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

Abstract

The application provides a glass fiber surface treatment agent, a preparation method thereof, glass fiber, a fabric and application thereof. The glass fiber surface treatment agent comprises effective components and water, and the weight percentage of the effective components in the glass fiber surface treatment agent is 4.5-11.4%; according to the weight percentage of the effective components, the effective components comprise: a coupling agent 5.6-14.4%, a lubricant 8.3-15.3%, a film forming agent 65.31-84.15%, a polymerization inhibitor 0.05-0.83% and an auxiliary agent 1.90-4.16%; wherein the film forming agent is a combination of phenolic epoxy resin and modified epoxy resin. The glass fiber produced by using the glass fiber surface treatment agent has excellent bundling, wear resistance and weaving performance, and the interface bonding degree of the glass fabric in unsaturated polyester resin can be controlled, so that the reinforced composite material meets the performance requirements of energy absorption and impact-resistant composite materials.

Description

TECHNICAL FIELD

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

[0002] In recent years, as people pay more and more attention to safety, the demand for impact-resistant composite materials in the market is increasing year by year. Impact-resistant composite materials have wide application potential in the field of high-speed impact protection, including wide application in airplanes, cars, financial institutions, building bridges, gas stations and some safety facilities with impact resistance requirements. Traditional materials such as metal materials have strong rigidity, and when subjected to high-speed impact, they can resist direct damage or destruction, but the impact force cannot be effectively released, and they will be indirectly damaged or destroyed by inertial force; another material such as plastic material has poor rigidity and cannot effectively resist high-speed impact objects. Therefore, the sandwich composite material of metal plate + glass steel + metal plate emerges as the times require. By appropriately reducing the interfacial bonding of the glass fiber fabric and the target resin, i.e. unsaturated polyester resin, the glass fiber reinforced composite material has certain integrity, improves toughness and reduces the rigidity of the glass steel, thereby forming a heterogeneous material with the outer metal plate. The impact force acting on the outer metal plate causes the metal plate to deform, while the middle layer composite material can quickly and effectively decompose the impact force in multiple ways, such as cracking, overall deformation or delamination of the composite material, which can effectively absorb impact energy and prevent external objects from damaging it, achieving the purpose of energy absorption and impact resistance.

[0003] The existing glass fiber fabric on the market is designed to enhance a specific resin system to improve the mechanical properties of the glass steel composite material, thereby meeting the use requirements of different fields such as wind blades, glass steel fishing boats and recreational facilities. This makes the reinforced glass steel composite material have strong rigidity, and when subjected to high-speed impact force, stress concentration occurs, which cannot quickly and effectively decompose the impact force, and cannot achieve the purpose of energy absorption and impact resistance.

[0004] Therefore, how to reduce the rigidity (such as bending strength) of traditional glass steel products by reducing the interfacial bonding degree of glass fiber and unsaturated polyester resin, and retain the integrity of the composite material, improve the toughness and cushioning performance, so as to meet the industrial production requirements of energy-absorbing and impact-resistant composite materials, has been a technical problem that the composite material industry needs to overcome. The glass fiber surface treatment agent can change the surface state of the glass fiber, not only meet the processing performance requirements of the glass fiber raw silk in the subsequent process, but also promote the combination of the glass fiber reinforcement and the polymer polymer matrix in the composite material, and is an important factor to determine the final performance of the glass fiber reinforced composite material. In summary, the current composite material industry needs to develop a new type of glass fiber surface treatment agent, the glass fiber treated with the surface treatment agent has excellent bunching, wear resistance and weaving performance, and the interfacial bonding degree of the glass fiber fabric in the unsaturated polyester resin can be controlled, so that the reinforced composite material has certain integrity and is not easily damaged by low stress, has good toughness and low rigidity, and meets the performance requirements of energy-absorbing and impact-resistant composite materials.

[0005] The related glass fiber technical requirements are as follows (2000tex, glass fiber fabric unit area mass 850g / m 2 For example, reinforced unsaturated polyester resin):

[0006] Glass fiber performance index:

[0007] Test item Unit Test standard Index requirement Pilosity mg / kg / ≤60 Shear strength MPa ASTM D2344 45-60

[0008] The related glass fiber fabric technical requirements are as follows (reinforced unsaturated polyester resin):

[0009] Glass fiber fabric performance index:

[0010] Test item Unit Test standard Index requirement Tensile strength in warp direction N GB / T 7689.5 ≥7000 Tensile strength in weft direction N GB / T 7689.5 ≥7000 Bending strength MPa GB / T1449 250～400 SUMMARY

[0011] The main purpose of the present application is to provide a glass fiber surface treatment agent for energy-absorbing and impact-resistant composite materials, a preparation method thereof, glass fiber, fabric and application thereof. The glass fiber treated with the surface treatment agent has excellent bunching, wear resistance and weaving performance, and the interfacial bonding degree of the glass fiber fabric in the unsaturated polyester resin can be controlled, so that the reinforced composite material has certain integrity and is not easily damaged by low stress, has good toughness and low rigidity, and meets the performance requirements of energy-absorbing and impact-resistant composite materials.

[0012] In order to achieve the above-mentioned purpose, according to one 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 4.5-11.4% of the glass fiber surface treatment agent by weight; the effective component comprises, by weight of the effective component: 5.6-14.4% of a coupling agent, 8.3-15.3% of a lubricant, 65.31-84.15% of a film-forming agent, 0.05-0.83% of a polymerization inhibitor, and 1.90-4.16% of an auxiliary agent; wherein the film-forming agent is a combination of a phenolic aldehyde epoxy resin and a modified epoxy resin.

[0013] Further, the effective component comprises, by weight of the effective component: 7.8-12.8% of a coupling agent, 9.7-14.1% of a lubricant, 68.6-80.1% of a film-forming agent, 0.14-0.62% of a polymerization inhibitor, and 2.31-3.88% of an auxiliary agent.

[0014] Further, the phenolic aldehyde epoxy resin is one of a bisphenol A phenolic aldehyde epoxy resin, a phenol phenolic aldehyde epoxy aqueous dispersion, and an o-methyl phenol phenolic aldehyde epoxy resin; preferably, the phenolic aldehyde epoxy resin is the phenol phenolic aldehyde epoxy aqueous dispersion; preferably, the average functionality of the phenolic aldehyde epoxy resin is 3-4.

[0015] Further, the modified epoxy resin is one of an isocyanate modified bisphenol A epoxy resin, an acrylic modified epoxy resin, and an organic silicon blended modified epoxy; preferably, the modified epoxy resin is the isocyanate modified bisphenol A epoxy resin; preferably, the average functionality of the modified epoxy resin is 1-2.

[0016] Further, the phenolic aldehyde epoxy resin accounts for 38.25-44.51% of the effective component by weight; the modified epoxy resin accounts for 20.8-45.9% of the effective component by weight, and the weight ratio of the phenolic aldehyde epoxy resin to the modified epoxy resin is 1:1.2-2.14:1.

[0017] Further, the coupling agent is a combination of a coupling agent A, a coupling agent B, and a coupling agent C; wherein the coupling agent A is an epoxy-containing silane coupling agent, the coupling agent B is an amino-containing silane coupling agent, and the coupling agent C is a polyazidosilane-containing coupling agent; preferably, the coupling agent A accounts for 1.4-7.2% of the effective component by weight, the coupling agent B accounts for 1.4-5.4% of the effective component by weight, and the coupling agent C accounts for 1.8-2.8% of the effective component by weight; more preferably, the weight ratio of the coupling agent A to the coupling agent B to the coupling agent C is 1:1:2-4:3:1.

[0018] Further, the lubricant is a combination of one or more of a silicone oil type, a PEG type, and a hydrogenated vegetable oil type lubricant.

[0019] Further, the polymerization inhibitor is hydroquinone and / or p-tert-butyl hydroquinone; preferably, the polymerization inhibitor is p-tert-butyl hydroquinone.

[0020] Further, the auxiliary agent is an organic acid; preferably, the auxiliary agent is citric acid and / or acetic acid.

[0021] In order to achieve the above-mentioned object, according to an aspect of the present application, there is provided a preparation method of the above-mentioned glass fiber surface treatment agent, comprising: mixing an auxiliary agent, a coupling agent, a lubricant, a polymerization inhibitor, a film-forming agent and water to obtain the glass fiber surface treatment agent.

[0022] According to another aspect of the present application, there is provided a glass fiber treated by the above-mentioned glass fiber surface treatment agent prepared by the above-mentioned preparation method.

[0023] According to another aspect of the present application, there is provided a glass fiber fabric knitted by the above-mentioned glass fiber prepared by the above-mentioned preparation method.

[0024] According to another aspect of the present application, there is provided an application of the above-mentioned glass fiber fabric in energy-absorbing and impact-resistant composite materials.

[0025] The technical scheme of the application provides a glass fiber surface treatment agent, which comprises a coupling agent, a lubricant, a film forming agent, a polymerization inhibitor, an auxiliary agent and water; the coupling agent and the film forming agent are main components of the glass fiber surface treatment agent. The coupling agent plays a crucial role, which mainly adjusts the interfacial compatibility between the glass fiber and the resin matrix, thereby adjusting the bonding force between them. The realization of this effect benefits from the unique molecular structure and chemical properties of the coupling agent. The coupling agent molecule usually contains two parts, inorganic and organic groups; the inorganic group can chemically react with the inorganic matter on the surface of the glass fiber to form a chemical bond, so that the coupling agent is firmly attached to the glass fiber, while the organic group reacts with the organic matter in the resin matrix to form a chemical bond. In this way, the coupling agent acts as a bridge, determining the interfacial bonding degree of the glass fiber and the resin matrix. At the same time, the interfacial layer formed by the coupling agent can also transfer stress, so that the glass fiber and the resin matrix can work together to bear the load when stressed. The film forming agent is a key component of the surface treatment agent, which plays a key role in forming a protective layer and improving performance in the glass fiber surface treatment agent; it can uniformly cover the surface of the glass fiber to form a stable and active group-rich film, which not only effectively isolates the erosion of external environmental factors on the glass fiber, improving its durability, but also enhances the adhesion and adhesion of the glass fiber and other materials by changing the surface properties. In addition, the film forming agent can also optimize the processing performance of the glass fiber, making it more stable during the preparation of composite materials, thereby ensuring the quality and performance of the final product. Compared with other types of film forming agents, the biggest advantage of the combination of phenolic epoxy resin and modified epoxy resin film forming agent composition selected by the application is that it realizes comprehensive optimization and improvement of performance. First of all, phenolic epoxy resin provides a solid foundation for composite materials with its excellent heat resistance, mechanical strength and chemical corrosion resistance. The addition of modified epoxy resin further enhances the solvent resistance, flexibility and processing performance of the material, so that the composition can maintain excellent performance in various harsh environments. The combination of the two not only realizes the complementation of performance, but also improves the overall performance of the composite material, such as better heat resistance and wider applicability. The inventors found through experiments that the coupling agent, lubricant, film forming agent, polymerization inhibitor, auxiliary agent and water are combined in the ratio of the application to prepare the glass fiber surface treatment agent, and the glass fiber and its fabric are applied. The bundling property, wear resistance and weaving performance of the glass fiber are significantly better than those of other glass fiber surface treatment agents, and the interfacial bonding degree of the glass fiber fabric and the unsaturated polyester resin is significantly lower than that of other glass fiber surface treatment agents, and the composite material has good toughness and low rigidity, meeting the performance requirements of energy-absorbing and impact-resistant composite materials. DETAILED DESCRIPTION

[0026] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other in the case of no conflict. The present application will be described in detail below in combination with the embodiments.

[0027] In order 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 4.5-11.4% of the weight percentage of the glass fiber surface treatment agent; the effective component comprises, in terms of the weight percentage of the effective component: a coupling agent 5.6-14.4%, a lubricant 8.3-15.3%, a film forming agent 65.31-84.15%, a polymerization inhibitor 0.05-0.83%, and an auxiliary agent 1.90-4.16%; wherein the film forming agent is a combination of a phenolic epoxy resin and a modified epoxy resin, and the weight ratio of the phenolic epoxy resin to the modified epoxy resin is 1:1.2-2.14:1.

[0028] The glass fiber surface treatment agent of the present application comprises a coupling agent, a lubricant, a film forming agent, a polymerization inhibitor, an auxiliary agent, and water.

[0029] The coupling agent and the film-forming agent are the main components of the glass fiber surface treatment agent. The coupling agent plays a crucial role and is one of the focuses of the present application. Its main function is to adjust the interfacial compatibility between the glass fiber and the resin matrix, thereby adjusting the bonding force between the two. The realization of this effect benefits from the unique molecular structure and chemical properties of the coupling agent. The coupling agent molecule usually contains both inorganic and organic groups. The inorganic group can chemically react with the inorganic material on the surface of the glass fiber to form a chemical bond, allowing the coupling agent to adhere firmly to the glass fiber. The organic group, on the other hand, reacts with the organic material in the resin matrix to form a chemical bond as well. In this way, the coupling agent acts as a bridge, determining the interfacial bonding degree of the glass fiber and the resin matrix. At the same time, the interfacial layer formed by the coupling agent can also transmit stress, allowing the glass fiber and the resin matrix to work together when under stress and share the load. Compared to other types of film-forming agents, the film-forming agent is a key component of the surface treatment agent and is another focus of the present application. The film-forming agent plays a key role in forming a protective layer and improving performance in the glass fiber surface treatment agent. It can uniformly cover the surface of the glass fiber to form a stable and active group-rich film. This film not only effectively isolates the glass fiber from external environmental factors, improving its durability, but also enhances the adhesion and bonding ability of the glass fiber with other materials by changing the surface properties. In addition, the film-forming agent can also optimize the processing performance of the glass fiber, making it more stable during the preparation of composite materials, thereby ensuring the quality and performance of the final product. Compared to other types of film-forming agents, the combination of phenolic epoxy resin and modified epoxy resin used in the present application has the greatest advantage of achieving comprehensive optimization and improvement in performance. First, phenolic epoxy resin provides a solid foundation for composite materials due to its excellent heat resistance, mechanical strength, and chemical corrosion resistance. The addition of modified epoxy resin further enhances the material's solvent resistance, flexibility, and processing performance, allowing the composition to maintain excellent performance in a variety of harsh environments. The combination of the two not only achieves performance complementarity but also improves the overall performance of the composite material, such as better heat resistance and wider applicability. The applicant found through experiments that the coupling agent, lubricant, film-forming agent, polymerization inhibitor, auxiliary agent, and water were combined in the proportions specified in the present application to produce a glass fiber surface treatment agent. When applied to glass fibers and their fabrics, the glass fibers' bundling, wear resistance, and weaving performance were significantly better than those of other glass fiber surface treatment agents. The interfacial bonding degree of the glass fiber fabric with unsaturated polyester resin was significantly lower than that of other glass fiber surface treatment agents, and the composite material had good toughness and low rigidity, meeting the performance requirements of energy-absorbing and impact-resistant composite materials.

[0030] 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 7.8-12.8%, lubricant 9.7-14.1%, film forming agent 68.6-80.1%, polymerization inhibitor 0.14-0.62%, and auxiliary agent 2.31-3.88%.

[0031] 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 70-78% by weight.

[0032] The inventors have found through experiments that the combination of phenolic epoxy resin and modified epoxy resin can improve the limitations of single component, make full use of the high heat resistance and brittleness of phenolic epoxy resin after curing, balance the processability and toughness of modified epoxy resin, and realize complementary advantages. In a preferred embodiment, the weight percentage of phenolic epoxy resin in the effective component is 38.25-44.51%, the weight percentage of modified epoxy resin in the effective component is 20.8-45.9%, and the weight ratio of phenolic epoxy resin to modified epoxy resin is 1:1.2-2.14:1. According to the above ratio, it is more beneficial to obtain the performance of the glass fiber surface treatment agent required by the present application.

[0033] In a preferred embodiment, the phenolic epoxy resin is one of bisphenol A phenolic epoxy resin, phenol novolac epoxy water dispersion, and o-methyl phenol novolac epoxy resin. The above three epoxy resins can provide excellent weather resistance and mechanical properties. Specifically, bisphenol A phenolic epoxy resin exhibits excellent mechanical strength, electrical insulation, water resistance, and chemical stability due to its high crosslinking density and glass transition temperature; phenol novolac epoxy water dispersion can provide excellent chemical resistance, heat resistance, and mechanical strength, while greatly reducing VOC emissions, meeting the requirements of green building and environmental protection manufacturing; o-methyl phenol novolac epoxy resin can impart excellent thermal stability, mechanical strength, electrical insulation performance, and water resistance to the cured product, and exhibits good process stability and processing properties. Preferably, the phenolic epoxy resin is phenol novolac epoxy water dispersion; more preferably, the average functionality of the phenolic epoxy resin is 3-4. It has been found through experiments that by adjusting the functionality of the phenolic epoxy resin, the performance of the product can be precisely controlled; the phenolic epoxy resin with an average functionality of 3-4 selected by the present application can exhibit more excellent performance in terms of heat resistance, corrosion resistance, and mechanical properties, meeting the requirements of specific application scenarios.

[0034] In a preferred embodiment, the modified epoxy resin is one of isocyanate modified bisphenol A epoxy resin, acrylic modified epoxy resin, and silicone blended modified epoxy resin. It is found in experiments that the above modified resins have improved weather resistance, mechanical properties, chemical resistance, etc., and broaden their application range. Specifically, the isocyanate modified bisphenol A epoxy resin can enhance the crosslinking density and heat resistance of the epoxy resin, while improving the hardness and wear resistance, and the adhesion to the substrate. The acrylic modified epoxy resin combines the weather resistance and ultraviolet resistance of the acrylic resin, and the high adhesion strength and mechanical strength of the epoxy resin, so that the modified resin performs better in water resistance, solvent resistance and chemical resistance. The silicone blended modified epoxy resin can reduce the internal stress of the epoxy resin, improve the flexibility and impact resistance, and the modified resin has better high temperature resistance and weather resistance, and is suitable for high temperature environment and outdoor application; at the same time, the water resistance and chemical resistance of the silicone also enhance the corrosion resistance of the epoxy resin. Preferably, the modified epoxy resin is isocyanate modified bisphenol A epoxy resin; more preferably, the average functionality of the modified epoxy resin is 1-2. It is found in experiments that the modified epoxy resin with lower functionality has relatively lower reactivity in the curing process, which helps to control the rate and temperature of the curing reaction, so that the smooth curing process is more easily realized. The modified epoxy resin with average functionality of 1-2 is selected in the present application, which has lower viscosity, helps to improve the flowability in the processing process, so that the processing process is more smooth, and at the same time helps to reduce the energy consumption. And the crosslinking structure formed after the curing of the modified epoxy resin with functionality of 1-2 is relatively sparse, so that the cured product has good toughness and can better withstand external impact and stress.

[0035] The selection of the coupling agent can further improve the processability of the glass fiber, effectively control the adhesion between the reinforcing material and the resin, reduce the rigidity of the composite material, improve the energy absorption and impact resistance while ensuring the integrity of the composite material, and play a crucial role. It is one of the focuses of the present application. In a preferred embodiment, the coupling agent is a combination of coupling agent A, coupling agent B and coupling agent C; wherein the coupling agent A is an epoxy-containing silane coupling agent, the coupling agent B is an amino-containing silane coupling agent, and the coupling agent C is a polyazidosilane-containing coupling agent; preferably, the weight percentage of the coupling agent A in the effective component is 1.4-7.2%, the weight percentage of the coupling agent B in the effective component is 1.4-5.4%, and the weight percentage of the coupling agent C in the effective component is 1.8-2.8%; more preferably, the weight ratio of the coupling agent A, the coupling agent B and the coupling agent C is 1:1:2-4:3:1. The coupling agent selected in the present application has a unique mechanism of action in the glass fiber processing process, and they can produce significant synergistic effects. Specifically, the epoxy-containing silane coupling agent and the amino-containing silane coupling agent selected in the present application have good wettability, which can improve the wetting state of the glass fiber surface and fully react with the active groups on the surface of the glass fiber, play a role in repairing the micro-cracks on the surface of the fiber, and form an effective and continuous protective layer on the surface of the glass fiber, improving the processability; at the same time, the epoxy group and the amino group can chemically react with the hydroxyl group, carboxyl group and other functional groups in the resin to form chemical bonds, thereby improving the adhesion between the glass fiber and the resin. Since the unsaturated polyester resin contains carboxyl or hydroxyl groups, these groups will chemically react with the glass fiber containing epoxy-containing silane coupling agent and amino-containing silane coupling agent, ensuring the integrity of the composite material; at the same time, since the main components of the unsaturated polyester resin are ester bonds and unsaturated double bonds, they cannot usually chemically react with epoxy groups and amino groups, thus ensuring that the composite material has the characteristics of low rigidity, and the amount of epoxy groups and amino groups plays a decisive role in effectively controlling the rigidity of the composite material. The polyazidosilane group in the polyazidosilane-containing coupling agent can form various chemical bonding modes (such as silicon-oxygen bond, nitrogen-silicon bond, hydrogen bond, etc.) with the epoxy group and the amino group and produce synergistic effects, which can more effectively control the rigidity of the composite material and improve the energy absorption and impact resistance. However, due to the high reactivity and large cross-linking degree of the polyazidosilane-containing coupling agent, excessive use will cause the glass fiber to become hard and brittle, reducing the infiltration speed of the glass fiber in the resin, but it cannot be too small, otherwise the expected synergistic effect cannot be achieved. According to the number of active groups produced after the hydrolysis of each coupling agent, the coupling agent A, the coupling agent B and the coupling agent C are combined, and it has been proved through practice that the weight ratio of the coupling agent A, the coupling agent B and the coupling agent C is 1:1:2-4:3:1, achieving the best synergistic effect. For example, the coupling agent of the present application can be selected from 3-glycidyloxypropyltrimethoxysilane, aminopropyltriethoxysilane and polyazidosilane.In a preferred embodiment, the content of the coupling agent in the present application can be further preferably 7.8-12.8%.

[0036] The main function of the lubricant is to reduce the friction between materials, thereby reducing wear and tear and protecting the surface of the material. In a preferred embodiment, the lubricant is a combination of one or more of the following: silicone oil, PEG, and hydrogenated vegetable oil. The above-mentioned preferred lubricant in the present application can significantly reduce the wear and tear damage of the glass fiber when it comes into contact with the process accessories during production, improve the process performance of the glass fiber during the preparation or processing of the composite material, reduce the generation of glass fiber hairiness, and improve the production efficiency. In a preferred embodiment, the content of the lubricant can be further preferably 8.6-12.3%.

[0037] In order to improve the impact resistance of the composite material, in a preferred embodiment, the polymerization inhibitor is hydroquinone and / or p-tert-butyl catechol; preferably, the polymerization inhibitor is p-tert-butyl catechol. Exemplarily, the polymerization inhibitor is p-tert-butyl catechol. The use of the polymerization inhibitor mainly reduces the crosslinking degree of the unsaturated polyester resin and the rigidity of the material through its mechanism of inhibiting free radical polymerization. The polymerization inhibitor can preferentially combine with the free radicals in the system to form inactive substances or low-activity free radicals, thereby slowing down or preventing the progress of the polymerization reaction, resulting in a decrease in the crosslinking structure formed during the curing process of the resin, a decrease in the crosslinking density, and thus a decrease in the rigidity of the material when subjected to external force. At the same time, the addition of the polymerization inhibitor can also lead to an increase in the toughness of the material, because the decrease in the crosslinking degree enhances the mobility of the resin molecular chain, which can better absorb energy. Practice shows that in a preferred embodiment of the present application, the amount of the polymerization inhibitor is 0.6-1.6% for the best effect, and excessive use can lead to too low rigidity of the composite material, and if too little is used, the impact resistance effect does not increase significantly. Therefore, the use of the polymerization inhibitor is one of the focuses of the present application.

[0038] In order to improve the dispersibility of the coupling agent, 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 citric acid. The skilled person should control the amount of the auxiliary agent used in the present application, and if the amount added is too much, on the one hand, it can lead to the failure of some components in the surface treatment agent, and on the other hand, it can cause acid corrosion to the glass fiber and its production equipment and process accessories; and if the amount used is too little, it cannot fully achieve the dispersing effect of the coupling agent and the sterilization and mildew prevention effect. In a preferred embodiment, the amount of the auxiliary agent is preferably 2.31-3.88%.

[0039] According to another aspect of the present application, a preparation method of the above-mentioned glass fiber surface treatment agent is provided, comprising: mixing an additive, a coupling agent, a lubricant, a polymerization inhibitor, 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 fibers, and the obtained glass fibers have excellent bundling property, wear resistance and weaving property, and the interface bonding degree of the glass fabric in unsaturated polyester resin can be controlled.

[0040] According to another aspect of the present application, a glass fabric produced by the glass fiber treated by the above-mentioned glass fiber surface treatment agent is provided, and the interface bonding degree of the glass fabric in unsaturated polyester resin can be controlled, so that the reinforced composite material has certain integrity and is not easily damaged by low stress, and has good toughness and low rigidity, meeting the performance requirements of energy absorption and impact-resistant composite material. The main fabric structure is as follows:

[0041]

[0042]

[0043] In a preferred embodiment, the preparation method of the present application can be carried out according to the following steps:

[0044] 1S: water is added to a container, then the additive is added, and after stirring for 2-3 minutes, the coupling agent is added; continue to stir for 25-35 minutes until the coupling agent is uniformly dispersed, and the aqueous solution is clear and free of oil beads on the surface;

[0045] 2S: the lubricant is diluted with water and stirred uniformly, and then added to the container;

[0046] 3S: the polymerization inhibitor is diluted with water and stirred uniformly, and then added to the container;

[0047] 4S: the film forming agent is diluted with water and stirred uniformly, and then added to the container;

[0048] 5S: the remaining amount of water is added to the container and stirred uniformly.

[0049] In step 1S, preferably 30-45% of the total amount of the treatment agent is added to the water, and each coupling agent is added at an interval of 20-30 minutes;

[0050] In step 2S, preferably 5-10 times the amount of the lubricant is added to 50-60°C water to dissolve and dilute the lubricant;

[0051] In step 3S, preferably 30-40 times the amount of the polymerization inhibitor is added to 15-25°C water to dissolve and dilute the polymerization inhibitor;

[0052] In step 4S, preferably, 2-3 times of the film forming agent is added into 15-25℃ water to dilute the film forming agent.

[0053] The above preparation method is only for example. Without departing from the aforementioned preparation method provided by the present application, the skilled person can adjust the order of several steps or the parameters of specific steps according to the actual situation to obtain the corresponding glass fiber surface treatment agent.

[0054] According to another aspect of the present application, a glass fiber treated by the glass fiber surface treatment agent prepared by the aforementioned preparation method is provided.

[0055] According to another aspect of the present application, a glass fiber fabric woven by the glass fiber prepared by the aforementioned preparation method is provided.

[0056] According to another aspect of the present application, the aforementioned glass fiber fabric is applied in energy-absorbing and impact-resistant composite materials.

[0057] The present application will be further described in detail in combination with specific examples, which cannot be understood as limiting the scope of the present application.

[0058] Examples 1-10

[0059] The ratio of Examples 1-10 and the corresponding performance test results of glass fiber products and glass fiber fabrics in energy-absorbing and impact-resistant composite materials are shown in Table 1.

[0060] Examples 1-10 are specific test results of applying glass fiber surface treatment agent to 2000tex direct yarn.

[0061] Unless otherwise specified, in Examples 1-6, the epoxy-containing silane coupling agent is 3-glycidyloxypropyltrimethoxysilane; the amino-containing silane coupling agent is aminopropyltriethoxysilane; and the polyazidosilane coupling agent is polyazidosilane.

[0062] The silicone oil lubricant is dimethyl silicone oil; the PEG lubricant is PEG MO; and the hydrogenated vegetable oil lubricant is hydrogenated vegetable oil.

[0063] Unless otherwise specified, in the film forming agent, the average functionality of the phenolic epoxy resin is 3.5; and the average functionality of the modified epoxy resin is 2.

[0064] The phenolic epoxy resin is a phenol novolac epoxy aqueous dispersion; and the modified epoxy resin is an isocyanate-modified bisphenol A epoxy resin.

[0065] In Examples 7-10, the epoxy-containing silane coupling agent is 3-glycidoxypropyltrimethoxysilane; the amino-containing silane coupling agent is aminopropyltriethoxysilane; and the polyazidosilane coupling agent is polyazidosilane.

[0066] The silicone oil lubricant is dimethyl silicone oil; the PEG lubricant is PEG MO; and the hydrogenated vegetable oil lubricant is hydrogenated vegetable oil.

[0067] The average functionality of the phenolic epoxy resin in the film-forming agent is 3, and the average functionality of the modified epoxy resin is 1.5, unless otherwise specified.

[0068] The phenolic epoxy resin is o-methyl phenol novolac epoxy resin, and the modified epoxy resin is silicone blended modified epoxy resin.

[0069] Comparative Example 1

[0070] The components of the glass fiber surface treatment agent are specifically as follows:

[0071] Coupling agent A: vinyltrimethoxysilane (10%);

[0072] Coupling agent B: γ-methacryloxypropyltrimethoxysilane (4%);

[0073] Lubricant: PEG 800 (14.5%);

[0074] Film-forming agent: waterborne epoxy (66%);

[0075] Auxiliary: acetic acid (5.5%).

[0076] Comparative Example 2

[0077] The components of the glass fiber surface treatment agent are specifically as follows:

[0078] Coupling agent A: γ-methacryloxypropyltrimethoxysilane (6%);

[0079] Coupling agent B: 3-glycidoxypropyltrimethoxysilane (4%);

[0080] Lubricant: PPG 3000 (15%);

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

[0082] Auxiliary: citric acid (5%).

[0083] Comparative Examples 3 and 4 are examples of other content ratios, and the specific types of components selected are the same as in Examples 1-6. The performance test results of the glass fiber products, glass fiber fabric, and energy-absorbing, impact-resistant composite materials corresponding to Comparative Examples 1-4 are shown in Table 1.

[0084] Table 1 (continued) each embodiment ratio and product performance test results and comparative product performance test results

[0085]

[0086]

[0087] Table 1 (continued) each embodiment ratio and product performance test results and comparative product performance test results

[0088]

[0089] From the above description, it can be seen that the above-mentioned embodiments of the application achieve the following technical effects:

[0090] From the above formula test examples, it can be seen that by designing the components and component contents, we can obtain a required treatment agent, and each performance data is better than that of the comparative example; among them, the comprehensive effect of embodiments 3 and 4 is better. It can be seen that each component in the treatment agent can fully exert the advantages of each component when matched in a suitable ratio, and the more beneficial technical effects intended by the application are achieved.

[0091] In summary, the glass fiber fabric produced by the glass fiber treated by the glass fiber surface treatment agent of the application can control the interfacial bonding degree of the glass fiber in the unsaturated polyester resin, so that the reinforced composite material has certain integrity and is not easily damaged by low stress, and has good toughness and low rigidity, meeting the performance requirements of energy-absorbing and impact-resistant composite materials.

[0092] The above only describes the preferred embodiments of the application and is not intended to limit the application. For those skilled in the art, the application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the application shall be included in the protection scope of the application.

[0093] The above embodiments are only used to illustrate the technical solutions of the application, and not to limit it. Although the application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacements to some 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 application.

Claims

1. A glass fiber surface treatment agent characterized by, The effective component comprises 5.6-14.4% of coupling agent, 8.3-15.3% of lubricant, 65.31-84.15% of film forming agent, 0.05-0.83% of polymerization inhibitor and 1.90-4.16% of auxiliary agent by weight percentage of the effective component; The film forming agent is a combination of phenolic aldehyde epoxy resin and modified epoxy resin; The phenolic aldehyde epoxy resin accounts for 38.25-44.51% of the weight percentage of the effective component; the modified epoxy resin accounts for 20.8-45.9% of the weight percentage of the effective component, and the weight ratio of the phenolic aldehyde epoxy resin to the modified epoxy resin is 1:1.2-2.14:1; The coupling agent is a combination of coupling agent A, coupling agent B and coupling agent C; the coupling agent A is an epoxy-containing silane coupling agent, the coupling agent B is an amino-containing silane coupling agent, and the coupling agent C is a polyazidosilane-containing coupling agent; The coupling agent is a combination of coupling agent A, coupling agent B and coupling agent C; the coupling agent A accounts for 1.4-7.2% of the weight percentage of the effective component; the coupling agent B accounts for 1.4-5.4% of the weight percentage of the effective component, and the coupling agent C accounts for 1.8-2.8% of the weight percentage of the effective component; the weight ratio of the coupling agent A, the coupling agent B and the coupling agent C is 1:1:2-4:3:

1.

2. The glass fiber surface-treatment agent according to claim 1, characterized by, The effective component comprises 7.8-12.8% of coupling agent, 9.7-14.1% of lubricant, 68.6-80.1% of film forming agent, 0.14-0.62% of polymerization inhibitor and 2.31-3.88% of auxiliary agent by weight percentage of the effective component; the total amount of all components is 100%.

3. The glass fiber surfacing agent according to claim 1, wherein The phenolic aldehyde epoxy resin is one of bisphenol A phenolic aldehyde epoxy resin, phenol phenolic aldehyde epoxy aqueous dispersion and o-methyl phenol phenolic aldehyde epoxy resin; the average functionality of the phenolic aldehyde epoxy resin is 3-4; The modified epoxy resin is one of isocyanate modified bisphenol A epoxy resin, acrylic modified epoxy resin and organic silicon blended modified epoxy resin; the average functionality of the modified epoxy resin is 1-2.

4. The glass fiber surfacing agent according to claim 1, wherein The phenolic aldehyde epoxy resin is phenol phenolic aldehyde epoxy aqueous dispersion; the modified epoxy resin is isocyanate modified bisphenol A epoxy resin.

5. The glass fiber surfacing agent according to claim 1, wherein The lubricant is a combination of one or more of silicone oil, PEG and hydrogenated vegetable oil; the polymerization inhibitor is hydroquinone and / or p-tert-butyl hydroquinone; the auxiliary agent is organic acid.

6. A method for producing the glass fiber surface treatment agent according to any one of claims 1 to 5, characterized by, The method comprises the following steps: The glass fiber surface treatment agent is prepared by mixing the auxiliary agent, the coupling agent, the lubricant, the polymerization inhibitor, the film forming agent and water.

7. A glass fiber characterized in that, The glass fiber surface treatment agent is prepared by the preparation method of claim 6.

8. A glass fiber fabric characterized in that, The glass fiber is prepared by the preparation method of claim 7.

9. The glass fiber fabric of claim 8 is applied in energy absorption and impact resistance composite material.

Images