion. Epoxy pultruded sheets made from expanded yarn produced by this sizing agent have superior performance compared to conventional products, meeting the urgent needs of the market.

[0043] Film-forming agents are the main components of sizing agents used in glass fibers. They protect glass fibers and improve their bundle structure and stiffness, having a decisive impact on the continuous production and application of glass fibers. Therefore, the selection of film-forming agents is also a key focus of this application. This application uses a mixture of film-forming agents A, B, and C. Film-forming agent A is an aqueous aliphatic epoxy emulsion; film-forming agent B is a nonionic aqueous polyurethane-modified epoxy emulsion; and film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion. Film-forming agents A, B, and C are all used in the form of emulsions to prepare the sizing agent. The use of water-based aliphatic epoxy emulsion film-forming agents can make the yarn slightly stiffer, which is more conducive to yarn drawing and forming. The use of non-ionic water-based polyurethane modified epoxy emulsion film-forming agents can enhance the toughness of the yarn and make it easier for the yarn to unfurl during the swelling process. The use of water-soluble bisphenol A / F type epoxy emulsions can be used as a regulating component to bring the yarn to the desired optimal state. At the same time, the dosage of the three film-forming agents needs to be controlled within an appropriate range: film-forming agent A is 20% to 49%, film-forming agent B is 12% to 30%, and film-forming agent C is 5% to 20%; preferably, film-forming agent A is 26% to 46%, film-forming agent B is 15% to 27%, and film-forming agent C is 6% to 18%; more preferably, film-forming agent A is 30% to 40%, film-forming agent B is 16% to 22%, and film-forming agent C is 10% to 14%.

[0044] Coupling agents act as chemical bridges between the glass fiber surface, the sizing agent layer, and the emulsion matrix layer. Silane coupling agents contain both organic and inorganic functional groups. The silanol bonds resulting from the hydrolysis of the silane coupling agent can condense with the hydroxyl groups on the glass fiber surface, forming chemical bonds on the glass fiber surface. The organic functional groups of the silane coupling agent molecule have good compatibility with the emulsion matrix, which can enhance the bonding force between the glass fiber and the composite matrix emulsion. Therefore, the structure of the silane coupling agent is key to determining the bonding ability between the glass fiber and the surface coating adhesive. The silane coupling agent in this application is a mixture of silane coupling agent A and silane coupling agent B. The amounts of the two silane coupling agents need to be controlled within a suitable range: silane coupling agent A is 5%–12%, and silane coupling agent B is 1%–6%; preferably, silane coupling agent A is 6%–11%, and silane coupling agent B is 2%–5%; more preferably, silane coupling agent A is 7%–10%, and silane coupling agent B is 3%–4%.

[0045] The lubricant used in this application is mainly to meet the lubrication and anti-friction damage requirements of glass fiber drawing and post-processing, and to help the glass fiber quickly and completely impregnate and uniformly disperse in the epoxy emulsion. However, excessive lubricant will affect the bundle properties of the glass fiber yarn, ultimately affecting the mechanical properties of the fiberglass product. The lubricant used in this application is a mixture of lubricant A and lubricant B. The dosage of the two lubricants needs to be controlled within a suitable range: lubricant A is 5% to 14%, and lubricant B is 1% to 7%; preferably, lubricant A is 6% to 11%, and lubricant B is 2% to 6%; more preferably, lubricant A is 8% to 10%, and lubricant B is 3% to 5%.

[0046] This application incorporates a fluffing and softening agent to give the yarn both good fullness and smoothness, making it easier to swell during the yarn swelling process. However, the fluffing and softening agent cannot be added in excess. Through multiple tests, it has been verified that adding too much will affect the yarn's bundle properties and make the yarn softer. The percentage of the solid mass of the fluffing and softening agent to the total solid mass of the sizing agent is 1% to 6%, preferably 2% to 5%, and more preferably 3% to 4%.

[0047] The pH adjuster is mainly used to adjust the pH value of the wetting agent, so that the silane coupling agent can be better and faster to disperse evenly in water. The solid mass of the pH adjuster accounts for 1% to 6% of the total solid mass of the wetting agent, preferably 2% to 5%, and more preferably 3% to 4%.

[0048] This application uses water as the dispersed phase of the various components of the wetting agent, resulting in a solid content of 3% to 6%. Compared to solvent-dispersed phases, water is more environmentally friendly and safer. Deionized water is preferred.

[0049] In some optional embodiments, the mass ratio of film-forming agent A, film-forming agent B and film-forming agent C is (1-10):(1.5-2):1.

[0050] The dosage of the three film-forming agents needs to be controlled within an appropriate range. If too much film-forming agent A (waterborne aliphatic epoxy emulsion) is used, it will result in poor yarn toughness and wave resistance, affecting the yarn's penetration speed in the emulsion. If too much film-forming agent B (nonionic waterborne polyurethane modified epoxy emulsion) is used, the toughness will be too high, resulting in soft yarn that is easy to unravel and has poor bundle properties. If too much film-forming agent C (water-soluble bisphenol A / F type epoxy emulsion) is used, it will result in uneven film formation of the sizing agent, excessively stiff yarn, and difficulty in swelling. When the mass ratio of film-forming agent A, film-forming agent B, and film-forming agent C is (1-10):(1.5-2):1, the resulting waterborne aliphatic epoxy emulsion, polyurethane-modified epoxy emulsion, and bisphenol A / F epoxy emulsion are uniform and stable, and have good compatibility with the matrix emulsion. During use, the yarn can swell well, greatly increasing the contact area between the yarn and the epoxy emulsion, thereby improving the impregnation speed and impregnation effect, and significantly improving the fiberglass performance of epoxy pultruded sheets. The mass ratio of film-forming agent A, film-forming agent B and film-forming agent C can also be (2.5-4):(1.5-2):1; for example, the mass ratio of film-forming agent A, film-forming agent B and film-forming agent C can also be 2:1.5:1, 2.5:1.5:1, 3:1.5:1, 3.5:1.5:1, 4:1.5:1, 4.5:1.5:1, 5:1.5:1, 2:2:1, 2.5:2:1, 3:2:1, 3.5:2:1, 4:2:1, 4.5:2:1, 5:2:1.

[0051] In some optional embodiments, film-forming agent A is a small-molecule aliphatic epoxy emulsion with a molecular weight of 350–800. In some optional embodiments, film-forming agent A is an aqueous aliphatic epoxy emulsion with a pH value of 6–7 and a particle size of 0.12–1.0 μm. Aliphatic epoxy emulsions with these parameters exhibit good chemical stability.

[0052] In some optional embodiments, film-forming agent B is a nonionic waterborne polyurethane-modified epoxy emulsion with a molecular weight of 1500–3500. In some optional embodiments, film-forming agent B is a nonionic waterborne polyurethane-modified epoxy emulsion with a pH value of 5–7 and a particle size of 0.2–2.0 μm. Nonionic waterborne polyurethane-modified epoxy emulsions with these parameters exhibit excellent dispersibility and dispersion stability. In some optional embodiments, the nonionic waterborne polyurethane-modified epoxy emulsion is generated by reacting isophorone diisocyanate, polyethylene glycol, and epoxy emulsion under certain conditions.

[0053] In some optional embodiments, the film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion with an average molecular weight of 300–1000. In some optional embodiments, the film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion with a pH value of 5–7 and a particle size of 0.15–2.0 μm. Water-soluble bisphenol A / F type epoxy emulsions with these parameters exhibit good dispersibility and strong stability.

[0054] In some optional embodiments, silane coupling agent A is an epoxy silane coupling agent, and silane coupling agent B is an amino silane coupling agent.

[0055] Epoxy-silane coupling agents and amino-silane coupling agents not only provide silanol groups for chemical bonding with the glass fiber surface, but also offer polar organic functional groups (epoxy and amino groups) at their other ends. These groups form strong interactions with the epoxy and amino groups contained in the film-forming molecules of the main components of the sizing agent, thus strengthening the bond between the sizing agent and the glass fiber. The combined use of epoxy-silane and amino-silane coupling agents can give the glass fiber precursor better smoothness, reduce mechanical wear, and effectively protect the glass fiber. Simultaneously, it strengthens the connection between the glass fiber and the epoxy emulsion matrix, resulting in a higher bonding strength between the glass fiber and the composite emulsion. This significantly enhances the mechanical properties of the epoxy pultruded sheet composed of glass fiber reinforced composite materials, thereby improving the fiberglass performance of the epoxy pultruded sheet.

[0056] In some optional embodiments, silane coupling agent A is γ-glycidoxypropyltrimethoxysilane, and silane coupling agent B is γ-aminopropyltriethoxysilane.

[0057] In some optional embodiments, the mass ratio of epoxy silane coupling agent to amino silane coupling agent is 2:1 to 5:1.

[0058] In this application, if the amount of epoxy silane coupling agent is too large, the improvement in the mechanical properties of the product is not significant; if the amount of amino silane coupling agent is too large, it will cause the glass fiber yarn to be too stiff, and the yarn clumps will turn yellow. The inventors have found that when the mass ratio of epoxy silane coupling agent to amino silane coupling agent is 2:1 to 5:1, the synergistic effect of the two is better, which can significantly enhance the fiberglass performance of epoxy pultruded sheets. The mass ratio of epoxy silane coupling agent to amino silane coupling agent can also be 2:1 to 3:1; for example, the mass ratios of epoxy silane coupling agent to amino silane coupling agent are 2:1, 2.5:1, 3:1, 3.5:1, and 4:1.

[0059] In some optional embodiments, lubricant A is at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant; lubricant B is a hydrophilic organosilicon lubricant. Specifically, lubricant B can be water-based dimethyl silicone oil. In some optional embodiments, the average molecular weight of lubricant A (at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant) is 2000-3000, and the molecular weight of lubricant B (hydrophilic organosilicon lubricant) can be 3000-5000. Lubricant mixtures within this range are viscous liquids with minimal viscosity change with temperature, providing not only good lubrication but also helping to improve the problem of glass not easily spreading.

[0060] In some optional embodiments, the mass ratio of lubricant A (at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant) to lubricant B (hydrophilic organosilicon lubricant) is 2:1 to 5:1.

[0061] Excessive use of lubricant A (at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant) will affect the forming of the glass fiber bobbin and easily cause it to soften and deform. Excessive use of lubricant B (hydrophilic silicone lubricant) will reduce the mechanical properties of the fiberglass products. When the mass ratio of lubricant A (at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant) to lubricant B (hydrophilic silicone lubricant) is 2:1 to 5:1, the glass fiber has both good formability and mechanical properties. The mass ratio of lubricant A (at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant) to lubricant B (hydrophilic silicone lubricant) can also be 2:1 to 3:1; for example, 2:1, 2.5:1, 3:1, 3.5:1, and 4:1.

[0062] In some optional embodiments, the fluffing softener is a hydrophilic silicone oil-based binary copolymer compound.

[0063] This application uses hydrophilic silicone oil-based binary copolymer compounds as fluffing and softening agents, which can reduce friction between fibers, make glass fiber yarns relatively soft, and increase the gaps between fibers, thus facilitating the production and processing of fiber products.

[0064] In some optional embodiments, the pH adjuster is an organic acid with a pH of 3 to 6.

[0065] The pH adjuster used in this application is an organic acid with a pH value of 3 to 6. This organic acid has a better dispersing effect and is more suitable for this wetting agent system.

[0066] In some optional embodiments, a method for preparing the above-mentioned glass fiber impregnating agent is provided, comprising the following steps:

[0067] After adding the pH adjuster to water and stirring evenly, add silane coupling agent A and silane coupling agent B, stir evenly, and obtain a solution containing silane coupling agent A and silane coupling agent B.

[0068] Film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, and fluffing softener, diluted separately with water, are mixed with a solution containing silane coupling agent A and silane coupling agent B. The remaining water is added, and the mixture is stirred evenly to obtain a glass fiber impregnating agent.

[0069] In some optional embodiments, film-forming agent A is an aqueous aliphatic epoxy emulsion with a pH value of 6 to 7 and a particle size of 0.12 to 1.0 μm.

[0070] In some optional embodiments, film-forming agent B is a nonionic waterborne polyurethane-modified epoxy emulsion with a pH value of 5 to 7 and a particle size of 0.2 to 2.0 μm.

[0071] In some optional embodiments, the film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion with a pH value of 5 to 7 and a particle size of 0.15 to 2.0 μm.

[0072] In some optional embodiments, a method for preparing the above-mentioned glass fiber impregnating agent is provided, comprising the following steps:

[0073] 1S: Add water equal to approximately 40% of the total mass of the wetting agent to the first container, then add the pH adjuster and silane coupling agent A in sequence, stir for 30-40 minutes, then add silane coupling agent B, stir for 15-20 minutes, and obtain a mixed solution containing silane coupling agent A and silane coupling agent B.

[0074] 2S: Dilute film-forming agent A, film-forming agent B, and film-forming agent C with 3 to 5 times their respective weights of water, stir well, and then add them to the first container;

[0075] 3S: Dilute lubricant A and lubricant B with 4 to 6 times their weight of water and stir well before adding them to the first container;

[0076] 4S: Dilute the fluffing and softening agent with 3 to 5 times its weight of water and stir evenly. Add the mixture to the first container, add the remaining water to the first container, and stir evenly to obtain the glass fiber impregnating agent of this application.

[0077] In some alternative embodiments, a glass fiber product produced by coating with the aforementioned glass fiber sizing agent is provided.

[0078] In some alternative embodiments, an application of the aforementioned glass fiber product in the production of epoxy pultruded sheets is provided.

[0079] The specific formulations of some embodiments of the glass fiber impregnating agent of this application are shown in Table 1. The values ​​in Table 1 are the percentages of the solid mass of the effective component to the total solid mass of the impregnating agent. It should be noted that the specific types, contents, and combinations of the effective components selected in Table 1 do not constitute a limitation on the scope of protection of this application.

[0080] Table 1. Wetting agent formulations for the embodiments.

[0081]

[0082] Table 1 (continued) - Immersion agent formulations for examples

[0083]

[0084]

[0085] To further illustrate the beneficial effects of this application, four comparative examples of glass fiber impregnating agents were selected for comparison, namely Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. The formulations of Comparative Examples 1 to 4, as well as the amounts of each component and the percentage of solid mass, are shown below.

[0086] Comparative Example 1:

[0087] Coupling agent: Methacryloxypropyltrimethoxysilane coupling agent, product brand A-174, 9%;

[0088] Lubricant: Water-soluble silicone oil, 10%;

[0089] Film-forming agent 1: Epoxy emulsion, 56%;

[0090] Film-forming agent 2: Polypropylene emulsion (solid content 34.5-35.5%, pH: 3.5-6.5), 19.5%;

[0091] Surfactant: Cationic surfactant, organic quaternary ammonium salt 1831, 5.5%;

[0092] pH adjuster: Acetic acid, 3%.

[0093] Comparative Example 2:

[0094] Coupling agent: silane coupling agent, 33%;

[0095] Film-forming agent: waterborne epoxy emulsion, 27%;

[0096] Surfactant: Nonionic surfactant, 27%;

[0097] Enhancer: Aryl carboxylic acid esters, diisodecyl phthalate, 13%.

[0098] Comparative Example 3:

[0099] Coupling agent: silane coupling agent, KH560, KH570, 20%;

[0100] Lubricant: Cationic quaternary ammonium salt, alkyl cationic amide, 10%;

[0101] Film-forming agents: waterborne epoxy emulsion 681, water-soluble polyester emulsion SR-2, 65%;

[0102] pH adjuster: glacial acetic acid, 5%.

[0103] Comparative Example 4:

[0104] Coupling agent: silane coupling agent, KH550, KH570, 20%;

[0105] Lubricant: Cationic quaternary ammonium salt, alkyl cationic amide, 10%;

[0106] Film-forming agents: waterborne epoxy emulsion 682, water-soluble polyester emulsion SR-2, 65%;

[0107] pH adjuster: glacial acetic acid, 5%.

[0108] The prepared sizing agent (Examples 1-14 and Comparative Examples 1-4) was coated onto glass fiber yarn, dried, and then expanded. The glass fiber was drawn using a 4000H platinum-rhodium alloy spinneret, and the expanded filament had a linear density of 1200 tex and a single fiber diameter of 17 μm. The final combustible content of the product was 0.35 ± 0.15%. The performance of the pultruded composite material reinforced with the glass fiber yarn coated with the above sizing agent was tested. The performance test results are shown in Table 2, where all performance parameters were characterized under the same conditions and for the same time.

[0109] Table 2 Comparison of various performance aspects between the examples and comparative examples.

[0110]

[0111] Table 2 (continued) Comparison of various performance aspects between the examples and comparative examples

[0112]

[0113] In Examples 1-14, the film-forming agent is an aqueous aliphatic epoxy emulsion with a molecular weight of 350-800; film-forming agent B is a nonionic aqueous polyurethane-modified epoxy emulsion with a molecular weight of 1500-3500; film-forming agent C is a bisphenol A / F type epoxy emulsion with a molecular weight of 300-1000; lubricant A is at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant; fluffing and softening agent is a hydrophilic silicone oil binary copolymer compound; and pH adjuster is an organic acid.

[0114] As can be seen from the test data in Table 2, the alkali-free expanded glass fiber yarn produced by using the glass fiber sizing agent of this application, following conventional glass fiber production processes in the art, and after expansion, has a combustible content (i.e., the proportion of the amount of sizing agent coated on the glass fiber to the mass of the glass fiber) between 0.34% and 0.40%. This ensures the uniformity of the sizing agent coating on the glass fiber surface and the wetting speed with the matrix resin, thus guaranteeing good production efficiency. The linear density is between 1182 and 1214, ensuring a suitable glass fiber content in the final pultruded sheet and further ensuring a suitable performance fluctuation range for the pultruded sheet. The average fuzz content of the raw yarn in the examples was 7.14 mg / kg, while the comparative examples were 17 mg / kg, 16 mg / kg, 19 mg / kg, and 21 mg / kg, respectively. The fuzz content in the examples was higher than in the examples, indicating that the direct yarn prepared with the sizing agent provided in this application has excellent raw yarn bundle properties, does not break fibers, and has fewer yarn clumps. The average swelling rate of the examples was 4.82%, higher than the 4.3%, 4.6%, 4.1%, and 3.9% of the comparative examples, indicating that the raw yarn swelling rate provided in this application is higher. In particular, the average shear strength of the pultruded plate of this alkali-free glass fiber expanded yarn reinforced composite material was 44.82 MPa, higher than the 41.3 MPa, 41.8 MPa, 36.9 MPa, and 39.8 MPa of the comparative examples, showing a significant improvement in fiberglass strength. Therefore, it can be concluded that the fiberglass performance of the pultruded plate of the alkali-free glass fiber expanded yarn reinforced composite material coated with the sizing agent of this application is relatively good.

[0115] In summary, the glass fiber impregnating agent of this application has the following beneficial effects: First, the film-forming agent imparts bundled properties and flexibility to the yarn. This application uses three different types of epoxy emulsion film-forming agents, which, after being dissolved in water, form an aqueous aliphatic epoxy emulsion, a nonionic water-soluble polyurethane-modified epoxy emulsion, and a water-soluble bisphenol A / F type epoxy emulsion. The synergistic use of the three film-forming agents will improve the bundled properties of the glass fiber yarn, which is beneficial for drawing and forming, and also beneficial for the subsequent expansion. Second, with the assistance of the fluffing and softening agent, the glass fiber yarn becomes relatively soft and the gap between fibers is increased, increasing the fullness of the yarn and providing a certain degree of smoothness, which facilitates the production and processing of fiber products. During the yarn expansion process, it is easier to expand and can spread out naturally, greatly increasing the contact area between the yarn and the epoxy emulsion, thereby improving the impregnation speed and impregnation effect. Therefore, it can greatly improve the fiberglass performance of epoxy pultruded sheets.

[0116] Finally, it should be noted that in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0117] 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 sizing agent comprises an effective component and water; the solid content of the glass fiber sizing agent is 3%–6%, and the effective component comprises silane coupling agent A, silane coupling agent B, film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, fluffing and softening agent, and pH adjuster. 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: Silane coupling agent A 5%~12%; Silane coupling agent B 1%~6%; Film-forming agent A: 20%~49%; Film-forming agent B12%~30%; Film-forming agent C 5%~20%; Lubricant A: 5%~14%; Lubricant B1%~7%; Softener 1%~6%; pH adjuster 1%~6%; Wherein, film-forming agent A is an aqueous aliphatic epoxy emulsion; film-forming agent B is a nonionic aqueous polyurethane-modified epoxy emulsion; and film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion. The silane coupling agent A is an epoxy silane coupling agent, and the silane coupling agent B is an amino silane coupling agent; Lubricant A is at least one of polyoxypropylene ether lubricant, fatty acid amide lubricant, and higher alkane ammonium salt lubricant; lubricant B is a hydrophilic organosilicon lubricant. The fluffing and softening agent is a hydrophilic silicone oil-based binary copolymer compound.

2. The wetting agent according to claim 1, characterized in that: The mass ratio of film-forming agent A, film-forming agent B and film-forming agent C is (1~10):(1.5~2):

1.

3. The wetting agent according to claim 1, characterized in that, The molecular weight of the aqueous aliphatic epoxy emulsion is 350-800; the molecular weight of the nonionic aqueous polyurethane modified epoxy emulsion is 1500-3500; and the average molecular weight of the water-soluble bisphenol A / F type epoxy emulsion is 300-1000.

4. The wetting agent according to claim 1, characterized in that, The mass ratio of the epoxy silane coupling agent to the amino silane coupling agent is 2:1 to 5:

1.

5. The wetting agent according to claim 1, characterized in that, The lubricant B is water-based dimethyl silicone oil.

6. A method for preparing an impregnating agent as described in any one of claims 1-5, characterized in that, include: After adding the pH adjuster to water and stirring evenly, add silane coupling agent A and silane coupling agent B, stir evenly, and obtain a solution containing silane coupling agent A and silane coupling agent B. Film-forming agent A, film-forming agent B, film-forming agent C, lubricant A, lubricant B, and fluffing softener, diluted with water respectively, are mixed with a solution containing silane coupling agent A and silane coupling agent B. The remaining water is added, and the mixture is stirred evenly to obtain the glass fiber impregnating agent.

7. The method for preparing the wetting agent according to claim 6, characterized in that, The film-forming agent A is an aqueous aliphatic epoxy emulsion with a pH value of 6-7 and a particle size of 0.12-1.0 μm. The film-forming agent B is a nonionic waterborne polyurethane-modified epoxy emulsion with a pH value of 5-7 and a particle size of 0.2-2.0 μm. The film-forming agent C is a water-soluble bisphenol A / F type epoxy emulsion, the pH value of the water-soluble bisphenol A / F type epoxy emulsion is 5 to 7, and the particle size of the water-soluble bisphenol A / F type epoxy emulsion is 0.15 to 2.0 μm.

8. A glass fiber product produced by coating with the sizing agent according to any one of claims 1-5.

9. An application of the glass fiber product as described in claim 8 in the production of epoxy pultruded sheets.

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