Glass fiber surface treatment agent and preparation method therefor, glass fiber and use

Abstract

The present application provides a glass fiber surface treatment agent and a preparation method therefor, a glass fiber, and a use. The glass fiber surface treatment agent comprises an effective component and water, wherein the effective component accounts for 4.6-10.3% of the weight percentage of the glass fiber surface treatment agent; and based on the weight percentage of the effective component, the effective component comprises: 6.3-19.6% of a silane coupling agent, 1.8-5.9% of a surfactant, 3.4-7.8% of a lubricant, 60.7-84.8% of a film-forming agent, and 2.9-6.4% of an auxiliary agent, wherein the film-forming agent is an acrylic acid-modified polyester resin and / or a silicone-modified polyester resin. A glass fiber produced by means of the glass fiber surface treatment agent of the present application has excellent use smoothness and glass fiber-reinforced plastic mechanical properties and meets various use requirements of food-grade glass fiber-reinforced plastic containers.

Description

Glass fiber surface treatment agent, preparation method thereof, glass fiber and application thereof

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on December 4, 2023, with application number 202311643135.5 and invention name “A glass fiber surface treatment agent, its preparation method, glass fiber and application”, the entire contents of which are incorporated by reference into this application. Technical Field

[0002] The present application relates to the technical field of glass fiber reinforced composite materials, and more specifically, to a glass fiber surface treatment agent and a preparation method thereof, glass fiber and applications, and especially to the application of glass fiber in the field of food-grade fiberglass reinforced plastic container products. Background Art

[0003] Food safety has always been a hot topic of public concern. In recent years, food safety incidents have occurred frequently, raising concerns among the public and prompting governments worldwide to proactively address the issue. Considering the supply chain as the primary barrier to mitigating and mitigating food safety risks, food safety testing agencies, as a crucial system for ensuring food safety, play a crucial role in preventing these risks. ACS, the French health certification body (Academia constiintei de sine), primarily develops safety and hygiene standards for products and materials such as metal, glass, and ceramics based on standards published by AFNOR (Association Francaise de Normalisation). Toxicity testing is used to determine whether materials and products release substances such as heavy metals, softeners, and stabilizers when placed in water. Organic matter testing is used to assess factors that affect material properties, including the taste, odor, and color of drinking water after contact. ACS is a globally recognized testing and certification organization for food contact piping and pressure vessels.

[0004] With the continuous emergence of new technologies, new materials, and new processes, the materials used for water supply pipelines are constantly being updated. FRP containers are increasingly favored by the market due to their corrosion resistance, light weight, high strength, easy transportation and installation, low friction coefficient, and strong conveying capacity. They are particularly advantageous when used for sewage transportation and water intake projects in water supply projects. However, the water distribution pipelines used for urban water supply are not yet mature enough. This field requires FRP products and their raw materials to meet ACS testing and certification requirements to prevent force majeure from causing microcracks in FRP containers, which can lead to the precipitation of some compounds into the water, affecting water quality and ultimately causing harm to human health. In particular, there are currently no products on the market that can meet these strict requirements for glass fiber raw materials, which has restricted the development of the FRP container industry.

[0005] Food-grade FRP containers have broad application prospects and can be used in the food industry, pharmaceutical industry, and other fields. In the food industry, food-grade FRP containers can replace traditional metal pipes, ensuring safe, hygienic, and economical transportation of beverages and food. In the pharmaceutical industry, FRP containers are non-toxic and hygienic, making them suitable for the transportation of pharmaceuticals and biological agents. Therefore, the market urgently needs a glass fiber that meets ACS testing and certification requirements, while also exhibiting excellent usability and FRP mechanical properties, meeting the requirements of urban water supply pipelines and promoting the high-quality development of the FRP pressure vessel industry.

[0006] Summary of the Invention

[0007] The main purpose of this application is to provide a glass fiber surface treatment agent and its preparation method, glass fiber and application. The glass fiber surface treatment agent of this application is safe and reliable, and the glass fiber prepared with it has excellent usability and glass fiber reinforced plastic mechanical properties.

[0008] In order to achieve the above-mentioned purpose, according to the first aspect of the present application, a glass fiber surface treatment agent is provided, which includes an effective component and water, wherein the effective component accounts for 4.6 to 10.3% by weight of the glass fiber surface treatment agent; calculated as a percentage by weight of the effective component, the effective component includes: 6.3 to 19.6% of a silane coupling agent, 1.8 to 5.9% of a surfactant, 3.4 to 7.8% of a lubricant, 60.7 to 84.8% of a film-forming agent, and 2.9 to 6.4% of an auxiliary agent; wherein the film-forming agent is an acrylic modified polyester resin and / or a silicone modified polyester resin.

[0009] Furthermore, the acrylic acid modified polyester resin includes: water-based acrylic acid modified saturated polyester resin and / or water-based acrylic acid modified unsaturated polyester resin; wherein the relative weight average molecular weight of the acrylic acid modified polyester resin is 3000-5000.

[0010] Furthermore, the organosilicon-modified polyester resin includes: organosilicon-modified saturated polyester resin and / or organosilicon-modified unsaturated polyester resin; wherein the relative weight average molecular weight of the organosilicon-modified polyester resin is 2000-4000.

[0011] Furthermore, the film-forming agent is a mixture of an acrylic acid-modified polyester resin and an organosilicon-modified polyester resin, wherein the mass ratio of the acrylic acid-modified polyester resin to the organosilicon-modified polyester resin is 1:3 to 6:1.

[0012] Furthermore, the surfactant is one or more of polyethylene oxide surfactants, ethoxylate surfactants, and acetylene glycol modified surfactants.

[0013] Furthermore, the silane coupling agent is an acyloxy-containing silane coupling agent and / or an amino-containing silane coupling agent;

[0014] When the silane coupling agent is an acyloxy-containing silane coupling agent and an amino-containing silane coupling agent, the mass ratio of the acyloxy-containing silane coupling agent to the amino-containing silane coupling agent is 1:1 to 8:1.

[0015] Furthermore, the silane coupling agent is an acyloxy-containing low-VOC silane coupling agent and / or an amino-containing low-VOC silane coupling agent.

[0016] Furthermore, the lubricant is one or more of fatty acids, fatty alcohols, fatty acid esters, and fatty acid triglycerides.

[0017] Furthermore, the auxiliary agent is citric acid and / or acetic acid.

[0018] In order to achieve the above-mentioned purpose, according to the second aspect of the present application, a method for preparing a glass fiber surface treatment agent as described in the first aspect is provided, which comprises: mixing an auxiliary agent, a silane coupling agent, a surfactant, a lubricant, a film-forming agent and water to obtain a glass fiber surface treatment agent.

[0019] According to a third aspect of the present application, a glass fiber is provided, which is obtained by treating the glass fiber surface treatment agent prepared by the preparation method of the second aspect.

[0020] According to a fourth aspect of the present application, there is provided an application of the glass fiber according to the third aspect in the field of food-grade fiberglass reinforced plastic container products.

[0021] The technical solution of the present application is applied to provide a glass fiber surface treatment agent, which comprises a silane coupling agent, a surfactant, a lubricant, a film-forming agent, an additive and water. The silane coupling agent and the film-forming agent are the main components of the glass fiber surface treatment agent of the present application, wherein the silane coupling agent mainly plays the role of repairing microcracks on the fiber surface, can form an effective and continuous protective layer on the surface of the glass fiber, improve the processing processability, and improve the physical and mechanical strength of the composite material; the film-forming agent mainly plays the role of improving the bundling and weather resistance of the glass fiber, improving the compatibility with the reinforcing resin and the physical and mechanical strength of the composite material; and compared with other types of film-forming agents such as epoxy resin, the biggest advantage of the acrylic modified polyester resin and silicone modified polyester resin selected in the present application is that they do not contain substances harmful to the human body such as ethylene oxide, and have stronger adhesion to the fiber surface, thereby giving the glass fiber excellent bundling, flexibility, weather resistance and water resistance; at the same time, they have good compatibility with food-grade unsaturated polyester resin and good solvent resistance, and can meet the performance requirements of food-grade pipes. The inventors discovered through experiments that when a glass fiber surface treatment agent is prepared by combining a silane coupling agent, a surfactant, a lubricant, a film-forming agent, an additive, and water according to the ratio of the present application and applied to glass fiber, the wear resistance, bundling properties, and mechanical properties of the glass fiber reinforced plastic are significantly better than those of glass fibers treated with other glass fiber surface treatment agents. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the present application will be clearly and completely described below in conjunction with the specific embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application. It should be noted that, in the absence of conflict, the embodiments in the present application and the features in the embodiments can be combined with each other in any way.

[0023] Some embodiments of the present application provide a glass fiber surface treatment agent, including effective components and water, wherein the effective components account for 4.6 to 10.3% by weight of the glass fiber surface treatment agent; calculated as a percentage by weight of the effective components, the effective components include: 6.3 to 19.6% of a silane coupling agent, 1.8 to 5.9% of a surfactant, 3.4 to 7.8% of a lubricant, 60.7 to 84.8% of a film-forming agent, and 2.9 to 6.4% of an auxiliary agent; wherein the film-forming agent is an acrylic modified polyester resin and / or a silicone modified polyester resin.

[0024] The glass fiber surface treatment agent of the present application comprises a silane coupling agent, a surfactant, a lubricant, a film-forming agent, an additive and water. The silane coupling agent and the film-forming agent are the main components of the glass fiber surface treatment agent of the present application, wherein the silane coupling agent mainly plays the role of repairing microcracks on the fiber surface, can form an effective and continuous protective layer on the surface of the glass fiber, improve the processing processability, and improve the physical and mechanical strength of the composite material; the film-forming agent mainly plays the role of improving the bundling and weather resistance of the glass fiber, improving the compatibility with the reinforcing resin and the physical and mechanical strength of the composite material; and compared with other types of film-forming agents such as epoxy resin, the biggest advantage of the acrylic modified polyester resin and silicone modified polyester resin selected in the present application is that they do not contain substances harmful to the human body such as ethylene oxide, and have stronger adhesion to the fiber surface, thereby making the glass fiber have excellent bundling, flexibility, weather resistance and water resistance, and at the same time have good compatibility with food-grade unsaturated polyester resin and good solvent resistance, meeting the performance requirements of food-grade pipelines. The inventors discovered through experiments that when a glass fiber surface treatment agent is prepared by combining a silane coupling agent, a surfactant, a lubricant, a film-forming agent, an additive, and water according to the ratio of the present application and applied to glass fiber, the wear resistance, bundling properties, and mechanical properties of the glass fiber reinforced plastic are significantly better than those of glass fibers treated with other glass fiber surface treatment agents.

[0025] In some preferred embodiments, a glass fiber surface treatment agent includes an effective component and water, wherein the effective component accounts for 5.2 to 9.8% by weight of the glass fiber surface treatment agent; calculated as a percentage by weight of the effective component, the effective component includes: 7.9 to 18.2% of a silane coupling agent, 2.8 to 5.1% of a surfactant, 4.2 to 6.9% of a lubricant, 62.1 to 80.5% of a film-forming agent, and 3.8 to 5.9% of an auxiliary agent; wherein the film-forming agent is an acrylic modified polyester resin and / or a silicone modified polyester resin.

[0026] The film-forming agent in this application is an acrylic-modified polyester resin and / or a silicone-modified polyester resin, which primarily improves the glass fiber's bundling and weather resistance, enhances its compatibility with the reinforcing resin, and improves the composite's physical and mechanical strength. The inventors have found that a film-forming agent dosage of 60.7% to 84.8% is optimal. In some preferred embodiments, the film-forming agent dosage is preferably 62.1% to 80.5%, more preferably 64% to 78%, which can further enhance the performance of the glass fiber surface treatment agent.

[0027] In some preferred embodiments, the acrylic acid-modified polyester resin includes: a water-based acrylic acid-modified saturated polyester resin and / or a water-based acrylic acid-modified unsaturated polyester resin. Preferably, the acrylic acid-modified polyester resin is a water-based acrylic acid-modified unsaturated polyester resin. Preferably, the acrylic acid-modified polyester resin has a relative weight-average molecular weight of 3,000 to 5,000. Using a glass fiber surface treatment agent containing these preferred acrylic acid-modified polyester resins is more advantageous for obtaining glass fibers with excellent bundling properties, salt spray resistance, boiling resistance, weather resistance, chemical resistance, and solvent resistance.

[0028] In some preferred embodiments, the organosilicon-modified polyester resin includes an organosilicon-modified saturated polyester resin and / or an organosilicon-modified unsaturated polyester resin. Furthermore, the organosilicon-modified polyester resin includes an organosilicon-modified polyester resin obtained by a condensation-dehydration reaction of a SiOH-containing siloxane and a hydroxyl-containing polyester resin and / or an organosilicon-modified polyester resin obtained by a condensation-dealcoholization reaction of a SiOR-containing siloxane and a hydroxyl-containing polyester resin. Preferably, the organosilicon-modified polyester resin is an organosilicon-modified saturated polyester resin. Preferably, the relative weight-average molecular weight of the organosilicon-modified polyester resin is 2,000 to 4,000. The use of a glass fiber surface treatment agent containing the preferred organosilicon-modified polyester resin described above is more conducive to obtaining glass fibers with excellent flexibility, heat resistance, weather resistance, corrosion resistance, electrical insulation, and bending resistance.

[0029] In some preferred embodiments, when the film-forming agent is an acrylic acid-modified polyester resin, the weight percentage of the film-forming agent in the effective component is 75-84.8%; or, when the film-forming agent is an organosilicon-modified polyester resin, the weight percentage of the film-forming agent in the effective component is 67-76%; or, when the film-forming agent is a mixture of an acrylic acid-modified polyester resin and an organosilicon-modified polyester resin, the weight percentage of the film-forming agent in the effective component is 60.7-72%. The above ratios are more conducive to improving the performance of the glass fiber surface treatment agent.

[0030] In some preferred embodiments, the film-forming agent is a mixture of an acrylic acid-modified polyester resin and an organosilicon-modified polyester resin, and the mass ratio of the acrylic acid-modified polyester resin to the organosilicon-modified polyester resin is 1:3 to 6:1. Preferably, the mass ratio of the acrylic acid-modified polyester resin to the organosilicon-modified polyester resin is 1:2 to 5:1. In some specific embodiments, the mass ratio of the acrylic acid-modified polyester resin to the organosilicon-modified polyester resin is 1:2 to 5.63:1. Exemplarily, the mass ratio of the acrylic acid-modified polyester resin to the organosilicon-modified polyester resin is 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 1:1.17, 1.99:1, 1.41:1, 1:1.94, 1:1.62, 1.23:1, and 5.63:1. In the present application, the combination of the acrylic acid-modified polyester resin and the organosilicon-modified polyester resin has a complementary and additive effect on performance. Since acrylic modified polyester resin has good bundling properties, its dosage should not be too high. Otherwise, the yarn will be too well bundled and difficult to spread out, and the penetration rate in the resin will be reduced, affecting the appearance and mechanical properties of FRP products. However, it should not be too low. Otherwise, the yarn will have poor bundling properties and poor smoothness of use, affecting production efficiency. Similarly, silicone modified polyester resin can give yarn excellent flexibility, but its bundling properties are average. Therefore, excessive dosage will cause the yarn to be soft and easy to disperse, which is not conducive to the winding molding process. Conversely, too little dosage will lead to excessive use of acrylic modified polyester resin, making the yarn hard, lacking flexibility and reprocessing processability. Practice has shown that within the above preferred ratio range, glass fiber products that meet production and processing requirements and can be used to prepare FRP products with excellent appearance and mechanical properties can be obtained.

[0031] In some preferred embodiments, the surfactant is one or more of a polyethylene oxide surfactant, an ethoxylate surfactant, and an acetylene glycol modified surfactant. Preferably, the surfactant is one or more of an ethoxylate surfactant and an acetylene glycol modified surfactant. In the present application, the mechanism of action of the surfactant is to utilize its own polar groups (i.e., hydrophilic groups) such as -OH and -O- to reduce the surface tension of the glass fiber surface treatment agent solution, making the glass fiber surface treatment agent easier to wet when in contact with the glass fiber, and enhancing the adsorption performance of the glass fiber surface treatment agent on the glass fiber surface, thereby making it easier to evenly coat the glass fiber surface. The surfactant of the present application is selected from one or more of a polyethylene oxide surfactant, an ethoxylate surfactant, and an acetylene glycol modified surfactant, which can reduce the surface tension of the glass fiber, improve the uniformity of the coating of the glass fiber surface treatment agent on the glass fiber surface, improve the dispersibility of the glass fiber surface treatment agent, make it easier to evenly disperse particles such as resin, prevent the precipitation and agglomeration of particles, and improve the stability of the liquid and the quality of the product. The inventors have found through research that a surfactant dosage of 1.8 to 5.9% is more suitable. If the surfactant is used too little, the coating effect of the glass fiber surface treatment agent on the glass fiber surface will be affected, resulting in more hairiness during use, affecting production efficiency and the performance of FRP products; while too much surfactant will affect the formation of glass fiber yarns, easily causing deformation such as ovalization and elongation, making it difficult to package and transport, and affecting normal use by customers. In some preferred embodiments, the amount of surfactant used is preferably 2.8-5.1%, more preferably 3.0-4.7%.

[0032] To further improve the processing properties of glass fiber and enhance the physical and mechanical strength of the composite material, in some preferred embodiments, the silane coupling agent is an acyloxy-containing silane coupling agent and / or an amino-containing silane coupling agent. Preferably, the silane coupling agent is an acyloxy-containing low-VOC silane coupling agent and / or an amino-containing low-VOC silane coupling agent. More preferably, the acyloxy-containing low-VOC silane coupling agent is an acyloxy-containing water-based modified silane coupling agent; illustratively, the acyloxy-containing low-VOC silane coupling agent is Degussa HYDROSIL 2929 and / or Degussa HYDROSIL 2990. Alternatively, the acyloxy-containing low-VOC silane coupling agent may be γ-methacryloyloxypropyltrimethoxysilane coupling agent. More preferably, the amino-containing low-VOC silane coupling agent is an amino-containing water-based modified silane coupling agent; illustratively, the amino-containing low-VOC silane coupling agent is one or more of Degussa silane coupling agent HYDROSIL 1151, Degussa silane coupling agent HYDROSIL 1153, Degussa silane coupling agent HYDROSIL 2627, Degussa silane coupling agent HYDROSIL 2776, and Degussa silane coupling agent HYDROSIL 2909. The amino-containing low-VOC silane coupling agent may also be N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane. The silane coupling agent of the present application has good wettability on the surface of glass fiber and high reactivity. When it reacts with glass fiber, the alkoxy group at one end after hydrolysis captures the silanol group produced by the decomposition of glass fiber and water to form a chemical bond, forming a molecular layer covering the silane coupling agent on the surface of the glass, repairing defects such as microcracks on the glass surface. At the same time, the hydrolysis of the silane coupling agent also produces another organic group that tends to the surface of the organic material and undergoes a cross-linking and curing chemical reaction with the film-forming agent, thereby completing the "bridging" process between the inorganic material (glass fiber) and the organic material (film-forming agent), ensuring the strength and wear resistance of the glass fiber. Specifically, the acyloxy group contained in the acyloxy-containing low-VOC silane coupling agent molecule of the present application is a functional group with a -OC(=O)-CH3 structure, which can undergo chemical cross-linking and physical entanglement with the polymer molecule, ultimately combining the glass fiber and other components of the treatment agent well, improving the flexibility and tensile strength of the material. The preferred amino-containing low-VOC silane coupling agent in this application is specifically a silane coupling agent containing two or more amino groups, and its molecular structure has two or more amino functional groups and two or more hydrolyzable alkoxy groups. This dual or multiple reactivity enables it to improve the bonding, adhesion and compatibility between inorganic materials (glass) and organic polymers (thermosetting resins) through a two-way chemical reaction, thereby improving the mechanical properties of resin-based composite materials or improving the bonding strength and water resistance of resin coatings.In some preferred embodiments, the content of the silane coupling agent in the present application is preferably 7.9 to 18.2%, more preferably 8.5 to 17.8%.

[0033] In some preferred embodiments, the silane coupling agent is a mixture of an acyloxy-containing silane coupling agent and an amino-containing silane coupling agent, wherein the mass ratio of the acyloxy-containing silane coupling agent to the amino-containing silane coupling agent is 1:1 to 8:1. The combination of the acyloxy-containing and amino-containing silane coupling agents can produce a synergistic effect, resulting in high strength, long shelf life, good compatibility with the target resin, i.e., unsaturated polyester resin, and significantly improved mechanical properties of the composite material. However, since amino-containing silane coupling agents are prone to yellowing reactions, the amount of the amino-containing silane coupling agent should not be excessive, and should not be greater than that of the acyloxy-containing silane coupling agent, otherwise the appearance quality of the glass fiber product will be affected. The amount of the amino-containing silane coupling agent should also not be too low, otherwise the expected synergistic effect will not be achieved. A mass ratio of the acyloxy-containing silane coupling agent to the amino-containing silane coupling agent of 1:1 to 8:1 is particularly suitable. Preferably, the mass ratio of the silane coupling agent containing an acyloxy group to the silane coupling agent containing an amino group is 1:1 to 6:1. In some specific embodiments, the mass ratio of the silane coupling agent containing an acyloxy group to the silane coupling agent containing an amino group is 1:1 to 4:1. Exemplarily, the mass ratio of the silane coupling agent containing an acyloxy group to the silane coupling agent containing an amino group is 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 1.39:1, 2.17:1, 2.22:1, 2.88:1, 2.57:1, or 3.32:1.

[0034] In order to reduce the wear and tear of glass fibers during production, improve the reprocessing performance of glass fibers, and reduce the generation of hairiness, in some preferred embodiments, the lubricant is one or more of fatty acids, fatty alcohols, fatty acid esters, and fatty acid triglycerides; specifically, one or more of saturated fatty acids, unsaturated fatty acids, hydroxy fatty acids, higher saturated fatty alcohols, carbonated glycerol fatty acid esters, and C12-18 acid triglycerides. The preferred lubricants in this application do not contain toxic substances, heavy metals, harmful volatile compounds, or other substances that are harmful to human health, and can reduce the frictional resistance of the friction pair, which is more conducive to improving the performance of the process. In some preferred embodiments, the content of the lubricant is preferably 4.2-6.9%, and more preferably 4.5-6.3%.

[0035] To improve the dispersibility of the silane coupling agent and achieve its bactericidal and mildew-proofing effects, in some preferred embodiments, the auxiliary agent is citric acid and / or acetic acid. For example, the auxiliary agent can be a combination of acetic acid and citric acid. Technicians should control the amount of auxiliary agent used in this application. If added in excessive amounts, on the one hand, some components of the glass fiber surface treatment agent may become ineffective, and on the other hand, acid corrosion may occur on the glass fiber. On the other hand, if used in too little amount, the silane coupling agent's dispersing effect and bactericidal and mildew-proofing effects cannot be fully achieved. In some preferred embodiments, the amount of auxiliary agent used is preferably 3.8-5.9%, and more preferably 4.0-5.5%.

[0036] Some embodiments of the present application provide a method for preparing the aforementioned glass fiber surface treatment agent, comprising: mixing an additive, a silane coupling agent, a surfactant, a lubricant, 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. The resulting glass fiber meets ACS testing and certification requirements, exhibits excellent usability and mechanical properties of fiberglass reinforced plastics (FRP), and meets the performance requirements of food-grade FRP containers.

[0037] In some preferred embodiments, the preparation method of the glass fiber surface treatment agent comprises:

[0038] 1S: Add water to the container, then add the additives, stir for 1 to 2 minutes, then add the silane coupling agent; continue stirring for 10 to 30 minutes until the silane coupling agent is evenly dispersed, the aqueous solution is clear, and there are no oil droplets on the surface;

[0039] 2S: Dilute the surfactant with water, stir evenly and add it to the container;

[0040] 3S: Dilute the lubricant with water, stir well and add it to the container;

[0041] 4S: Dilute the film-forming agent with water, stir well, and then add it to the container;

[0042] 5S: Add the remaining water to the container and stir evenly.

[0043] In step 1S, water is preferably added in an amount of 25 to 40% of the total weight of the glass fiber surface treatment agent;

[0044] In step 2S, water at 50-60°C is preferably used, which is 5-10 times the amount of the surfactant used, to dissolve and dilute the surfactant;

[0045] In step 3S, water at 50-60°C is preferably used, which is 2.3-3.3 times the amount of lubricant, to dissolve and dilute the lubricant;

[0046] In step 4S, the film-forming agent is preferably diluted with water at 15-25° C., which is 2-3 times the amount of the film-forming agent.

[0047] The above preparation method is only an example. Without violating the above preparation method provided in this application, technicians can adjust the order of several steps or the parameters of specific steps according to actual conditions to obtain the corresponding glass fiber surface treatment agent.

[0048] Some embodiments of the present application provide a glass fiber, which is obtained by treating the glass fiber surface treatment agent prepared by the aforementioned preparation method.

[0049] Some embodiments of the present application provide an application of the above-mentioned glass fiber in the field of food-grade fiberglass reinforced plastic container products.

[0050] The present application is further described in detail below with reference to specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in this application.

[0051] Examples 1 to 19

[0052] Table 1 records the formulations of Examples 1-19 and the performance test results of food-grade fiberglass reinforced plastic containers produced from their corresponding glass fiber products. Table 1 also records the performance test results of food-grade fiberglass reinforced plastic containers produced from the corresponding glass fiber products of Comparative Examples 1-2. The glass fiber surface treatment agents of Examples 1-19 and Comparative Examples 1-2 were applied to 2400 tex direct yarn, and the corresponding performance test results were obtained.

[0053] Comparative Example 1

[0054] The glass fiber surface treatment agent includes effective components and water, wherein the effective components account for 9.0% by weight of the glass fiber surface treatment agent. The effective components (by weight percentage) include:

[0055] Silane coupling agent: a combination of 3-aminopropyltriethoxysilane (2%) and γ-glycidyl ether propyltrimethoxysilane (6%);

[0056] Lubricant: PEGMO (6%);

[0057] Surfactant: polyethyleneimine (2.5%);

[0058] Film former: unmodified waterborne polyester resin (80.5%);

[0059] Additive: citric acid (3%).

[0060] Comparative Example 2

[0061] The glass fiber surface treatment agent includes an effective component and water, wherein the effective component accounts for 8.0% by weight of the glass fiber surface treatment agent. The effective components (in weight percentage) include:

[0062] Silane coupling agent: γ-glycidyl ether propyl trimethoxysilane (16%);

[0063] Lubricant: epoxy modified silicone oil emulsion (15%);

[0064] Film former: bisphenol A epoxy resin emulsion (65%);

[0065] Auxiliary agent: glacial acetic acid (4%).

[0066] Table 1

[0067] Table 1 (continued)

[0068] Table 1 (continued)

[0069] In Examples 1-19, the acyloxy-containing silane coupling agent is Degussa HYDROSIL 2929; the amino-containing silane coupling agent is Degussa HYDROSIL 1151 (3-aminopropyltrialkoxysilane hydrolyzate). In Examples 1-19, the fatty acid triglyceride is a C12-18 acid triglyceride. In Examples 1-19, the polyethylene oxide surfactant is a polyethylene glycol derivative, the ethoxylate surfactant is an ethoxylated nonionic surfactant, and the acetylene glycol-modified surfactant is an acetylene glycol polyoxyethylene ether. In Examples 1-19, the relative weight-average molecular weight of the acrylic acid-modified polyester resin in the film-forming agent is 4100±500, and the relative weight-average molecular weight of the silicone-modified polyester resin is 2800±500. In Examples 1 to 19, the acrylic acid-modified polyester resin is a water-based acrylic acid-modified unsaturated polyester resin; and the organosilicon-modified polyester resin is an organosilicon-modified saturated polyester resin prepared by condensation-dehydration reaction of SiOH-containing siloxane and hydroxyl-containing polyester resin.

[0070] The data in Table 1 show that, compared with the glass fiber surface treatment agents of Comparative Examples 1-2, the glass fibers prepared using the glass fiber surface treatment agents of the present application (Examples 1-19) have less hairiness, and the FRP containers prepared using the glass fibers of the present application have higher axial tensile strength and interlaminar shear strength. Furthermore, the inventors also used glass fiber surface treatment agents of other comparative examples for comparison with the glass fiber surface treatment agents of the present application (Examples 1-19). The film-forming agents and coupling agents used in these other comparative examples differed from those of the present application. The performance of the glass fibers and FRP containers prepared using the glass fiber surface treatment agents of these other comparative examples was also significantly inferior to that of the glass fiber surface treatment agents of Examples 1-19 of the present application.

[0071] In summary, the glass fiber surface treatment agent formulation and preparation process provided herein are scientifically sound. The components of the glass fiber surface treatment agent work synergistically, fully leveraging their respective advantages and achieving a more beneficial technical effect. Glass fiber produced using the glass fiber surface treatment agent of this application exhibits excellent usability and mechanical properties of fiberglass reinforced plastics (FRP). Furthermore, the agent can pass ACS testing and certification, meeting the performance requirements of food-grade FRP containers.

[0072] The above description is merely a preferred embodiment of the present application and is not intended to limit the present application. Various modifications and variations are possible for those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application. Industrial Applicability

[0073] The glass fiber surface treatment agent of the present application uses acrylic modified polyester resin and silicone modified polyester resin as film-forming agents. It does not contain substances harmful to the human body such as ethylene oxide and has stronger adhesion to the fiber surface, thereby giving the glass fiber excellent bundling, flexibility, weather resistance and water resistance. At the same time, it has good compatibility with food-grade unsaturated polyester resin and good solvent resistance, and can meet the performance requirements of food-grade pipes. According to the ratio of the present application, a silane coupling agent, a surfactant, a lubricant, a film-forming agent, an auxiliary agent and water are combined to prepare a glass fiber surface treatment agent. After applying it to glass fiber, the wear resistance, bundling and mechanical properties of the glass fiber are significantly better than those of glass fibers treated with other glass fiber surface treatment agents. In addition, the product can pass ACS testing and certification and meet the performance requirements of food-grade glass fiber reinforced plastic containers.

Claims

1. A glass fiber surface treatment agent, characterized in that: The invention comprises effective components and water, wherein the weight percentage of the effective components in the glass fiber surface treatment agent is 4.6-10.3%; and the effective components comprise: Silane coupling agent 6.3-19.6%, surfactant 1.8-5.9%, lubricant 3.4-7.8%, film former 60.7-84.8%, additive 2.9-6.4%; Wherein, the film-forming agent is acrylic acid-modified polyester resin and / or silicone-modified polyester resin.

2. The glass fiber surface treatment agent according to claim 1, characterized in that: The acrylic acid modified polyester resin includes: water-based acrylic acid modified saturated polyester resin and / or water-based acrylic acid modified unsaturated polyester resin; wherein the relative weight average molecular weight of the acrylic acid modified polyester resin is 3000-5000.

3. The glass fiber surface treatment agent according to claim 1, characterized in that: The organosilicon-modified polyester resin includes: organosilicon-modified saturated polyester resin and / or organosilicon-modified unsaturated polyester resin; wherein the relative weight average molecular weight of the organosilicon-modified polyester resin is 2000-4000.

4. The glass fiber surface treatment agent according to claim 1, characterized in that: The film-forming agent is a mixture of an acrylic acid-modified polyester resin and an organosilicon-modified polyester resin, wherein the mass ratio of the acrylic acid-modified polyester resin to the organosilicon-modified polyester resin is 1:3 to 6:

1.

5. The glass fiber surface treatment agent according to claim 1, characterized in that: The surfactant is one or more of a polyethylene oxide surfactant, an ethoxylate surfactant, and an acetylene glycol modified surfactant.

6. The glass fiber surface treatment agent according to claim 1, characterized in that: The silane coupling agent is an acyloxy-containing silane coupling agent and / or an amino-containing silane coupling agent.

7. The glass fiber surface treatment agent according to claim 1, characterized in that: The silane coupling agent is a mixture of an acyloxy-containing silane coupling agent and an amino-containing silane coupling agent, and the mass ratio of the acyloxy-containing silane coupling agent to the amino-containing silane coupling agent is 1:1 to 8:

1.

8. The glass fiber surface treatment agent according to claim 1, characterized in that: The silane coupling agent is an acyloxy-containing low-VOC silane coupling agent and / or an amino-containing low-VOC silane coupling agent.

9. The glass fiber surface treatment agent according to claim 1, characterized in that: The lubricant is one or more of fatty acids, fatty alcohols, fatty acid esters, and fatty acid triglycerides.

10. The glass fiber surface treatment agent according to claim 1, characterized in that: The auxiliary agent is citric acid and / or acetic acid.

11. A method for preparing a glass fiber surface treatment agent according to any one of claims 1 to 10, characterized in that: include: The auxiliary agent, silane coupling agent, surfactant, lubricant, film-forming agent and water are mixed to obtain the glass fiber surface treatment agent.

12. A glass fiber, characterized in that: The glass fiber surface treatment agent is obtained by treating the glass fiber surface treatment agent obtained by the preparation method according to claim 11.

13. Use of the glass fiber according to claim 12 in the field of food-grade glass fiber reinforced plastic container products.

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