A glass fiber surface treatment agent and its preparation method, glass fiber, fabric and its application

Abstract

This application provides a glass fiber surface treatment agent, its preparation method, glass fiber, fabric, and their applications. The glass fiber surface treatment agent comprises an effective component and water, with a solid content of 5.8–10.5%. The effective component, by weight percentage, includes: a coupling agent of 7.3–17.3%, a penetrant of 0.3–2.8%, a lubricant of 7.7–13.2%, a film-forming agent of 58.3–81.9%, a toughening agent of 0.4–1.8%, and additives of 2.4–6.6%. The film-forming agent comprises film-forming agent A and film-forming agent B. Film-forming agent A is a composition of phenolic epoxy emulsion and bisphenol A type epoxy emulsion, and film-forming agent B is an alicyclic epoxy resin emulsion. Glass fibers produced using this glass fiber surface treatment agent exhibit excellent bundle properties, wear resistance, and weaving performance. The glass fiber fabric undergoes rapid and complete static impregnation in epoxy resin, resulting in high mechanical strength and meeting the performance requirements of new energy vehicle battery casings.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass fiber reinforced composite materials, in particular to a glass fiber surface treatment agent for new energy automobile battery shells, a preparation method thereof, glass fibers, fabrics and applications thereof. BACKGROUND

[0002] New energy automobile refers to an automobile adopting unconventional vehicle fuel as power source (electricity, solar energy, hydrogen energy, etc.), and combining advanced technologies in power control and driving of the vehicle to form an automobile with advanced technical principles and new technologies and structures. At present, the battery automobile using electricity as the main energy is relatively mature in the market. Compared with traditional automobiles, the battery automobile has the following advantages: zero or near-zero emission, effectively reducing the emission of greenhouse gases, improving economic efficiency, stable operation and basically no noise.

[0003] At present, most new energy battery automobiles will choose steel or aluminum alloy material as the protective shell of the battery pack in order to ensure the safety of the chassis power battery. Although steel or aluminum alloy can protect the safety of the power battery to a great extent, the density of steel and aluminum alloy is large, which increases the weight of the whole vehicle, causes the increase of electricity consumption during the operation of the automobile, reduces the endurance, and even has different degrees of influence on the control of the vehicle. In addition, although the density of aluminum alloy is relatively small, the price of aluminum alloy is high, which also limits its large-scale application. The endurance of new energy automobile is a problem that users pay much attention to, and the cost is a problem that automobile enterprises focus on. New energy automobile enterprises in the forefront are looking for battery shell replacement and solution.

[0004] Glass steel products have higher specific strength, lower density, corrosion resistance, and lower cost than metal products, and can completely replace stainless steel or aluminum alloy as new energy vehicle battery shell. In 2022, among the top ten power battery enterprises, Chinese enterprises accounted for 6 seats, with a market share of 64.5%. Different battery manufacturers are trying to use glass steel to replace metal as the battery shell, which can not only greatly reduce the weight of the vehicle, but also greatly improve the endurance level of new energy vehicles. The relatively optimal solution for the performance and cost of the battery shell in the new energy vehicle industry at present is to use glass fabric and epoxy resin (solid at room temperature) pre-impregnation and then mold forming, i.e. PCM process. This process requires that the glass fabric can quickly penetrate the high-viscosity epoxy resin (the viscosity of the solid epoxy is still very large even after heating and melting) to ensure the strength and appearance of the subsequent product. However, the existing glass fiber products and glass fabric on the market are designed for low-viscosity unsaturated polyester resin or low-viscosity epoxy resin, and the penetration in high-viscosity epoxy resin is very slow and insufficient, which can easily form white silk and other appearance problems and cause the mechanical strength of the product to be substandard. At the same time, the slow penetration speed also seriously affects the production efficiency, which seriously restricts the development of PCM process new energy vehicle battery shell.

[0005] Therefore, how to reduce the surface tension of glass fiber in high-viscosity epoxy resin, improve the static penetration speed, penetration end state and interface bonding effect of glass fiber fabric in high-viscosity epoxy resin, and meet the requirements of industrial production of PCM process new energy vehicle battery shell has always been a technical problem that needs to be overcome in the composite material industry. The glass fiber treated with the treating agent has excellent bundling, wear resistance and weaving performance, and the glass fabric has fast and complete static penetration speed in high-viscosity epoxy resin, high mechanical strength of the product, and meets various performance requirements of new energy vehicle battery shell

[0006] The related glass fiber technical requirements are as follows (600tex, glass fabric unit area mass 400g / m 2 For example, reinforcing high-viscosity epoxy resin):

[0007] Glass fiber performance index:

[0008] Test item Unit Test standard Index requirement Pilosity mg / kg / ≤30 Shear strength MPa ASTM D2344 ≥68

[0009] The related glass fiber fabric technical requirements are as follows (reinforcing high-viscosity epoxy resin):

[0010] Glass fabric performance index:

[0011] Test item Unit Test standard Index requirement Tensile strength in warp direction N GB / T 7689.5 ≥4000 Tensile strength in weft direction N GB / T 7689.5 ≥4000 Bending strength in warp direction MPa GB / T1449 ≥500 Bending strength in weft direction MPa GB / T1449 ≥500

[0012] In summary, the current composite industry is in urgent need of developing a new type of glass fiber surface treatment agent to meet the performance requirements of new energy vehicle battery shell. SUMMARY

[0013] The main purpose of the present application is to provide a glass fiber treatment agent for new energy vehicle battery shell. The glass fiber treated with the treatment agent has excellent bundling, wear resistance and weaving performance. The glass fabric produced by the glass fiber treated with the surface treatment agent can quickly and completely penetrate in high viscosity epoxy resin, and the product has high mechanical strength, which meets the performance requirements of new energy vehicle battery shell.

[0014] To achieve the above-mentioned purpose, according to one aspect of the present application, a glass fiber surface treatment agent is provided, which comprises effective components and water, and the solid content of the glass fiber surface treatment agent is 5.8-10.5%; the effective components comprise, by weight percentage of the effective components: coupling agent 7.3-17.3%, penetrating agent 0.3-2.8%, lubricant 7.7-13.2%, film forming agent 58.3-81.9%, toughening agent 0.4-1.8%, and auxiliary agent 2.4-6.6%; wherein the film forming agent is a combination of phenolic epoxy and bisphenol A type epoxy and a combination of alicyclic epoxy resin.

[0015] Further, the effective components comprise, by weight percentage of the effective components: coupling agent 7.8-16.9%, penetrating agent 0.5-2.4%, lubricant 8.6-12.3%, film forming agent 62.4-79.9%, toughening agent 0.6-1.6%, and auxiliary agent 2.6-6.4%.

[0016] Further, the phenolic epoxy comprises ortho-methylphenol epoxy resin and / or bisphenol A type phenolic epoxy resin; the bisphenol A type epoxy comprises one or more of bisphenol A type epoxy, polyether modified bisphenol A type epoxy, and organic silicon blended modified bisphenol A type epoxy; and the alicyclic epoxy resin is a mixture of one or more of epoxy methane resin, epoxy propane resin, epoxy butane resin, alicyclic phenolic epoxy resin, and epoxy acrylate resin.

[0017] Preferably, the phenolic epoxy is bisphenol A type phenolic epoxy resin; the bisphenol A type epoxy is bisphenol A type epoxy and / or polyether modified bisphenol A type epoxy; and the alicyclic epoxy resin is a mixture of one or more of epoxy methane resin, epoxy propane resin, and epoxy acrylate resin.

[0018] Further, the epoxy equivalent weight of the phenolic epoxy is 160-260 g / eq; the epoxy equivalent weight of the bisphenol A type epoxy is 240-350 g / eq; and the epoxy equivalent weight of the alicyclic epoxy resin is 200-300 g / eq.

[0019] Further, the weight percentage of the combination of phenolic epoxy and bisphenol A type epoxy in the effective components is 30.8-44.7%; and the weight ratio of phenolic epoxy to bisphenol A type epoxy is (0.31-1.48):1; the weight percentage of the alicyclic epoxy resin in the effective components is 27.5-37.2%, and the weight ratio of the combination of phenolic epoxy and bisphenol A type epoxy to the alicyclic epoxy resin is (0.83-1.63):1.

[0020] Further, the coupling agent comprises coupling agent A and coupling agent B, the weight percentage of coupling agent A in the effective components is 3.4-9.6%; the weight percentage of coupling agent B in the effective components is 3.9-7.7%;

[0021] Among them, coupling agent A is one or a combination of two of vinyl silane containing coupling agent, acyloxy silane containing coupling agent, and epoxy silane containing coupling agent; coupling agent B is amino silane containing coupling agent or poly nitrogen silane based coupling agent.

[0022] Preferably, coupling agent A is acyloxy silane containing coupling agent and / or epoxy silane containing coupling agent, and coupling agent B is poly nitrogen silane based coupling agent; the weight ratio of coupling agent A to coupling agent B is (0.44-2.46):1.

[0023] Further, the penetrating agent is one or a combination of two of ethoxylated acetylenic diol type, polyether modified siloxane type, and fatty alcohol polyoxyalkyl ether type penetrating agent; the lubricant is one or a combination of two or more of silicone oil type, quaternary ammonium salt type compound, and polyethylene glycol type lubricant; the toughening agent is reactive polyphenyl ether resin and / or polycaprolactone polyol; and the auxiliary agent is organic acid.

[0024] Preferably, the penetrating agent is ethoxylated acetylenic diol type and / or polyether modified siloxane type penetrating agent; the toughening agent is polycaprolactone polyol; and the auxiliary agent is citric acid and / or acetic acid.

[0025] In order to achieve the above-mentioned purpose, according to one aspect of the present application, a preparation method of the above-mentioned glass fiber surface treatment agent is provided, which comprises: mixing auxiliary agent, coupling agent, penetrating agent, lubricant, toughening agent, film forming agent, and water to obtain the glass fiber surface treatment agent.

[0026] According to a third aspect of the present application, a glass fiber is provided, which is obtained by treating the glass fiber with the glass fiber surface treatment agent prepared by the above-mentioned preparation method.

[0027] According to a fourth aspect of the present application, a glass fiber fabric is provided, which is obtained by weaving the above-mentioned glass fiber.

[0028] According to a fifth aspect of the present application, the above-mentioned glass fiber fabric is applied in a new energy automobile battery shell.

[0029] The technical scheme of the present application provides a glass fiber surface treatment agent, which comprises a coupling agent, a penetrating agent, a lubricant, a film forming agent, a toughening agent, an auxiliary agent and water. The coupling agent and the film forming agent are the main components of the glass fiber surface treatment agent of the present application, wherein the coupling agent is essentially a kind of silane with organic functional groups, which has a reactive group capable of chemical combination with inorganic materials (such as glass, silica sand, metal, etc.) and a reactive group capable of chemical combination with organic materials (synthetic resin, etc.) in its molecule. The reactive group capable of chemical combination with inorganic materials plays a role in repairing the micro-cracks on the surface of the fiber, and at the same time can form an effective and continuous protective layer on the surface of the glass fiber, improving the processability of the glass fiber; and the reactive group capable of chemical combination with organic materials can have strong bonding ability with different matrix resins, improving the adhesion between the glass fiber and the resin, and greatly improving the strength, electrical, water resistance, weather resistance and other properties of the glass fiber reinforced composite material. The film forming agent is the key component of the surface treatment agent, and is also the basis for determining the performance and classification of the surface treatment agent. The film forming agent has the largest amount in the surface treatment agent, which can not only determine the bundling property and post-processing property of the glass fiber filament, but also improve the compatibility of the glass fiber and the reinforcing resin and the mechanical properties of the composite product. Compared with other types of film forming agents, the film forming agent selected in the present application, which is a combination of phenolic epoxy, bisphenol A type epoxy and alicyclic epoxy resin, has the greatest advantage of stronger adhesion on the surface of the fiber. While retaining the good bundling property of the glass fiber, it has good compatibility with the epoxy resin system and is stable at high temperature and not easy to decompose, meeting the weaving performance requirements of the glass fiber fabric for new energy automobile battery shell and the mechanical performance requirements of the glass steel for new energy automobile battery shell. The inventors have found through experiments that, after the glass fiber surface treatment agent prepared by combining the coupling agent, the penetrating agent, the lubricant, the film forming agent, the toughening agent, the auxiliary agent and water according to the ratio of the present application is applied to the glass fiber and its fabric, the bundling property and wear resistance of the glass fiber, as well as the static penetration property of the glass fiber fabric in high viscosity epoxy resin and the mechanical properties of the glass steel are obviously better than those of other glass fiber surface treatment agents. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme of the present application will be described clearly and completely below in combination with specific embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below in combination with the embodiments.

[0031] To solve the problems in the prior art as described above, according to an aspect of the present application, a glass fiber surface treatment agent is provided, comprising an effective component and water, wherein the effective component accounts for 5.8-10.5% of the glass fiber surface treatment agent by weight percentage; the effective component comprises, by weight percentage of the effective component: a coupling agent 7.3-17.3%, a penetrating agent 0.3-2.8%, a lubricant 7.7-13.2%, a film-forming agent 58.3-81.9%, a toughening agent 0.4-1.8%, and an auxiliary agent 2.4-6.6%; wherein the film-forming agent is a combination of phenolic epoxy and bisphenol A type epoxy and a combination of alicyclic epoxy resin, and the weight ratio of the phenolic epoxy and the bisphenol A type epoxy is (0.31-1.48):1; the weight ratio of the combination of the phenolic epoxy and the bisphenol A type epoxy and the alicyclic epoxy resin is (0.83-1.63):1.

[0032] The glass fiber surface treatment agent of the present application comprises a coupling agent, a penetrating agent, a lubricant, a film-forming agent, a toughening agent, an auxiliary agent, and water. The coupling agent and the film-forming agent are the main components of the glass fiber surface treatment agent of the present application. The coupling agent is essentially a kind of silane with organic functional groups. The silane coupling agent can form a very strong chemical bond with the glass surface to generate a siloxane bond (-Si-O-Si-) to achieve firm bonding to the glass, and form a dense siloxane protective layer on the glass surface to endow the glass fiber with good water resistance, solvent resistance, and corrosion resistance. At the same time, the glass surface treated with silane has a very large surface free energy, which can have a very strong physical attraction with the matrix resin, thereby obtaining a very high adhesion, improving the adhesion of the glass fiber and the resin, and greatly improving the strength, electrical, water resistance, and weather resistance of the glass fiber reinforced composite material. The film-forming agent is a key component of the surface treatment agent and is also the basis for determining the performance and classification of the surface treatment agent. The film-forming agent is used in the largest amount in the surface treatment agent, not only determines the bundling property of the glass fiber filaments and the post-processing processability, but also improves the compatibility of the glass fiber and the reinforcing resin and the mechanical properties of the composite material product. Compared with other types of film-forming agents, the combination of the phenolic epoxy, the bisphenol A type epoxy, and the alicyclic epoxy resin selected by the present application has the greatest advantage of stronger adhesion on the fiber surface. While retaining the good bundling property of the glass fiber, it has good compatibility with the epoxy resin system and is stable and not easy to decompose at high temperatures, meeting the weaving performance requirements of the glass fiber fabric for the battery shell of new energy vehicles and the mechanical performance requirements of the glass steel for the battery shell of new energy vehicles. The inventors have found through experiments that, after the coupling agent, the penetrating agent, the lubricant, the film-forming agent, the toughening agent, the auxiliary agent, and water are combined in the proportions of the present application to prepare the glass fiber surface treatment agent and the glass fiber surface treatment agent is applied to the glass fiber and its fabric, the bundling property and wear resistance of the glass fiber and the static penetration of the glass fiber fabric in the high-viscosity epoxy resin and the mechanical properties of the glass steel are also significantly better than those of other glass fiber surface treatment agents.

[0033] In order to further improve the effect of the glass fiber surface treatment agent of the present application, in a preferred embodiment, the effective component includes, in terms of weight percentage of the effective component: coupling agent 7.8-16.9%, penetrating agent 0.5-2.4%, lubricant 8.6-12.3%, film forming agent 62.4-79.9%, toughening agent 0.6-1.6%, and auxiliary agent 2.6-6.4%.

[0034] For the purpose of further improving the performance of the glass fiber surface treatment agent, in a preferred embodiment, the film forming agent is more preferably 65-77% by weight.

[0035] In a preferred embodiment, the phenolic epoxy includes o-cresol novolac epoxy resin and / or bisphenol A type phenolic epoxy resin; preferably, the phenolic epoxy is bisphenol A type phenolic epoxy resin; more preferably, the epoxy equivalent weight of the phenolic epoxy is 160-260 g / eq. The epoxy equivalent weight has an important influence on the performance of the epoxy resin. In the curing reaction, the increase of the epoxy equivalent weight in the epoxy resin can promote the crosslinking reaction, improve the heat resistance and hardness of the material, but too high epoxy equivalent weight will lead to too high crosslinking degree, the epoxy resin becomes too hard, resulting in the material too fragile, poor scratch resistance; while too low epoxy equivalent weight will lead to insufficient crosslinking degree, the epoxy resin becomes soft, the hardness index decreases, weakening the hardness and toughness of the material. Therefore, by reasonably selecting the size of the epoxy equivalent weight, the curing reaction rate and the curing degree can be effectively adjusted, thereby improving the comprehensive performance of the epoxy resin such as hardness, heat resistance and scratch resistance. It has been proved by practice that the phenolic epoxy with epoxy equivalent weight of 160-260 g / eq selected by the present application has high crosslinking density after curing, and the product has good heat resistance, scratch resistance, solvent resistance, chemical resistance and dimensional stability, which meets the high efficiency production requirements and various performance index requirements of new energy automobile battery shell. Compared with traditional phenolic epoxy resin, the preferred bisphenol A type phenolic epoxy resin of the present application has higher heat resistance and excellent comprehensive performance, but it is not appropriate to use too much, otherwise the brittleness of the product will increase, affecting the impact resistance of the product.

[0036] In a preferred embodiment, the bisphenol A type epoxy includes one or more of bisphenol A type epoxy, polyether modified bisphenol A type epoxy, and organosilicon blended modified bisphenol A type epoxy; preferably, the bisphenol A type epoxy is bisphenol A type epoxy and / or polyether modified bisphenol A type epoxy; more preferably, the epoxy equivalent weight of the bisphenol A type epoxy is 240-350 g / eq. The bisphenol A type epoxy selected by the present application can endow the resin with reactivity, so that the cured resin has strong cohesion and adhesion. Ether bond and hydroxyl group are polar groups, which help to improve wettability and adhesion. Ether bond and C-C bond make the macromolecule have flexibility. Benzene ring endows the polymer with heat resistance and rigidity. Isopropylidene group reduces the intermolecular force and endows the resin with certain toughness.

[0037] In a preferred embodiment, the alicyclic epoxy resin is a mixture of one or more of an epoxy methane resin, an epoxy propane resin, an epoxy butane resin, an alicyclic phenolic epoxy resin, an epoxy acrylate resin; preferably, the alicyclic epoxy resin is a mixture of one or more of an epoxy methane resin, an epoxy propane resin, an epoxy acrylate resin; more preferably, the alicyclic epoxy resin has an epoxy equivalent weight of 200-300 g / eq. The preferred alicyclic epoxy resin of the present application has high heat resistance, small shrinkage, stable electrical properties, and excellent weather resistance, and the finished product will not crack or deform. The use of the glass fiber surface treatment agent containing the preferred alicyclic epoxy resin described above is more conducive to obtaining glass fibers with excellent weather resistance, and the glass fiber reinforced glass steel composite material has higher compression and tensile strength, and can maintain good mechanical properties under long-term outdoor high temperature conditions.

[0038] The inventors have further found through experiments that the use of a phenolic epoxy resin in combination with a bisphenol A epoxy resin can improve the brittleness of the product after curing of a single component, effectively improving the toughness, heat resistance, and dimensional stability of the product. In a preferred embodiment, the combination of phenolic epoxy and bisphenol A type epoxy accounts for 30.8-44.7% by weight of the effective components; and the weight ratio of phenolic epoxy to bisphenol A type epoxy is (0.31-1.48):1 for the best effect; the alicyclic epoxy resin accounts for 27.5-37.2% by weight of the effective components, and the weight ratio of the combination of phenolic epoxy and bisphenol A type epoxy to the alicyclic epoxy resin is (0.83-1.63):1. According to the above ratio, the performance of the glass fiber surface treatment agent is more improved.

[0039] The penetrating agent of the present application can improve the rapid penetration of glass fibers and their fabrics in high viscosity epoxy resin, and quickly remove air bubbles in the glass fibers and their fabrics during the PCM molding process, thereby improving the mechanical properties of the composite material. In a preferred embodiment, the penetrating agent is one or a combination of two of ethoxylated acetylenic diols, polyether-modified siloxanes, and fatty alcohol polyoxyalkyl ether penetrating agents; preferably, it is ethoxylated acetylenic diols and / or polyether-modified siloxane penetrating agents. The penetrating agent selected by the present application has excellent spreading and penetrating properties, can effectively reduce the dynamic surface tension, and form a continuous phase of liquid on the solid surface, thereby improving the penetration of glass fibers and their fabrics in the resin. The inventors have found through research that too little penetrating agent will not significantly improve the penetration of glass fibers and their fabrics in the resin, and too much penetrating agent will affect the interlayer adhesion and negatively affect the performance of the glass steel composite material. Therefore, the amount of penetrating agent is most suitable when controlled at 0.3-2.8%. In a preferred embodiment, the amount of penetrating agent is 0.5-2.4%.

[0040] In order to further improve the processability of glass fiber, the adhesion strength between the reinforcing material and the resin, the physical and mechanical strength of the composite material, and the aging resistance and stress resistance of the glass steel product. In a preferred embodiment, the coupling agent is a combination of coupling agent A and coupling agent B; wherein the coupling agent A is one or a combination of two of the vinyl silane coupling agent, the acyloxy silane coupling agent, and the epoxy silane coupling agent, and the coupling agent B is an amino-containing silane coupling agent or a poly-nitrogen silane coupling agent. The coupling agent selected by the present application has a faster hydrolysis rate, can produce more hydroxyl groups under given conditions, and thus reacts with other components in the surface treatment agent to form more chemical bonds, resulting in better treatment effect; at the same time, it has a slower polymerization rate, so that the silane molecules can fully react and polymerize with the matrix resin, enhancing the modification effect of the glass steel composite material. Specifically, the vinyl silane coupling agent, the acyloxy silane coupling agent, and the epoxy silane coupling agent selected by the present application have good wettability on the surface of glass fiber, high reactivity, can fully react with the active groups on the surface of the glass fiber reinforcing material, play a role in repairing the micro-cracks on the surface of the fiber, and at the same time can form an effective and continuous protective layer on the surface of the glass fiber, improving the processability; at the same time, it can also react with epoxy resin, thereby enhancing the adhesion strength between the reinforcing material and the resin and improving the performance of the composite material. The amino-containing silane coupling agent selected by the present application has two functional groups, namely amino and X oxy. Among them, the hydrolyzable group (X oxy) is first hydrolyzed to generate silanol in the reaction. Since silanol is unstable, it is easy to combine with the hydroxyl group on the surface of inorganic or metal and dehydrate, thereby combining with inorganic materials such as glass or metal. The active hydrogen on the amino group can react with various polymers, thereby tightly combining two materials with completely different properties through chemical bonds. The poly-nitrogen silane coupling agent selected by the present application has a Si-NH-Si bond in its molecular structure, which can be cured at room temperature. The main reactions involved in curing are the hydrolysis and oxidation of Si-NH-Si. At the same time, the Si-NH-Si bond and the -OH on the surface of inorganic materials (glass) are easy to react, thereby bringing good bonding force with glass fiber, which can effectively improve the oxidation resistance and high temperature stability of glass fiber. Under high temperature conditions, it can be converted into SiCNO, SiCN, etc. Combined with the reinforcing resin, it can promote the reaction of Si-H and Si-NH-Si, so that the resin forms a three-dimensional cross-linked structure after curing, giving the material excellent corrosion resistance, oxidation resistance, radiation resistance, high temperature resistance, and glass steel mechanical properties, and is widely used in the fields of aerospace, semiconductors, photovoltaic cells, high temperature resistant coatings, ceramic materials, resin materials, etc. The preferred coupling agent A of the present application is a combination of acyloxy silane coupling agent and / or epoxy silane coupling agent, and the coupling agent B is a poly-nitrogen silane coupling agent; this combination can produce a synergistic effect, the treated glass fiber has high strength, long storage period, good compatibility with epoxy resin, and can significantly improve the corrosion resistance, high temperature resistance, and dry and wet glass steel mechanical properties of the composite material.However, due to the high reactivity and large cross-linking degree of the polyazidosilane-based coupling agent, excessive use of the coupling agent will cause the glass fiber to become hard and brittle, and reduce the infiltration speed of the glass fiber in the resin. However, the coupling agent cannot be used too little, otherwise the expected synergistic effect cannot be achieved. According to the number of active groups generated after the hydrolysis of each coupling agent, the coupling agents are combined. It has been proved through practice that the weight ratio of coupling agent A to coupling agent B is (0.44-2.46): 1, and the best synergistic effect is achieved. For example, the coupling agent of the present application can be selected from γ-methacryloxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy) propylmethyldimethoxysilane and polyazidosilane. In a preferred embodiment, the content of the coupling agent in the present application can be 7.3-17.3%, and further preferably 7.8-16.9%. More preferably, the weight percentage of coupling agent A in the effective component is 3.4-9.6%; the weight percentage of coupling agent B in the effective component is 3.9-7.7%.

[0041] The lubricant is beneficial to reduce the wear and tear damage of the glass fiber when it is in contact with the process accessories during production, improve the process performance of the glass fiber in reprocessing, and reduce the generation of glass fiber hair. In a preferred embodiment, the lubricant is a combination of one or more of silicone oil, quaternary ammonium salt compound and polyethylene glycol lubricant. The above-mentioned preferred lubricant in the present application can effectively reduce the friction resistance in the glass fiber drawing process, reduce the fiber damage, and at the same time, it is more beneficial to improve the process performance of the glass fiber in reprocessing, reduce the generation of hair, and improve the production efficiency. In a preferred embodiment, the content of the lubricant is 7.7-13.2%, and further preferably 8.6-12.3%.

[0042] The toughening agent can improve the bundling and flexibility of the glass fiber, reduce the brittleness of the composite material and improve the impact resistance of the composite material. In a preferred embodiment, the toughening agent is a reactive polyphenyl ether resin and / or a polycaprolactone polyol; preferably a polycaprolactone polyol. For example, the toughening agent is selected from polycaprolactone diol. The use of the toughening agent can change the microstructure of the material by introducing an elastic phase or a tough phase. These phases interact with the matrix material to form a composite structure, providing enhanced energy absorption and plastic deformation capability. Reduce the impact or stress. By absorbing and dispersing energy, the toughening agent can prevent crack propagation and fracture propagation, thereby improving the impact resistance of the material. Practice shows that in a preferred embodiment, the amount of toughening agent is 0.4-1.8%, and excessive use will affect the stiffness of the composite material. If too little is used, the impact resistance will not increase significantly; more preferably, 0.6-1.6%.

[0043] The auxiliary agent can improve the dispersibility of the coupling agent and has the effect of sterilization and mold prevention. In a preferred embodiment, the auxiliary agent is an organic acid; preferably the auxiliary agent is citric acid and / or acetic acid. Exemplarily, the auxiliary agent can be selected from a combination of acetic acid and citric acid. It is found through experiments that the amount of the auxiliary agent needs to be controlled. If the amount is too large, on the one hand, it can cause some components in the surface treatment agent to be ineffective, and on the other hand, it can cause acid corrosion to the glass fiber. If the amount is too small, the dispersing effect of the coupling agent and the sterilization and mold prevention effect cannot be fully achieved. In a preferred embodiment, the amount of the auxiliary agent is 2.4-6.6%, preferably 2.6-6.4%.

[0044] According to another aspect of the present application, a preparation method of the above-mentioned glass fiber surface treatment agent is provided, which comprises: mixing an auxiliary agent, a coupling agent, a penetrating agent, a lubricant, a toughening agent, a film-forming agent and water to obtain the glass fiber surface treatment agent. The glass fiber surface treatment agent obtained by the preparation method of the present application is applied to glass fiber, and the obtained glass fiber has excellent bunching property, wear resistance and weaving performance, good compatibility with epoxy resin, and high interfacial bonding degree.

[0045] According to another aspect of the present application, a glass fiber fabric produced by the glass fiber treated by the above-mentioned glass fiber surface treatment agent is provided, which can have fast and complete static penetration speed in high-viscosity epoxy resin, high mechanical strength of the product, and can meet various performance requirements of the battery shell of new energy vehicles. The main fabric structure is as follows:

[0046]

[0047] In a preferred embodiment, the preparation method of the present application can be carried out according to the following steps:

[0048] 1S: water is added to a container, then the auxiliary agent is added, after stirring for 2-3 minutes, the coupling agent is added; continue to stir for 50-75 minutes until the coupling agent is uniformly dispersed, the aqueous solution is clear and the surface is free of oil beads;

[0049] 2S: the penetrating agent is diluted with water and stirred uniformly, then added to the container;

[0050] 3S: the lubricant is diluted with water and stirred uniformly, then added to the container;

[0051] 4S: the toughening agent is diluted with water and stirred uniformly, then added to the container;

[0052] 5S: the film-forming agent is diluted with water and stirred uniformly, then added to the container;

[0053] 6S: the remaining amount of water is added to the container and stirred uniformly.

[0054] In step 1S, preferably, 35-40% of the total amount of the treating agent is added with water, and each coupling agent is added with an interval of 25-30 minutes.

[0055] In step 2S, preferably, 20-30 times of the amount of the penetrating agent is added with water at 40-50°C to dissolve and dilute the penetrating agent.

[0056] In step 3S, preferably, 4-6 times of the amount of the lubricant is added with water at 50-60°C to dissolve and dilute the lubricant.

[0057] In step 4S, preferably, 25-35 times of the amount of the toughening agent is added with water at 50-60°C to dissolve and dilute the toughening agent.

[0058] In step 5S, preferably, 2-3 times of the amount of the film-forming agent is added with water at 15-25°C to dilute the film-forming agent.

[0059] The above preparation method is only an example. Without departing from the aforementioned preparation method provided in the present application, the skilled person can adjust the order of the steps and the parameters of the specific steps according to the actual situation to obtain a corresponding glass fiber surface treating agent.

[0060] The present application will be further described in detail below in combination with specific examples, which should not be understood as limiting the scope of the present application.

[0061] Examples 1-12

[0062] The proportions of Examples 1-6 and the performance test results of the corresponding glass fiber products and glass fiber fabrics for producing new energy automobile battery shells are shown in Table 1; the proportions of Examples 7-12 and Comparative Examples 1-2 and the performance test results of the corresponding glass fiber products and glass fiber fabrics for producing new energy automobile battery shells are shown in Table 2.

[0063] Examples 1-12 are specific test results of applying the glass fiber surface treating agent to 600 tex direct yarn.

[0064] In the examples, the vinyl silane coupling agent, the acyloxy silane coupling agent, the epoxy silane coupling agent, and the polyazidosilane coupling agent are selected as γ-methacryloxypropyltrimethoxysilane, 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, and polyazidosilane, respectively, unless otherwise specified.

[0065] In the examples, the quaternary ammonium salt compound is selected as polyethyleneimine quaternary ammonium salt, the silicone oil lubricant is selected as dimethyl silicone oil, and the polyethylene glycol lubricant is selected as PEG800.

[0066] In the examples, the ethoxylated acetylenic diol penetrant is Dynol 604 (American Gas), the polyether-modified siloxane penetrant is Greeso H91 (Yueyang Kaimen Water-based Additives Co., Ltd.), and the fatty alcohol polyoxyalkyl ether penetrant is Plurafac LF221 (BASF).

[0067] In the examples, the epoxy equivalent weight of the phenolic epoxy in the film-forming agent is 200 g / eq; the epoxy equivalent weight of the bisphenol A type epoxy is 280 g / eq; and the epoxy equivalent weight of the alicyclic epoxy resin is 260 g / eq, unless otherwise specified.

[0068] In the examples, the phenolic epoxy is a bisphenol A type phenolic epoxy resin; the bisphenol A type epoxy is a polyether-modified bisphenol A type epoxy resin; and the alicyclic epoxy resin is an epoxy propane resin.

[0069] In the examples, the toughening agent is poly-caprolactone polyol (PCL-2200A, Hunan Juren New Material Co., Ltd.).

[0070] In the examples, the auxiliary agent is acetic acid and / or citric acid.

[0071] Comparative Example 1

[0072] The components of the glass fiber surface treatment agent are as follows:

[0073] Coupling agent: vinyl trimethoxysilane (14%);

[0074] Lubricant: dimethyl silicone oil (14.5%);

[0075] Film-forming agent: bisphenol A epoxy (66%);

[0076] Auxiliary agent: citric acid (5.5%).

[0077] Comparative Example 2

[0078] The components of the glass fiber surface treatment agent are as follows:

[0079] Coupling agent: γ-methacryloyloxypropyl trimethoxysilane (10%);

[0080] Lubricant: PEG2000 (15%);

[0081] Film-forming agent: polyester-modified epoxy resin (70%);

[0082] Auxiliary agent: citric acid (1%) combined with glacial acetic acid (4%).

[0083] Table 1

[0084]

[0085] Table 2

[0086]

[0087]

[0088] From the above performance test comparison, it can be seen that by designing the components and component content, the required treatment agent can be obtained, and the performance data is better than the comparative examples; among them, the effects of examples 3, 5, 8, 9 and 11 are better, because in the above five kinds of proportion, each component in the treatment agent can fully exert the advantages of each component.

[0089] In summary, the glass fiber fabric produced by the glass fiber treated by the glass fiber surface treatment agent of the present application has a fast and complete static penetration speed in high viscosity epoxy resin, and the mechanical strength of the product is high, which can meet the performance requirements of new energy automobile battery shell.

[0090] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Those skilled in the art can make various changes and modifications to the present application. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the protection scope of the present application.

[0091] Finally, it should be noted that: the above examples are only used to illustrate the technical solutions of the present application, and not to limit it. Although the present application has been described in detail with reference to the foregoing examples, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing examples, or make equivalent replacement to part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A glass fiber surface treatment agent characterized by, The surface treatment agent comprises effective components and water, and the solid content of the surface treatment agent is 5.8-10.5%; the effective components comprise, in terms of weight percentage of the effective components, 7.3-17.3% of coupling agent, 0.3-2.8% of penetrating agent, 7.7-13.2% of lubricant, 58.3-81.9% of film forming agent, 0.4-1.8% of toughening agent, and 2.4-6.6% of auxiliary agent; wherein, The film forming agent comprises film forming agent A and film forming agent B, the film forming agent A is a combination of phenolic aldehyde epoxy emulsion and bisphenol A type epoxy emulsion, and the film forming agent B is alicyclic epoxy resin emulsion.

2. The glass fiber surface-treatment agent according to claim 1, characterized by, The effective components comprise, in terms of weight percentage of the effective components, 7.8-16.9% of coupling agent, 0.5-2.4% of penetrating agent, 8.6-12.3% of lubricant, 62.4-79.9% of film forming agent, 0.6-1.6% of toughening agent, and 2.6-6.4% of auxiliary agent.

3. The glass fiber surfacing agent according to claim 1, wherein The phenolic aldehyde epoxy comprises ortho-methylphenol aldehyde epoxy resin and / or bisphenol A type phenolic aldehyde epoxy resin; the bisphenol A type epoxy comprises one or more of bisphenol A type epoxy, polyether modified bisphenol A type epoxy, and organosilicon blended modified bisphenol A type epoxy; and the alicyclic epoxy resin is a mixture of one or more of epoxy methane resin, epoxy propane resin, epoxy butane resin, alicyclic phenolic aldehyde epoxy resin, and epoxy acrylate resin.

4. The glass fiber surfacing agent according to claim 3, characterized by, The phenolic aldehyde epoxy is bisphenol A type phenolic aldehyde epoxy resin; the bisphenol A type epoxy is bisphenol A type epoxy and / or polyether modified bisphenol A type epoxy; and the alicyclic epoxy resin is a mixture of one or more of epoxy methane resin, epoxy propane resin, and epoxy acrylate resin.

5. The glass fiber surfacing agent according to claim 3, wherein The epoxy equivalent weight of the phenolic aldehyde epoxy is 160-260 g / eq; the epoxy equivalent weight of the bisphenol A type epoxy is 240-350 g / eq; and the epoxy equivalent weight of the alicyclic epoxy resin is 200-300 g / eq.

6. The glass fiber surfacing agent according to claim 1, wherein The weight percentage of the combination of the phenolic aldehyde epoxy and the bisphenol A type epoxy in the effective components is 30.8-44.7%, and the weight ratio of the phenolic aldehyde epoxy to the bisphenol A type epoxy is (0.31-1.48):1; the weight percentage of the alicyclic epoxy resin in the effective components is 27.5-37.2%, and the weight ratio of the combination of the phenolic aldehyde epoxy and the bisphenol A type epoxy to the alicyclic epoxy resin is (0.83-1.63):

1.

7. The glass fiber surfacing agent according to claim 1, wherein The coupling agent comprises coupling agent A and coupling agent B, the weight percentage of the coupling agent A in the effective components is 3.4-9.6%, and the weight percentage of the coupling agent B in the effective components is 3.9-7.7%; The coupling agent A is one or a combination of vinyl silane containing coupling agent, acyloxy silane containing coupling agent, and epoxy group containing silane coupling agent; and the coupling agent B is amino group containing silane coupling agent or polyazidosilane coupling agent.

8. The glass fiber surfacing agent according to claim 7, characterized by The coupling agent A is acyloxy silane containing coupling agent and / or epoxy group containing silane coupling agent, and the coupling agent B is polyazidosilane coupling agent; and the weight ratio of the coupling agent A to the coupling agent B is (0.44-2.46):

1.

9. The glass fiber surfacing agent of claim 1, wherein The penetrating agent is one or a combination of ethoxylated acetylenic diols, polyether-modified siloxanes, and fatty alcohol polyoxyalkyl ether; The lubricant is a combination of one or more of silicone oil, quaternary ammonium salt compound, and polyethylene glycol; The toughening agent is reactive polyphenyl ether resin and / or polycaprolactone polyol; The auxiliary agent is an organic acid.

10. The glass fiber surfacing agent according to claim 9, wherein The penetrating agent is ethoxylated acetylenic diols and / or polyether-modified siloxane; the toughening agent is polycaprolactone polyol; and the auxiliary agent is citric acid and / or acetic acid.

11. A method for producing the glass fiber surface treatment agent according to any one of claims 1 to 10, characterized by, The application further discloses a glass fiber surface treatment agent prepared by the method. The glass fiber surface treatment agent prepared by the method of claim 11 is used.

12. A glass fiber characterized in that, The glass fiber prepared by the method of claim 12 is woven.

13. A glass fiber fabric characterized in that, 14. The application of the glass fiber fabric of claim 13 in a new energy automobile battery shell. ​

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