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

Abstract

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

Description

Technical Field

[0001] 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 in particular to applications of glass fiber in the field of food-grade glass fiber reinforced plastic container products. Background Art

[0002] Food safety has always been a hot topic of social concern. In recent years, food safety incidents have occurred frequently, and more and more people have begun to pay attention to food safety issues. Governments of various countries have also actively taken measures to respond. Considering that the supply chain is the first barrier to avoid and reduce food safety risks, as one of the important systems to ensure food safety, food safety testing agencies play an important role in preventing food safety risks. ACS is a French health certification agency, and its full name is (Academia constiintei de sine). It mainly formulates corresponding safety and health standards for metal glass and ceramic products and materials based on the standards issued by AFNOR (Association Francaise deNormalisation). Among them, toxicity testing is used to detect whether materials and products are placed in water to separate out heavy metals, softeners and stabilizers, etc., and organic matter testing is used to detect the characteristics that affect the materials, including the taste, smell and color of the water quality after the products come into contact with drinking water. It is a global authoritative testing and certification agency in the field of food contact pipes and pressure vessels.

[0003] With the continuous emergence of new technologies, new materials, and new processes, the materials of water supply pipelines are constantly updated. FRP containers are increasingly favored by the market because of their corrosion resistance, light weight, high strength, convenient transportation and installation, low friction coefficient, and strong transportation capacity. They are undoubtedly very advantageous when used for sewage transportation and water intake projects in water supply projects. However, the water supply and 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 factors from causing micro cracks in FRP containers, causing some compounds to precipitate and float in the water, affecting water quality, and ultimately causing damage to human health. In particular, there are no products on the market that can meet the above requirements, which restricts the development of the FRP container industry.

[0004] 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 to achieve the safety, hygiene and economic benefits of beverage and food transportation; in the pharmaceutical industry, FRP containers have the advantages of being non-toxic and hygienic, and can be used for the transportation of pharmaceuticals and biological agents. Therefore, the market urgently needs a glass fiber that meets the ACS testing and certification requirements, and at the same time has excellent smoothness of use and FRP mechanical properties, meets the requirements of urban water supply and distribution pipelines, and promotes the high-quality development of the FRP pressure vessel industry. Summary of the invention

[0005] The main purpose of the present application is to provide a glass fiber surface treatment agent and a preparation method thereof, glass fiber and application. The glass fiber surface treatment agent of the present application is safe and reliable, and the glass fiber prepared therefrom has excellent smoothness of use and mechanical properties of glass fiber reinforced plastics.

[0006] 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 effective components and water, wherein the weight percentage of the effective components in the glass fiber surface treatment agent is 4.6-10.3%; calculated by weight percentage of the effective components, the effective components include: 6.3-19.6% of silane coupling agent, 1.8-5.9% of surfactant, 3.4-7.8% of lubricant, 60.7-84.8% of film-forming agent, and 2.9-6.4% of auxiliary agent; wherein the film-forming agent is acrylic modified polyester resin and / or silicone modified polyester resin.

[0007] 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.

[0008] 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.

[0009] 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.

[0010] Furthermore, the surfactant is one or more of polyethylene oxide surfactants, ethoxylate surfactants, and acetylene glycol-modified surfactants.

[0011] Furthermore, the silane coupling agent is an acyloxy-containing silane coupling agent and / or an amino-containing silane coupling agent;

[0012] 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.

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

[0014] Furthermore, the lubricant is one or more of fatty acids, fatty alcohols, fatty acid esters, and fatty acid triglycerides.

[0015] Furthermore, the auxiliary agent is citric acid and / or acetic acid.

[0016] 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.

[0017] 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.

[0018] According to a fourth aspect of the present application, there is provided an application of the glass fiber of the third aspect in the field of food-grade glass fiber reinforced plastic container products.

[0019] The technical solution of the present application is applied to provide a glass fiber surface treatment agent, which includes a silane coupling agent, a surfactant, a lubricant, a film-forming agent, an auxiliary agent and water. Silane coupling agent and 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 a role in repairing microcracks on the fiber surface, can form an effective and continuous protective layer on the surface of the glass fiber, improve the processing technology, and improve the physical and mechanical strength of the composite material; wherein the film-forming agent mainly plays a role in 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. Compared with other types of film-forming agents such as epoxy resin, the biggest advantage of the film-forming agent 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 on the fiber surface, so that the glass fiber has excellent bundling, flexibility, weather resistance and water resistance, and at the same time has good compatibility with food-grade unsaturated polyester resin and good solvent resistance, meeting the performance requirements of food-grade pipelines. The inventors have found 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 are significantly better than those of other glass fiber surface treatment agents. DETAILED DESCRIPTION

[0020] 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 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 the field without making creative work are within the scope of protection of the present 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 arbitrarily combined with each other.

[0021] Some embodiments of the present application provide a glass fiber surface treatment agent, including effective components and water, wherein the weight percentage of the effective components in the glass fiber surface treatment agent is 4.6-10.3%; calculated by weight percentage of the effective components, the effective components include: 6.3-19.6% of silane coupling agent, 1.8-5.9% of surfactant, 3.4-7.8% of lubricant, 60.7-84.8% of film-forming agent, and 2.9-6.4% of auxiliary agent; wherein the film-forming agent is acrylic modified polyester resin and / or silicone modified polyester resin.

[0022] 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. Silane coupling agent and 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 a role in repairing microcracks on the fiber surface, can form an effective and continuous protective layer on the surface of the glass fiber, improve the processing technology, and improve the physical and mechanical strength of the composite material; wherein the film-forming agent mainly plays a role in 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. Compared with other types of film-forming agents such as epoxy resin, the biggest advantage of the film-forming agent 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 on the fiber surface, so that the glass fiber has excellent bundling, flexibility, weather resistance and water resistance, and at the same time has good compatibility with food-grade unsaturated polyester resin, good solvent resistance, and meets the performance requirements of food-grade pipelines. The inventors have found 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 are significantly better than those of other glass fiber surface treatment agents.

[0023] In some preferred embodiments, a glass fiber surface treatment agent includes effective components and water, wherein the effective components account for 5.2-9.8% by weight of the glass fiber surface treatment agent; calculated by weight percentage of the effective components, the effective components include: 7.9-18.2% of silane coupling agent, 2.8-5.1% of surfactant, 4.2-6.9% of lubricant, 62.1-80.5% of film-forming agent, and 3.8-5.9% of auxiliary agent; wherein the film-forming agent is acrylic modified polyester resin and / or silicone modified polyester resin.

[0024] The film-forming agent in the present application is an acrylic modified polyester resin and / or a silicone modified polyester resin. The film-forming agent mainly plays a role in 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. The inventors have found through research that the amount of the film-forming agent is more suitable when it is 60.7-84.8%. In some preferred embodiments, the amount of the film-forming agent is preferably 62.1-80.5%, more preferably 64-78%, which can further improve the performance of the glass fiber surface treatment agent.

[0025] In some preferred embodiments, 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. Preferably, the acrylic acid modified polyester resin is a water-based acrylic acid modified unsaturated polyester resin. Preferably, the relative weight average molecular weight of the acrylic acid modified polyester resin is 3000 to 5000. The use of the glass fiber surface treatment agent containing the above preferred acrylic acid modified polyester resin is more conducive to obtaining glass fibers with excellent bundling, salt spray resistance, boiling resistance, weather resistance, chemical resistance, and solvent resistance.

[0026] In some preferred embodiments, the organosilicon-modified polyester resin includes an organosilicon-modified saturated polyester resin and / or an organosilicon-modified unsaturated polyester resin. Further, the organosilicon-modified polyester resin includes an organosilicon-modified polyester resin obtained by condensation-dehydration reaction of SiOH-containing siloxane and hydroxyl-containing polyester resin and / or an organosilicon-modified polyester resin obtained by condensation-dealcoholization reaction of SiOR-containing siloxane and 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 2000 to 4000. The use of a glass fiber surface treatment agent containing the above-mentioned preferred organosilicon-modified polyester resin is more conducive to obtaining glass fibers with excellent flexibility, heat resistance, weather resistance, corrosion resistance, electrical insulation and bending resistance.

[0027] 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%. According to the above ratio, the performance of the glass fiber surface treatment agent is more improved.

[0028] In some preferred embodiments, the film-forming agent is a mixture of an acrylic modified polyester resin and an organosilicon modified polyester resin, and the mass ratio of the acrylic modified polyester resin to the organosilicon modified polyester resin is 1:3 to 6:1. Preferably, the mass ratio of the acrylic modified polyester resin to the organosilicon modified polyester resin is 1:2 to 5:1. Exemplarily, the mass ratio of the acrylic modified polyester resin to the organosilicon modified polyester resin is 1:2, 1:1, 2:1, 3:1, 4:1, 5:1. In the present application, the use of acrylic modified polyester resin and organosilicon modified polyester resin plays a role of complementary and additive performance. Because of its good bundling property, the amount of acrylic modified polyester resin should not be too much, otherwise it will cause the yarn to be too well bundled, not easy to spread, and the penetration speed in the resin will be reduced, affecting the appearance and mechanical properties of the glass fiber reinforced plastic products; but it should not be too little, otherwise the yarn bundling property is poor, the smoothness of use is not good, and the production efficiency is affected. Similarly, silicone-modified polyester resin gives yarn excellent flexibility, but general bundling properties, so excessive use will result in soft yarn, easy dispersion, and unfavorable winding molding process, while too little use will result in excessive use of acrylic-modified polyester resin, resulting in hard yarn, lack of flexibility and reprocessing processability. Practice has shown that within the above preferred ratio range, glass fiber products that meet production and processing processability and can prepare glass fiber reinforced plastic products with excellent appearance and mechanical properties can be obtained.

[0029] 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 use 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, so that the glass fiber surface treatment agent is easier to wet when in contact with the glass fiber, and enhance the adsorption performance of the glass fiber surface treatment agent on the glass fiber surface, so that it is easier to be evenly coated on 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 glass fiber surface treatment agent on the glass fiber surface, improve the dispersibility of the glass fiber surface treatment agent, make it easier to disperse particles such as resins, prevent the precipitation and agglomeration of particles, and improve the stability of the liquid and the quality of the product. The inventor found through research that the amount of surfactant is more suitable when it is 1.8 to 5.9%. If the surfactant is used too little, it will affect the coating effect of the glass fiber surface treatment agent on the glass fiber surface, and more hairiness will be generated during use, affecting the production efficiency and the performance of the glass fiber reinforced plastic products; while too much surfactant will affect the yarn forming of the glass fiber, which is prone to deformation such as elliptical and long height, making it difficult to package and transport, and affecting the normal use of customers. In some preferred embodiments, the amount of surfactant is preferably 2.8-5.1%, more preferably 3.0-4.7%.

[0030] In order to further improve the processing properties of glass fiber and improve 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 silane coupling agent HYDROSIL 2929 and / or Degussa silane coupling agent HYDROSIL 2990, and the acyloxy-containing low-VOC silane coupling agent can also be γ-methacryloxypropyl trimethoxy silane 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 can 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 reaction activity. When it acts on glass fiber, the alkoxy group at one end after hydrolysis takes away 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 surface of the glass, and at the same time, the hydrolysis of the silane coupling agent will also produce another organic group tending to the surface of the organic material, and undergo 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, and finally well combines the glass fiber and other components of the treatment agent, thereby improving the flexibility and tensile strength of the material. The preferred amino-containing low-VOC silane coupling agent of the present 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 combination, 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%, and more preferably 8.5 to 17.8%.

[0031] 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 silane coupling agent and the amino-containing silane coupling agent can produce a synergistic effect, and the treated glass fiber has high strength, a long storage period, good compatibility with the target resin, i.e., the unsaturated polyester resin, and can significantly improve the mechanical properties of the composite material. However, since the amino-containing silane coupling agent is very prone to yellowing reaction, the amount of the amino-containing silane coupling agent should not be too much, and should not be higher than the amount of the acyloxy-containing silane coupling agent, otherwise it will affect the appearance quality of the glass fiber product. The amount of the amino-containing silane coupling agent should not be too little, otherwise the expected synergistic effect cannot be achieved. When the mass ratio of the acyloxy-containing silane coupling agent to the amino-containing silane coupling agent is 1:1 to 8:1, it is more suitable. Preferably, the mass ratio of the silane coupling agent containing acyloxy group to the silane coupling agent containing amino group is 1: 1 to 6: 1. Exemplarily, the mass ratio of the silane coupling agent containing acyloxy group to the silane coupling agent containing amino group is 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1.

[0032] In order to reduce the wear and tear of glass fiber during the production process, improve the reprocessing performance of glass fiber, 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. The above-mentioned preferred lubricants in this application do not contain substances harmful to human health such as toxic substances, heavy metals, and harmful volatile compounds, and reduce the friction resistance of the friction pair, which is more conducive to improving the use process performance. In some preferred embodiments, the content of the lubricant is preferably 4.2-6.9%, and more preferably 4.5-6.3%.

[0033] In order to improve the dispersibility of the silane coupling agent and to achieve the bactericidal and mildew-proof effects, in some preferred embodiments, the auxiliary agent is citric acid and / or acetic acid. Exemplarily, the auxiliary agent can be a composition of acetic acid and citric acid. The technician should control the amount of auxiliary agent used in this application. If the amount added is too much, on the one hand, it may cause some components in the glass fiber surface treatment agent to fail, and on the other hand, it will cause acid corrosion to the glass fiber; and too little use cannot fully achieve the dispersing effect of the silane coupling agent and the bactericidal and mildew-proof effects. In some preferred embodiments, the amount of auxiliary agent is preferably 3.8-5.9%, more preferably 4.0-5.5%.

[0034] Some embodiments of the present application provide a method for preparing the above-mentioned glass fiber surface treatment agent, comprising: 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. 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 meets the ACS test certification requirements, has excellent smoothness of use and glass fiber reinforced plastic mechanical properties, and meets the performance requirements of food-grade glass fiber reinforced plastic containers.

[0035] In some preferred embodiments, the preparation method of the glass fiber surface treatment agent comprises:

[0036] 1S: Add water to the container, then add the additive, 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 is no oil droplets on the surface;

[0037] 2S: Dilute the surfactant with water, stir evenly and add it into the container;

[0038] 3S: Dilute the lubricant with water, stir well and add it into the container;

[0039] 4S: Dilute the film former with water, stir evenly and add into the container;

[0040] 5S: Add excess water to the container and stir evenly.

[0041] Wherein, in step 1S, preferably 25 to 40% of water is added based on the total weight of the glass fiber surface treatment agent;

[0042] Wherein, in step 2S, preferably 5 to 10 times the amount of surfactant used, water at 50 to 60°C is used to dissolve and dilute the surfactant;

[0043] Among them, in step 3S, preferably 2.3 to 3.3 times the amount of lubricant used, water at 50 to 60°C is used to dissolve and dilute the lubricant;

[0044] Among them, in step 4S, it is preferred that 2 to 3 times the amount of the film-forming agent be used, with water at 15 to 25° C. to dilute the film-forming agent.

[0045] The above preparation method is only used as an example. Without violating the above preparation method provided in this application, technicians can adjust the sequence of several steps or the parameters of specific steps according to actual conditions to obtain the corresponding glass fiber surface treatment agent.

[0046] Some embodiments of the present application provide a glass fiber, which is obtained by treating the glass fiber surface treatment agent obtained by the aforementioned preparation method.

[0047] Some embodiments of the present application provide an application of the above-mentioned glass fiber in the field of food-grade fiberglass container products.

[0048] The present application is further described in detail below in conjunction with specific embodiments. These embodiments should not be construed as limiting the scope of protection claimed in the present application.

[0049] Examples 1 to 19

[0050] Table 1 records the performance test results of food-grade FRP containers produced by the glass fiber products corresponding to Examples 1 to 19, and also records the performance test results of food-grade FRP containers produced by the glass fiber products corresponding to Comparative Examples 1 to 2. The glass fiber surface treatment agents of Examples 1 to 19 and Comparative Examples 1 to 2 were applied to 2400tex direct yarns, respectively, and the corresponding performance test results were obtained.

[0051] Comparative Example 1

[0052] 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, and the effective components (by weight percentage) include:

[0053] Silane coupling agent: a combination of 3-aminopropyltriethoxysilane (2%) and γ-glycidyl ether propyltrimethoxysilane (6%);

[0054] Lubricant: PEGMO (6%);

[0055] Surfactant: polyethyleneimine (2.5%);

[0056] Film former: unmodified waterborne polyester resin (80.5%);

[0057] Additive: citric acid (3%).

[0058] Comparative Example 2

[0059] The glass fiber surface treatment agent comprises effective components and water, wherein the effective components account for 8.0% by weight of the glass fiber surface treatment agent, and the effective components (by weight percentage) include:

[0060] Silane coupling agent: γ-glycidyl ether propyl trimethoxysilane (16%);

[0061] Lubricant: epoxy modified silicone oil emulsion (15%);

[0062] Film former: bisphenol A epoxy resin emulsion (65%);

[0063] Auxiliary agent: glacial acetic acid (4%).

[0064] Table 1

[0065]

[0066] Table 1 (continued)

[0067]

[0068] Table 1 (continued)

[0069]

[0070] In Examples 1 to 19, the silane coupling agent containing acyloxy groups may be Degussa silane coupling agent HYDROSIL2929; the silane coupling agent containing amino groups may be Degussa silane coupling agent HYDROSIL 1151 (3-aminopropyltrialkoxysilane hydrolyzate). In Examples 1 to 19, the fatty acid triglyceride may be C12-18 acid triglyceride. In Examples 1 to 19, the polyethylene oxide surfactant may be a derivative of polyethylene glycol, the ethoxylate surfactant may be an ethoxylated nonionic surfactant, and the acetylene glycol modified surfactant may be an acetylene glycol polyoxyethylene ether. In Examples 1 to 19, the relative weight average molecular weight of the acrylic acid modified polyester resin in the film-forming agent may be 4100±500, and the relative weight average molecular weight of the silicone modified polyester resin may be 2800±500. In Examples 1 to 19, the acrylic acid-modified polyester resin may be a water-based acrylic acid-modified unsaturated polyester resin; and the silicone-modified polyester resin may be a silicone-modified saturated polyester resin prepared by condensation-dehydration reaction of SiOH-containing siloxane and hydroxyl-containing polyester resin.

[0071] It can be seen from the data in Table 1 that, compared with the glass fiber surface treatment agents of comparative examples 1 to 2, the glass fiber prepared using the glass fiber surface treatment agents of the present application (Examples 1 to 19) has less hairiness, and the glass fiber reinforced plastic container prepared using the glass fiber of the present application has higher pipeline axial tensile strength and interlaminar shear strength. In addition, the inventors also used glass fiber surface treatment agents of other comparative examples to compare with the glass fiber surface treatment agents of the present application (Examples 1 to 19). The film-forming agents and coupling agents used in the other comparative examples are different from the film-forming agents and coupling agents of the present application. Compared with the glass fiber surface treatment agents of Examples 1 to 19 of the present application, the performance of the glass fiber and the glass fiber reinforced plastic container prepared by the glass fiber surface treatment agents of other comparative examples is also significantly worse.

[0072] In summary, the formula and preparation process of the glass fiber surface treatment agent provided by the present application are scientific and reasonable, and the components in the glass fiber surface treatment agent cooperate with each other, giving full play to the advantages and characteristics of each component, achieving the more beneficial technical effect that the present application wants to achieve. The glass fiber produced by the glass fiber surface treatment agent of the present application has excellent smoothness of use and mechanical properties of glass fiber reinforced plastics, and can pass ACS test certification to meet the performance requirements of food-grade glass fiber reinforced plastic containers.

[0073] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A glass fiber surface treatment agent, characterized in that: It comprises effective components and water, wherein the effective components account for 4.6-10.3% by weight of the glass fiber surface treatment agent; Calculated by weight percentage of effective components, the effective components include: silane coupling agent 6.3~19.6%, surfactant 1.8~5.9%, lubricant 3.4~7.8%, film former 67.2~84.8%, auxiliary agent 2.9~6.4%; Wherein, the film-forming agent is acrylic acid-modified polyester resin and / or silicone-modified polyester resin; The acrylic acid modified polyester resin is a water-based acrylic acid modified unsaturated polyester resin; wherein the relative weight average molecular weight of the acrylic acid modified polyester resin is 3600-4600; The organosilicon-modified polyester resin is an organosilicon-modified saturated polyester resin obtained by condensation-dehydration reaction of SiOH-containing siloxane and hydroxyl-containing polyester resin; wherein the relative weight-average molecular weight of the organosilicon-modified polyester resin is 2300-3300.

2. 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 1:3-6:

1.

3. 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.

4. 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; 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.

5. 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.

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

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

8. A method for preparing a glass fiber surface treatment agent as claimed in any one of claims 1 to 7, 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.

9. 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 8.

10. Use of the glass fiber according to claim 9 in the field of food-grade glass fiber reinforced plastic container products.

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