阅读说明：本技术 一种玻璃纤维直接纱用浸润剂及制备方法、产品和应用 (Impregnating compound for glass fiber direct roving, preparation method, product and application ) 是由 杨国明 费其锋 廖晚凤 李明 范泳宇 张志坚 于 2021-08-19 设计创作，主要内容包括：本申请公开了一种玻璃纤维直接纱用浸润剂,包括硅烷偶联剂、成膜剂、润滑剂、分散剂和pH值调节剂；其中,浸润剂的固含量为5～9％,余量为水；各组分的固体质量占浸润剂固体质量的百分比表示如下：硅烷偶联剂8～18％,成膜剂55～76％,润滑剂12～24％,分散剂0.1～1％,pH值调节剂1～3％；成膜剂由成膜剂A和成膜剂B组成,成膜剂A选用聚醚改性双酚A环氧乳液,成膜剂B选用水性脂肪族环氧树脂乳液。采用该浸润剂涂覆生产的玻璃纤维直接纱产品,不但纱线软硬适中、毛羽少、滑爽性好,而且抗拉强度高、韧性佳；可赋予复合材料制品较高的力学强度,满足更多的市场应用要求,有效地兼顾了纱线使用顺畅性和制品力学强度的要求。(The application discloses a sizing agent for glass fiber direct roving, which comprises a silane coupling agent, a film forming agent, a lubricant, a dispersing agent and a pH value regulator; wherein the solid content of the impregnating compound is 5-9%, and the balance is water; the solid mass of each component accounts for the solid mass of the impregnating compound, and the percentage of the solid mass of each component to the solid mass of the impregnating compound is as follows: 8-18% of a silane coupling agent, 55-76% of a film forming agent, 12-24% of a lubricating agent, 0.1-1% of a dispersing agent and 1-3% of a pH value regulator; the film forming agent consists of a film forming agent A and a film forming agent B, wherein the film forming agent A is polyether modified bisphenol A epoxy emulsion, and the film forming agent B is aqueous aliphatic epoxy resin emulsion. The glass fiber direct yarn product produced by coating the impregnating compound has moderate hardness, less hairiness, good smoothness, high tensile strength and good toughness; the composite material product can be endowed with higher mechanical strength, meets more market application requirements, and effectively gives consideration to the requirements of smoothness in use of the yarns and the mechanical strength of the product.)

1. The impregnating compound for the glass fiber direct roving is characterized by comprising a silane coupling agent, a film forming agent, a lubricating agent, a dispersing agent and a pH value regulator; wherein the solid content of the impregnating compound is 5-9%, and the balance is water; the solid mass of each component accounts for the solid mass of the impregnating compound, and the percentage of the solid mass of each component to the solid mass of the impregnating compound is as follows:

the film forming agent is composed of a film forming agent A and a film forming agent B, wherein the film forming agent A is polyether modified bisphenol A epoxy emulsion, and the film forming agent B is waterborne aliphatic epoxy resin emulsion.

2. A sizing agent for glass fiber direct roving according to claim 1, wherein the solid mass of each component in the sizing agent is expressed as follows:

3. a sizing agent for glass fiber direct roving according to claim 1 or 2, wherein the film-forming agent A has a molecular weight of 400 to 600 and an average particle diameter of 0.3 to 1.2 μm; the molecular weight of the film forming agent B is 600-1000, and the average particle size is 0.2-0.8 μm.

4. A wetting agent for directly roving glass fibers according to claim 1 or 2, wherein the mass ratio of the film forming agent A to the film forming agent B is (3-5): 1.

5. a sizing agent for glass fiber direct roving according to claim 1 or 2, wherein the silane coupling agent is a combination of a silane coupling agent a and a silane coupling agent B, the silane coupling agent a is a vinyl-based and/or epoxy-based silane coupling agent, and the silane coupling agent B is an aminosilane coupling agent; the mass ratio of the silane coupling agent A to the silane coupling agent B is (10-3): 1.

6. a sizing agent for glass fiber direct roving according to claim 5, wherein the silane coupling agent A is one or a mixture of several of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, (gamma-2, 3-epoxypropoxy) propylmethyldiethoxysilane coupling agents; the silane coupling agent B is gamma-aminopropyltriethoxysilane or aminoethylaminopropyltrimethoxysilane coupling agent.

7. A sizing agent for glass fiber direct roving according to claim 1 or 2, wherein the lubricant is a mixture of a modified polyoxypropylene ether lubricant and one or more of a fatty acid amide lubricant, a higher alkylamine salt and an aqueous silicone lubricant;

the dispersant is water-soluble modified silicone;

the pH value regulator is acid.

8. A sizing agent for glass fiber direct roving according to claim 7, wherein said lubricant is a mixture of a modified polyoxypropylene ether lubricant and an aqueous silicone lubricant; the molecular weight of the modified polyoxypropylene ether is 2000-3000, and the molecular weight of the water-based organic silicon is 3000-5000.

9. A method for preparing the impregnating compound for the direct roving of glass fibers according to any one of claims 1 to 8, comprising the steps of:

1S: preparing water 40-50 times the total mass of the silane coupling agent and the pH regulator according to the mass percentage, mixing the pH regulator with the water, regulating the pH value to 4-6, stirring the aqueous solution for 5-7 minutes, adding the silane coupling agent into the aqueous solution, and stirring for 30-40 minutes to obtain a silane coupling agent dispersion liquid;

2S: adding a lubricant into 5-10 times of water, dissolving and dispersing at 20-60 ℃ to obtain a lubricant diluent, and adding the lubricant diluent into the silane coupling agent dispersion liquid obtained in the step 1S to obtain a first mixed dispersion liquid;

3S: adding a dispersing agent into the first mixed dispersion liquid in the step 2S, and stirring for 10-20 minutes to obtain a second mixed dispersion liquid;

4S: and adding a film forming agent into the second mixed dispersion liquid in the step 3S, and uniformly stirring to obtain the impregnating compound for the direct glass fiber roving.

10. A glass fiber direct roving product produced by coating the glass fiber direct roving of any one of claims 1 to 8 with an impregnating compound.

11. Use of the fiberglass direct yarn product of claim 10 in a high tensile pultrusion process.

Technical Field

The application relates to the technical field of glass fiber production and manufacturing, in particular to an impregnating compound for glass fiber direct roving, a preparation method, a product and an application thereof, and is particularly suitable for production of the glass fiber direct roving for high-strength pultrusion.

Background

The glass fiber is an inorganic non-metallic material with excellent performances such as high modulus, light weight and the like, and is widely applied to reinforced resin to prepare composite materials. The glass fiber is a brittle inorganic material, and in order to overcome the defect that the glass fiber is easy to brittle fracture, people usually use a method of coating a sizing agent on the surface to protect the glass fiber, wherein a sizing agent layer can form chemical bonding with the surface of the fiber, and simultaneously, the glass fiber can form rapid infiltration in resin matrixes such as polyester, epoxy and the like, so that the mechanical strength of a composite material product is improved.

Fiber pultrusion is one of the common molding processes of reinforced composite materials, and relates to the fields of various profiles, bars, geogrids and the like. The consumption of the glass fiber direct yarn for pultrusion is also increasing day by day, and the annual demand is dozens of ten thousand tons. Unsaturated polyester, epoxy, polyurethane and the like can be selected as the base resin for pultrusion, wherein the polyester-based pultrusion usage amount is the largest. At present, a plurality of direct yarn products for pultrusion are available on the market, the resin emulsion is improved and optimized, the surface of the glass fiber is coated, the glass fiber yarn can be endowed with good flexibility and smoothness, and the use smoothness is good. And some direct yarn products have outstanding reinforcing effect and are applied to manufacturing pultrusion profiles with high mechanical strength.

At present, the pultrusion process has increasingly strict requirements on the use process performance of yarns, and in some fields with high application requirements (such as high-strength I-steel and the like), the requirements on the mechanical strength of products are more strict. However, the existing products are difficult to satisfy the requirements of smooth use of the yarns and the mechanical strength of the composite material product. The problems of hairiness, broken filaments, broken yarns and the like of the high-strength glass fiber direct yarns for pultrusion are often caused by friction and winding in the using process, even the mold holes are blocked, the pultrusion processing efficiency is seriously reduced, and the considerable economic loss is caused.

Disclosure of Invention

The technical problem to be solved by the application is to provide the impregnating compound for the glass fiber direct roving, and the glass fiber direct roving product produced by coating the impregnating compound has moderate softness and hardness, less hairiness, good smoothness, high tensile strength and good toughness; the composite material product can be endowed with higher mechanical strength, meets more market application requirements, and effectively gives consideration to the requirements of smoothness in use of the yarns and the mechanical strength of the product.

According to one aspect of the application, the impregnating compound for the direct roving of the glass fiber comprises a silane coupling agent, a film forming agent, a lubricating agent, a dispersing agent and a pH value regulator; wherein the solid content of the impregnating compound is 5-9%, and the balance is water; the solid mass of each component accounts for the solid mass of the impregnating compound, and the percentage of the solid mass of each component to the solid mass of the impregnating compound is as follows:

the film forming agent is composed of a film forming agent A and a film forming agent B, wherein the film forming agent A is polyether modified bisphenol A epoxy emulsion, and the film forming agent B is waterborne aliphatic epoxy resin emulsion.

Wherein the solid mass of each component accounts for the solid mass of the impregnating compound, and the percentage of the solid mass of each component is as follows:

wherein the molecular weight of the film forming agent A is 400-600, and the average particle size is 0.3-1.2 μm; the molecular weight of the film forming agent B is 600-1000, and the average particle size is 0.2-0.8 μm.

The film forming agent A and the film forming agent B are in a mass ratio of (3-5): 1.

the silane coupling agent is a combination of a silane coupling agent A and a silane coupling agent B, wherein the silane coupling agent A is a vinyl and/or epoxy silane coupling agent, and the silane coupling agent B is an aminosilane coupling agent; the mass ratio of the silane coupling agent A to the silane coupling agent B is (10-3): 1.

wherein, the silane coupling agent A is one or a mixture of a plurality of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and (gamma-2, 3-epoxypropoxy) propyl methyldiethoxysilane coupling agents; the silane coupling agent B is gamma-aminopropyltriethoxysilane or aminoethylaminopropyltrimethoxysilane coupling agent.

Wherein the lubricant is a mixture of one or more of a modified polyoxypropylene ether lubricant, a fatty acid amide lubricant, a higher alkane amine salt and a water-based organic silicon lubricant; the dispersant is water-soluble modified silicone; the pH value regulator is acid.

Wherein the lubricant is a mixture of a modified polyoxypropylene ether lubricant and a water-based silicone lubricant; the molecular weight of the modified polyoxypropylene ether is 2000-3000, and the molecular weight of the water-based organic silicon is 3000-5000.

The impregnating compound comprises a silane coupling agent, a film forming agent, a lubricating agent, a dispersing agent and a pH value regulator; wherein the solid content of the impregnating compound is 5-9%, and the balance is water. The following components are all the percentage of the solid mass of the component in the solid mass of the impregnating compound.

The silane coupling agent contains organic and inorganic functional groups, and silanol bonds hydrolyzed by the coupling agent can be condensed with hydroxyl groups on the surface of the glass fiber to generate chemical bonding on the surface of the glass fiber; the organic functional group of the coupling agent molecule has good compatibility with the resin matrix, and can enhance the binding force of the glass fiber and the matrix resin of the composite material. Therefore, the structure of the coupling agent is critical in determining the bonding ability of the glass fiber and the surface coating glue. The silane coupling agent of the present application preferably employs a combination of a silane coupling agent a and a silane coupling agent B; wherein, the silane coupling agent A is vinyl and/or epoxy silane coupling agent, and the silane coupling agent B is amino silane coupling agent. Preferably, the silane coupling agent is a combination of coupling agents containing vinyl, epoxy and amino, so that the glass fiber and the composite resin can form higher bonding strength, the silane coupling agent system can be widely applied to the production of composite materials of various resin systems such as polyesters, epoxy and the like, and the product has high mechanical strength and good fatigue resistance. More preferably, the silane coupling agent A is one or a mixture of more of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and (gamma-2, 3-epoxypropoxy) propylmethyldiethoxysilane coupling agents; the silane coupling agent B is gamma-aminopropyl triethoxysilane or aminoethylaminopropyl trimethoxysilane. Researches find that if the content of the silane coupling agent is too low, the inorganic property of the surface of the glass fiber causes poor compatibility with an organic resin matrix and cannot form effective chemical combination with the resin matrix; and if the content of the silane coupling agent is too high, the coupling agent is gathered on the surface of the glass fiber to form local defects, so that the chemical combination of the glass fiber and the resin is hindered, and the mechanical strength of the composite material is reduced. Therefore, the percentage of the solid mass of the silane coupling agent in the total solid mass of the impregnating compound is 8-18%, preferably 10-14%. In addition, the mass ratio of the silane coupling agent A to the silane coupling agent B is preferably controlled to be (10-3): 1, more preferably (10-5): 1. the silane coupling agent A is too much in dosage and has weaker reaction activity than the silane coupling agent B, so that the bonding strength of the glass fiber and the resin matrix is insufficient, and the mechanical strength of a pultruded product is limited; if the amount of the silane coupling agent A is too small, the amino coupling agent on the fiber surface will self-polymerize, and the chemical bonding between the glass fiber surface and the resin matrix will be inhibited.

The film forming agent is used as the main component of the impregnating compound for the glass fiber, plays a role in protecting the surface of the glass fiber, and can endow the glass fiber with bonding bundling property and wear resistance. Therefore, the choice of film former is one of the focus of the present application. The film forming agent adopts the combination of a film forming agent A and a film forming agent B, wherein the film forming agent A is preferably polyether modified bisphenol A epoxy emulsion, and the film forming agent B is preferably aqueous aliphatic epoxy resin emulsion. Tests show that the solid mass of the film forming agent A is greater than that of the film forming agent B, and the dosage of the film forming agent A and the dosage of the film forming agent B both need to be controlled in a proper range to achieve a better effect. The solid mass of the film forming agent A accounts for 45-60% of the total solid mass of the impregnating compound, and preferably 50-55%; the solid mass of the film forming agent B accounts for 10-16%, preferably 12-15% of the total solid mass of the impregnating compound. The polyether modified bisphenol A epoxy emulsion with a proper dosage can not only provide excellent bonding bundling property for glass fibers, but also enable yarns to have better stiffness; the waterborne aliphatic epoxy emulsion with proper dosage can endow the glass fiber with good flexibility and effectively improve the use smoothness of the fiber under the condition of low temperature. If the content of the polyether modified bisphenol A epoxy emulsion is too high, the yarn is hard, and the use is influenced due to too heavy adhesion; if the content of the polyether modified bisphenol A epoxy emulsion is too low, the yarn is soft, the stiffness is low, and the smoothness in use is insufficient at high temperature. Therefore, further, the mass ratio of the film forming agent A to the film forming agent B is controlled to be (3-5): 1, preferably (3.5-4): 1.

the film forming agent A is preferably polyether modified bisphenol A epoxy emulsion with the molecular weight of 400-600 and the average particle size of 0.3-1.2 mu m, and the film forming agent B is preferably aqueous aliphatic epoxy emulsion with the molecular weight of 600-1000 and the average particle size of 0.2-0.8 mu m. The film forming agent has moderate molecular weight, can provide a sizing agent layer with moderate hardness, can more fully play a role in protecting glass fibers, and simultaneously ensures that yarns are quickly wetted in matrix resin.

Use emollient mainly in this application in order to satisfy glass fiber wire drawing, the demand of the lubrication and the anti friction damage of back course of working, improve the wearability of yarn, help glass fiber to soak fast completely simultaneously, homodisperse. The present application preferably employs a mixture of the modified polyoxypropylene ether lubricant with one or more of a fatty acid amide lubricant, a higher alkylamine salt and an aqueous silicone lubricant. Preferably, the lubricant is a mixture of a modified polyoxypropylene ether lubricant and a water-based silicone lubricant, wherein the molecular weight of the modified polyoxypropylene ether is 2000-3000, and the molecular weight of the water-based silicone is 3000-5000. The lubricant mixture is viscous liquid, has small viscosity change along with temperature, has good lubricating effect, and can help to improve the problems of softening and filament scattering of the glass fiber due to over-high temperature. The solid mass of the lubricant accounts for 12-24% of the total solid mass of the impregnating compound, if the content of the lubricant is too small, the lubricating property is insufficient, and the problems of yarn friction and abrasion, burr generation, yarn breakage and the like are easily caused in the wire drawing process; and too much content can cause yarn scattering and increased hairiness, which affects the smoothness of use. Preferably, the content of the lubricant is 16-19%.

The dispersing agent is mainly used for reducing the surface affinity of the glass fiber, promoting the impregnating compound and the glass fiber interface to form complete coating, improving the wettability and the dispersibility of the glass fiber, accelerating the complete soaking of the glass fiber in resin, being beneficial to the molding of composite material products and more fully playing the reinforcing role of the glass fiber. Specifically, the water-soluble modified silicone dispersing agent is adopted, has strong affinity with the surface of the glass fiber and good compatibility with a silane coupling agent, and is favorable for increasing the bonding strength between the impregnating compound and the surface of the glass fiber. The solid mass of the dispersing agent accounts for 0.1-1% of the total solid mass of the impregnating compound, and if the content of the dispersing agent is too low, the surface of the glass fiber can not be fully modified; and too much content can cause the wetting agent to have too strong hydrophilicity, reduce the adhesion of resin emulsion particles to the surface of the glass fiber and be not beneficial to the uniform coating of the wetting agent on the surface of the glass fiber. Preferably, the content of the dispersant is 0.4-0.7%.

The pH value regulator is mainly used for regulating the pH value of the impregnating compound. The pH regulator can be acid, organic acid or inorganic acid, preferably acetic acid and/or citric acid. Wherein the solid mass of the pH value regulator accounts for 1-3% of the total solid mass of the impregnating compound.

The water is used as the dispersion phase of each component of the impregnating compound, and compared with a solvent dispersion phase, the water-based impregnating compound is more environment-friendly and safer. Among them, deionized water is preferred.

According to a second aspect of the present application, there is provided a method for preparing the sizing agent for direct roving of glass fiber, comprising the steps of:

1S: preparing water 40-50 times the total mass of the silane coupling agent and the pH regulator according to the mass percentage, mixing the pH regulator with the water, regulating the pH value to 4-6, stirring the aqueous solution for 5-7 minutes, adding the silane coupling agent into the aqueous solution, and stirring for 30-40 minutes to obtain a silane coupling agent dispersion liquid;

2S: adding a lubricant into 5-10 times of water, dissolving and dispersing at 20-60 ℃ to obtain a lubricant diluent, and adding the lubricant diluent into the silane coupling agent dispersion liquid obtained in the step 1S to obtain a first mixed dispersion liquid;

preferably, the lubricant except the modified polyoxypropylene ether emulsion is dissolved and dispersed with 5-10 times of water at 45-60 ℃, and when the solution is cooled to room temperature, a lubricant diluent is obtained, and the lubricant diluent is added into the silane coupling agent dispersion in the step 1S; then adding the modified polyoxypropylene ether emulsion with the formula amount, and stirring for 10-20 minutes to obtain a first mixed dispersion liquid; because the stability of the dispersed emulsion of the modified polyoxypropylene ether emulsion is influenced under the condition of higher temperature, the modified polyoxypropylene ether emulsion needs to be dispersed at normal temperature, contains more water as a dispersion liquid and can be directly added into a system without dilution, and therefore, the lubricant is added in two steps.

3S: adding a dispersing agent into the first mixed dispersion liquid in the step 2S, and stirring for 10-20 minutes to obtain a second mixed dispersion liquid;

4S: and adding a film forming agent into the second mixed dispersion liquid in the step 3S, and uniformly stirring to obtain the impregnating compound for the direct glass fiber roving.

According to a third aspect of the present application, there is provided a direct glass fiber veil product produced by coating the aforementioned direct glass fiber veil with a sizing agent.

According to a fourth aspect of the present application, there is provided the use of the aforementioned glass fiber direct yarn in a high tensile pultrusion process.

The combustible content of the glass fiber is generally controlled to be 0.2-1.0%, and the specific value needs to be adjusted according to performance indexes required to be achieved by the product.

Compared with the prior art, the glass fiber direct yarn product produced by coating the sizing agent can be quickly wetted on the surface of the yarn and form a tough coating film. In the sizing agent, the coupling agent can play a role in chemical bridging among the surface of the glass fiber, the sizing agent layer and the resin matrix layer, the film-forming agent endows the yarn with bundling property and flexibility, and the lubricant ensures the smoothness of the yarn; the components in the impregnating compound act synergistically, so that the glass fiber prepared by coating the impregnating compound has excellent comprehensive use performance. Therefore, the glass fiber direct yarn prepared by coating the sizing agent has good toughness and high wear resistance, and can form good sizing with a resin matrix. In the process of degradation, the yarn has no loose yarn, less filoplume, good yarn bundling property and high use smoothness, is particularly suitable for a pultrusion process, and the prepared product has high mechanical strength and can meet the requirement of high-strength pultrusion.

Detailed Description

To make the objects, technical solutions and advantages of the embodiments of the present application clearer, the embodiments of the present application will be described clearly and completely in conjunction with the specific embodiments of the present application, and it is obvious that the described embodiments are some, but not all embodiments of the present application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application. It should be noted that the embodiments and features of the embodiments in the present application may be arbitrarily combined with each other without conflict.

The impregnating compound for the glass fiber direct roving has the solid content of 5-9% and the balance of water; the solid mass of each component accounts for the solid mass of the impregnating compound, and the percentage of the solid mass of each component to the solid mass of the impregnating compound is as follows: 8-18% of a silane coupling agent, 55-76% of a film forming agent, 12-24% of a lubricating agent, 0.1-1% of a dispersing agent and 1-3% of a pH value regulator;

preferably, the solid mass of each component accounts for 10-14% of the solid mass of the impregnating compound, the film-forming agent accounts for 62-70%, the lubricant accounts for 16-19%, the dispersing agent accounts for 0.4-0.7%, and the pH value regulator accounts for 1.5-2.5%.

Preferably, the silane coupling agent adopts a combination of a silane coupling agent A and a silane coupling agent B; wherein, the silane coupling agent A is vinyl and/or epoxy silane coupling agent, and the silane coupling agent B is amino silane coupling agent; more preferably, the silane coupling agent A is one or a mixture of more of gamma-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and (gamma-2, 3-epoxypropoxy) propylmethyldiethoxysilane coupling agents; the silane coupling agent B is gamma-aminopropyl triethoxysilane or aminoethylaminopropyl trimethoxysilane. Further preferably, the mass ratio of the silane coupling agent A to the silane coupling agent B is controlled to be (10-3): 1, preferably (10-5): 1.

preferably, the film forming agent consists of a film forming agent A and a film forming agent B, wherein the film forming agent A is polyether modified bisphenol A epoxy emulsion, the molecular weight is 400-600, and the average particle size is 0.3-1.2 mu m; the film forming agent B is aqueous aliphatic epoxy resin emulsion, the molecular weight is 600-1000, and the average particle size is 0.2-0.8 mu m. The mass ratio of the film forming agent A to the film forming agent B is (3-5): 1, preferably (3.5-4): 1.

preferably, the lubricant is a mixture of the modified polyoxypropylene ether lubricant and one or more of fatty acid amide lubricant, higher alkane amine salt and water-based silicone lubricant; more preferably, the lubricant is a mixture of a modified polyoxypropylene ether lubricant and an aqueous silicone lubricant.

Preferably, the dispersant is a water-soluble modified silicone dispersant; the pH regulator is acid, preferably acetic acid and/or citric acid.

Specific examples of compositions of the sizing for glass fiber direct roving of the present invention are shown below.

Examples

Specific examples of the sizing agent for glass fibers of the present application are given in tables 1A to 1B, and the amounts of the components used in the formulation are the percentages of the solid mass of the components in the total solid mass of the sizing agent.

It should be noted that the specific types, contents and combinations of the components selected in tables 1A to 1B do not limit the scope of the present application.

TABLE 1A

TABLE 1B

The aqueous aliphatic epoxy emulsion used in the above embodiments can be obtained by autonomous emulsification modification, and specifically can be prepared in the following manner: mixing epoxy resin and a surfactant, pre-melting for 2-3 h at 80 ℃, transferring into an emulsifier, starting the emulsifier, and stirring to uniformly mix materials; connecting jacket condensate water, controlling the temperature at 50 + -2 deg.C, adding water for emulsification, stirring for 30min, controlling the temperature at 38 + -2 deg.C, adding water, stirring to the specified solid content ratio, and stirring for 30min to form uniform emulsion. Wherein, the epoxy emulsion is prepared by emulsifying liquid aliphatic epoxy resin with the molecular weight of 600-1000 and the epoxy equivalent of 300-500g/eq by a surfactant, the surfactant can be a nonionic surfactant, and the dosage of the surfactant is 10-25% of the weight of the aliphatic epoxy resin.

Comparative example

To further illustrate the benefits of the present application, two glass fiber sizes commonly used today were selected as comparative examples, comparative example 1 and comparative example 2. The formulations of comparative examples 1-2 are shown below, wherein the amounts of the components are the percentages of the solid mass of the components in the total solid mass of the sizing agent.

Comparative example 1

Coupling agent 1: gamma-methacryloxypropyltrimethoxysilane, 10%;

coupling agent 2: 3% of 3-aminopropyltriethoxysilane;

film-forming agent: bisphenol A epoxy resin emulsion (product trade name Neoxil965, produced by DSM in the Netherlands) 70%;

lubricant: polyoxyethylene fatty acid ester, 12.5%, fatty amide, 1.5%;

pH regulator: acetic acid, 3%.

Comparative example 2

Coupling agent: 10% of gamma-methacryloxypropyltrimethoxysilane and 3% of gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane;

film-forming agent 1: 20 percent of water-based polyester emulsion JS-111 (produced by Italy COIM company, the product brand is JS-111);

film-forming agent 2: bisphenol a type epoxy emulsion TX-608 (megalite self-made small molecular weight epoxy emulsion) 55%;

lubricant: fatty amide, 8%;

pH regulator: acetic acid, 4%.

The prepared sizing agents (examples 1-12 and comparative examples 1-2) are coated on glass fiber direct roving products, and the product performances of the glass fibers and the glass fiber reinforced polyester composite material are detected. Wherein the drawing process of the glass fiber is 4000H platinum bushing drawing, the linear density is 2400tex, and the diameter of a single fiber is 17 microns. The drying process can adopt tunnel hot air drying and microwave-assisted drying, the drying time is 14.5 hours, and the combustible content of the final product is 0.6 +/-0.15%.

The stiffness of the glass fibers was measured in cm according to GB/T7690.4-2013. The tensile breaking strength of the glass strands was tested in accordance with GB/7689.5. The breaking strength of the glass fibers was measured in accordance with GB/T7690.3 in N/tex. The results of testing the properties of the glass fiber and the properties of the composite material are shown in Table 2.

TABLE 2 product performance test results of glass fiber and composite material

TABLE 2 (continuation) testing results of product performance of glass fiber and composite material

It should be noted that the hardness of the yarns in table 2 is only evaluated according to the relative hardness of the examples, and the degree decreases from hard to soft.

From the above formula test examples, it can be seen that the properties of the glass fiber direct roving product coated with the glass fiber direct roving sizing agent formula of the present application and the glass fiber reinforced polyester composite product are superior to those of the comparative example data, wherein the comprehensive effects of the examples 4 and 5 are better.

In conclusion, the glass fiber direct yarn produced by the glass fiber sizing agent has excellent bundling property, low hairiness and wear resistance; and the compatibility with resin is good, and the mechanical strength of the pultruded product is high.

The above-described aspects may be implemented individually or in various combinations, and such variations are within the scope of the present application.

Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present application, and are not limited thereto. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.