A glass fiber sizing agent, product and application

Abstract

The present application provides a glass fiber sizing agent. The components contained in the glass fiber sizing agent and the mass percentages of each component in the total mass of the sizing agent are as follows: silane coupling agent 0.1 - 0.5%, lubricant 0.1 - 0.5%, film-forming agent 4.0 - 26.0%, defoaming agent 0.1 - 2.0%, antistatic agent 0.1 - 2.0%, pH value regulator 0.1 - 1.0%, and water 68 - 95.5%. Among them, the film-forming agent includes unsaturated polyester emulsion, polyurethane emulsion, and epoxy emulsion. The sizing agent of the present application is coated on the surface of glass fiber. By changing the physical and chemical properties of the glass fiber surface, it can not only improve the fluidity and fiber opening property of the yarn, but also enhance the compatibility between the glass fiber and the matrix resin. The glass fiber product coated with this sizing agent has excellent fluidity and fiber opening property. The SMC material for integral bathroom made therefrom has the characteristics of uniform glass fiber distribution, smooth product surface, excellent boiling water resistance, and high product yield.

Description

Technical Field

[0001] This application relates to the technical field of glass fiber sizing agents, and particularly relates to a glass fiber sizing agent, a product, and an application. Background Art

[0002] In the early days, traditional sanitary wares mostly used ceramic materials, which were heavy, prone to cracking, and easy to leak. Now, the more common practice is to use the SMC (Sheet Molding Compound) process to prepare integral sanitary wares. This method has the advantages of integral molding for anti-leakage, lightness, beauty, high strength, safety, environmental protection, and long service life.

[0003] Currently, conventional glass fibers for SMC can meet the requirements of general products. However, for SMC materials used in integral sanitary wares, which are home building materials, special attention needs to be paid to surface properties and water-boiling resistance. Therefore, higher requirements are placed on the fluidity of glass fibers and the water-boiling resistance of products. Glass fiber yarns coated with conventional sizing agents for SMC glass fibers have poor fluidity and fiber-opening properties. Poor glass fiber flow can easily cause problems such as material shortage in products and uneven distribution of glass fibers, and it can also lead to glass fiber patterns on the surface of products, affecting aesthetics and comfort. Even quality problems such as blistering and breakage after water boiling may occur. Summary of the Invention

[0004] The purpose of this application is to address the above problems by providing a glass fiber sizing agent. When this sizing agent is coated on the surface of glass fibers, it can change the physical and chemical properties of the glass fiber surface, not only improving the fluidity and fiber-opening properties of the yarn, but also enhancing the compatibility between the glass fiber and the matrix resin. The glass fiber product coated with this sizing agent has excellent fluidity and fiber-opening properties. The SMC material for integral sanitary wares made from it has the characteristics of uniform glass fiber distribution, smooth product surface, excellent water-boiling resistance, and high product yield.

[0005] To achieve the above technical effects, this application adopts the following technical solutions:

[0006] According to the first aspect of this application, a glass fiber sizing agent is provided. The sizing agent contains a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator, and water. The mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows:

[0007]

[0008] Among them, the film-forming agent contains an unsaturated polyester emulsion, a polyurethane emulsion, and an epoxy emulsion.

[0009] Among them, the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent.

[0010] Among them, the percentage of the mass of each component of the sizing agent in the total mass of the sizing agent is expressed as follows:

[0011]

[0012] Among them, the mass of the unsaturated polyester emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 8.0% of the total mass of the sizing agent.

[0013] Among them, the unsaturated polyester emulsion is an isophthalic unsaturated polyester emulsion; the polyurethane emulsion is an aqueous polyurethane emulsion; the epoxy emulsion is a bisphenol A epoxy resin emulsion.

[0014] Among them, the defoaming agent is a polyether defoaming agent; among them, the polyether defoaming agent is at least one of polyaliphatic ether, polyaryl ether and polyether ketone.

[0015] Among them, the silane coupling agent is a mixture of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and the mass ratio of γ-glycidoxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane is 4:1 - 2:1.

[0016] Among them, the lubricant is a mixture of a polyethyleneimine polyamide salt lubricant and a silicone oil lubricant, and the mass ratio of the polyethyleneimine polyamide salt lubricant to the silicone oil lubricant is 2:1 - 1:1.

[0017] Among them, the antistatic agent is a mixture of a quaternary ammonium salt and a nitrate, and the mass ratio of the quaternary ammonium salt to the nitrate is 5:1 - 2:1; the pH value regulator is an acidic regulator.

[0018] In the glass fiber sizing agent provided by the present application, the film-forming agent is composed of an unsaturated polyester emulsion, a polyurethane emulsion, and an epoxy emulsion. Preferably, the unsaturated polyester emulsion is an isophthalic unsaturated polyester emulsion, the polyurethane emulsion is an aqueous polyurethane emulsion, and the epoxy emulsion is a bisphenol A epoxy resin emulsion. In addition, the sizing agent of the present application also selects appropriate silane coupling agents, defoamers, lubricants, pH regulators, and antistatic agents, and controls the content ratio of each component, so that the glass fiber coated with the sizing agent of the present application has excellent fluidity and fiber-opening performance. The SMC material for integral bathroom prepared therefrom has the characteristics of uniform glass fiber distribution, smooth product surface, excellent boiling water resistance, and high yield rate.

[0019] In the glass fiber sizing agent provided by the present application, the functions and contents of each component are described as follows:

[0020] The film-forming agent of the present application is the main component of the sizing agent, which has a decisive influence on the processing performance of glass fiber, and plays the role of protecting glass fiber, improving the fluidity, bundling property of glass fiber, and the compatibility with the matrix resin; the use of the film-forming agent should not only ensure the smoothness of glass fiber production, but also ensure that the glass fiber can be mixed evenly and distributed uniformly with the matrix resin to be reinforced in the subsequent process. Among them, the dosage of the film-forming agent has a crucial influence on the performance of glass fiber. Therefore, the dosage of the film-forming agent needs to be controlled within a suitable range. If the dosage of the film-forming agent is too small, the bundling property and stiffness of the glass fiber yarn cannot be guaranteed; if the dosage of the film-forming agent is too large, it will lead to an increase in oil migration during baking, a stronger bonding force, affect the smoothness of glass fiber production, and is not conducive to cost control. Therefore, the present application controls the percentage of the mass of the film-forming agent in the total mass of the sizing agent to be 4.0 - 26.0%, preferably 6.0 - 20.00%.

[0021] In addition, the selection of the film-forming agent is one of the key points of the present application. The film-forming agent selected by the present application includes an unsaturated polyester emulsion, a polyurethane emulsion, and an epoxy emulsion. Among them, due to the protection of the ester bond by the steric hindrance effect, the mechanical properties, heat resistance, and corrosion resistance of isophthalic unsaturated polyester products are better than those of orthophthalic unsaturated polyester products. Therefore, the unsaturated polyester emulsion is preferably an isophthalic unsaturated polyester emulsion; since the aqueous polyurethane emulsion has better bundling property for glass fiber yarns, is more beneficial to the boiling water resistance of glass fiber products, and is also more healthy and environmentally friendly, the polyurethane emulsion is preferably an aqueous polyurethane emulsion; since the bisphenol A epoxy resin emulsion has a large space effect after copolymerization and curing with crosslinking agents such as styrene, which hinders the hydrolysis of the ester bond and can play a shielding and protecting role for the ester group, making the boiling water resistance of glass fiber products better, the epoxy emulsion is preferably a bisphenol A epoxy resin emulsion.

[0022] Through a large number of experiments, it is found that in this application, by controlling the mass percentages of unsaturated polyester emulsion, polyurethane emulsion, and epoxy emulsion in the film-forming agent within appropriate ranges and using them in combination, the fluidity, fibrillating property, and bundling property of glass fibers can be significantly improved, while ensuring the surface property and boiling water resistance of the final SMC products. Therefore, in this application, the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent; preferably, the mass of the unsaturated polyester emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 8.0% of the total mass of the sizing agent.

[0023] Since the silane coupling agent has both hydrophilic groups and hydrophobic groups on its surface, it can serve as a bridge between the inorganic glass fibers with hydrophilic hydroxyl groups on the surface and the hydrophobic film-forming agent organic polymer. Through physical and chemical actions, they are closely connected to achieve good interfacial bonding, thereby enhancing the strength of the glass fibers and the boiling water resistance of the glass fiber-reinforced sanitary ware products. Through a large number of experiments, it is found that by controlling the dosage of the silane coupling agent within an appropriate range and using it in combination with the film-forming agent and lubricant provided in this application, the compatibility between the glass fibers and the resin can be effectively improved; if the dosage of the silane coupling agent is too large, it is not conducive to cost control; if the dosage of the silane coupling agent is too small, the interfacial bonding between the film-forming agent and the glass fibers will be weakened, resulting in a decrease in the mechanical properties of the glass fibers. Therefore, in this application, the percentage of the mass of the silane coupling agent in the total mass of the sizing agent is controlled to be 0.1 - 0.5%, preferably 0.1 - 0.4%, and more preferably 0.2 - 0.4%.

[0024] In addition, the silane coupling agent selected in this application is a mixture of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane. Among them, γ-glycidoxypropyltrimethoxysilane contains epoxy groups, which can further promote the cross-linking reaction of the epoxy emulsion in the film-forming agent, thereby effectively improving the strength and moisture resistance of the glass fiber product; due to the action of the amino functional group, γ-aminopropyltriethoxysilane can effectively improve the shear strength and toughness of the glass fiber product; the combined use of the two makes the prepared SMC material have better boiling water resistance and higher strength. In addition, during the research process, the inventors also found that if the dosage of γ-glycidoxypropyltrimethoxysilane is too much, the color of the glass fiber yarn will turn yellow, and if the dosage of γ-aminopropyltriethoxysilane is too much, the odor of the glass fiber yarn will be aggravated. Therefore, in this application, the mass ratio of γ-glycidoxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane is controlled to be 4:1 to 2:1, preferably 3:1 to 2:1; exemplarily, the mass ratio of γ-glycidoxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane can be 3:1.

[0025] The lubricant is mainly used to ensure that the glass fiber remains smooth during the processes of wire drawing, post-treatment, and use, thereby reducing the friction of the yarn. If the dosage of the lubricant is too small, the lubricating effect cannot be achieved, and if the dosage is too much, the adhesiveness between the glass fiber rovings will be affected, and the compatibility and impregnation degree between the glass fiber and the matrix resin will also be affected, thereby having a negative impact on the mechanical properties of the glass fiber product. Therefore, in this application, the percentage of the mass of the lubricant in the total mass of the sizing agent is controlled to be 0.1 to 0.5%, preferably 0.1 to 0.4%.

[0026] In addition, the lubricant selected in this application is a mixture of a polyethyleneimine polyamide salt lubricant and a silicone oil lubricant. Among them, the polyethyleneimine polyamide salt lubricant has a wet lubricating effect, and the silicone oil lubricant has a dry lubricating effect. The combined use of the two can effectively reduce the surface tension of the sizing agent, thereby reducing the occurrence of loose and flying filaments, which is beneficial to ensuring the smooth progress of the wire drawing and winding operations during the production process and effectively improving the bundling property of the glass fiber. At the same time, in this application, the mass ratio of the polyethyleneimine polyamide salt lubricant to the silicone oil lubricant is controlled to be 2:1 to 1:1. If the dosage of the polyethyleneimine polyamide salt lubricant is too much, the color of the yarn will turn yellow, and if the dosage of the silicone oil lubricant is too much, the impregnation speed of the yarn in the matrix resin will be reduced.

[0027] The defoamer is mainly used to eliminate the fisheyes generated during the use of the sizing agent, ensure the uniform coating of the sizing agent on the surface of the glass fiber, thereby reducing the surface defects of the glass fiber, improving the interfacial bonding ability between the glass fiber and the matrix resin, and further improving the water-boiling resistance of the SMC product. If the dosage of the defoamer is too much, it is not conducive to cost control. If the dosage is too little, it is difficult to achieve the effects of defoaming, improving the yarn bundling property, reducing hairiness and stabilizing the sizing agent. Therefore, in this application, the percentage of the mass of the defoamer in the total mass of the sizing agent is controlled to be 0.1-2.0%, preferably 0.1-1.0%.

[0028] In addition, the defoamer selected in this application is a polyether defoamer, and the polyether defoamer is at least one of polyaliphatic ether, polyaryl ether, and polyether ketone. This defoamer has the characteristics of long foam suppression time, good effect, fast defoaming speed, and good thermal stability; during the research process, it was found that this defoamer can also improve the bundling property of the yarn, reduce hairiness, thereby improving the production workshop environment and the comfort of workers; more particularly, this defoamer also helps to improve the stability of the sizing agent. Generally, the glass fiber sizing agent can only be stored for 48 hours, while the sizing agent of this application can be stored for 96 hours without sedimentation, and its storage period can be extended by more than one time, bringing great convenience to production.

[0029] The pH value regulator is mainly used to adjust the pH value of the sizing agent. In order to meet the hydrolysis and dispersion requirements of the silane coupling agent in this application, the sizing agent of this application needs to be controlled to be in a slightly acidic environment. Therefore, the pH value regulator in this application is an acidic regulator. Preferably, the pH value regulator is acetic acid. If the dosage of the pH value regulator is too much, it will affect the smell of the yarn. If the dosage is too little, the required acidic environment cannot be achieved. Therefore, in this application, the percentage of the mass of the pH value regulator in the total mass of the sizing agent is controlled to be 0.1-1.0%, preferably 0.1-0.6%.

[0030] The antistatic agent is used to ensure that no static electricity accumulation and hairiness adsorption occur when the yarn is chopped, thereby ensuring the uniformity of the chopped yarn laying and the smoothness of use. The dosage of the antistatic agent needs to be controlled within a suitable range. If the dosage of the antistatic agent is too much, the yarn will absorb moisture and the stiffness will decrease. If the dosage is too little, the antistatic effect during yarn chopping will be affected, resulting in the yarn sticking to the roller. Therefore, in this application, the percentage of the mass of the antistatic agent in the total mass of the sizing agent is controlled to be 0.1-2.0%, preferably 0.1-1.0%.

[0031] In addition, the antistatic agent selected in this application is a mixture of quaternary ammonium salt and nitrate, and this antistatic agent can ensure the antistatic effect and chopped dispersion of the yarn. At the same time, in this application, the mass ratio of quaternary ammonium salt to nitrate is controlled to be 5:1-2:1. If the dosage of the quaternary ammonium salt antistatic agent is too much, it will affect the smell of the yarn. If the dosage of the nitrate antistatic agent is too much, it will affect the smoothness of winding the yarn.

[0032] The water in the present application is used to disperse each component in the sizing agent, preferably deionized water. In the present application, the percentage of the mass of water in the total mass of the sizing agent is controlled to be 68.0 - 95.5%, preferably 76.6 - 93.5%, and more preferably 82.0 - 91.4%.

[0033] According to the second aspect of the present application, there is provided a glass fiber product produced by coating with the aforementioned glass fiber sizing agent.

[0034] According to the third aspect of the present application, there is provided the application of the aforementioned glass fiber product in the field of manufacturing sheet molding compounds for integral bathroom.

[0035] Compared with the prior art, the glass fiber sizing agent of the present application has the following beneficial effects:

[0036] First, the film-forming agent of the present application includes unsaturated polyester emulsion, polyurethane emulsion and epoxy emulsion. By controlling the percentage of the mass of each of the above three in the total mass of the sizing agent within a suitable range, the fluidity, fibrillating property and bundling property of the glass fiber can be significantly improved, and further the surface performance of the glass fiber product is better;

[0037] Second, the silane coupling agent with a specific composition and ratio in the present application cooperates with the film-forming agent of the present application, which can improve the bundling property of the glass fiber and effectively improve the compatibility between the glass fiber and the matrix resin, and further significantly enhance the boiling water resistance of the SMC material;

[0038] Third, the sizing agent of the present application also selects suitable defoaming agent, lubricant, antistatic agent and pH regulator, and controls the percentage of the mass of each of the above components in the total mass of the sizing agent within a suitable range. The glass fiber product produced by coating with this sizing agent has good bundling property, few surface defects, few fiber ends and static electricity during short cutting, and is evenly dispersed, and has excellent use performance; during the molding process, the glass fiber is evenly distributed, has good compatibility with the matrix resin, and the product obtained has excellent appearance effect and boiling water resistance.

[0039] The beneficial effects of the selection of each component and its content of the glass fiber sizing agent of the present application will be illustrated by specific experimental data in the examples. Detailed Embodiments

[0040] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the following will clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the described embodiments are part of the embodiments of this application, rather than all of them. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in this application without creative efforts belong to the scope of protection of this application. It should be noted that, without conflict, the embodiments in this application and the features in the embodiments can be combined arbitrarily with each other.

[0041] The following are examples of the preferred value ranges of the components included in the glass fiber sizing agent according to this application.

[0042] Preferred Example 1

[0043] The glass fiber sizing agent according to this application contains a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator, and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are shown as follows:

[0044]

[0045] Among them, the film-forming agent contains an unsaturated polyester emulsion, a polyurethane emulsion, and an epoxy emulsion.

[0046] Preferred Example 2

[0047] The glass fiber sizing agent according to this application contains a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator, and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are shown as follows:

[0048]

[0049] Among them, the film-forming agent contains an unsaturated polyester emulsion, a polyurethane emulsion, and an epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent.

[0050] Preferred Example 3

[0051] The glass fiber sizing agent according to this application contains a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator, and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are shown as follows:

[0052]

[0053] Among them, the film-forming agent includes unsaturated polyester emulsion, polyurethane emulsion and epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 8.0% of the total mass of the sizing agent.

[0054] Preferred Example Four

[0055] The glass fiber sizing agent according to the present application includes a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows:

[0056]

[0057]

[0058] Among them, the film-forming agent includes unsaturated polyester emulsion, polyurethane emulsion and epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent; the unsaturated polyester emulsion is a m-phthalic type unsaturated polyester emulsion; the polyurethane emulsion is an aqueous polyurethane emulsion; the epoxy emulsion is a bisphenol A type epoxy resin emulsion.

[0059] Preferred Example Five

[0060] The glass fiber sizing agent according to the present application includes a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows:

[0061]

[0062] Among them, the film-forming agent includes unsaturated polyester emulsion, polyurethane emulsion and epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent; the unsaturated polyester emulsion is a m-phthalic type unsaturated polyester emulsion; the polyurethane emulsion is an aqueous polyurethane emulsion; the epoxy emulsion is a bisphenol A type epoxy resin emulsion; the antifoaming agent is a polyether antifoaming agent, and the polyether antifoaming agent is at least one of polyaliphatic ether, polyaryl ether and polyether ketone.

[0063] Preferred Example Six

[0064] The sizing agent for glass fiber according to the present application comprises a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows:

[0065]

[0066] Among them, the film-forming agent comprises an unsaturated polyester emulsion, a polyurethane emulsion and an epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent; the unsaturated polyester emulsion is an isophthalic unsaturated polyester emulsion; the polyurethane emulsion is an aqueous polyurethane emulsion; the epoxy emulsion is a bisphenol A epoxy resin emulsion; the antifoaming agent is a polyether antifoaming agent, and the polyether antifoaming agent is at least one of polyaliphatic ether, polyaryl ether and polyether ketone; the silane coupling agent is a mixture of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and the mass ratio of γ-glycidoxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane is 4:1 - 2:1.

[0067] Preferred Example Seven

[0068] The sizing agent for glass fiber according to the present application comprises a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows:

[0069]

[0070]

[0071] Among them, the film-forming agent comprises an unsaturated polyester emulsion, a polyurethane emulsion and an epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent; the unsaturated polyester emulsion is an isophthalic unsaturated polyester emulsion; the polyurethane emulsion is an aqueous polyurethane emulsion; the epoxy emulsion is a bisphenol A epoxy resin emulsion; the antifoaming agent is a polyether antifoaming agent, and the polyether antifoaming agent is at least one of polyaliphatic ether, polyaryl ether and polyether ketone; the silane coupling agent is a mixture of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and the mass ratio of γ-glycidoxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane is 4:1 - 2:1; the lubricant is a mixture of a polyethyleneimine polyamide salt lubricant and a silicone oil lubricant, and the mass ratio of the polyethyleneimine polyamide salt lubricant to the silicone oil lubricant is 2:1 - 1:1.

[0072] Preferred Example VIII

[0073] The glass fiber sizing agent according to the present application comprises a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows:

[0074]

[0075] Among them, the film-forming agent comprises an unsaturated polyester emulsion, a polyurethane emulsion and an epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 1.0 - 8.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 10.0% of the total mass of the sizing agent; the unsaturated polyester emulsion is an isophthalic unsaturated polyester emulsion; the polyurethane emulsion is an aqueous polyurethane emulsion; the epoxy emulsion is a bisphenol A epoxy resin emulsion; the antifoaming agent is a polyether antifoaming agent, and the polyether antifoaming agent is at least one of polyaliphatic ether, polyaryl ether and polyether ketone; the silane coupling agent is a mixture of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and the mass ratio of γ-glycidoxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane is 4:1 - 2:1; the lubricant is a mixture of a polyethyleneimine polyamide salt lubricant and a silicone oil lubricant, and the mass ratio of the polyethyleneimine polyamide salt lubricant to the silicone oil lubricant is 2:1 - 1:1; the antistatic agent is a mixture of a quaternary ammonium salt and a nitrate, and the mass ratio of the quaternary ammonium salt to the nitrate is 5:1 - 2:1; the pH regulator is an acidic regulator.

[0076] To more clearly explain and illustrate the technical solution of the present application, some Examples 1 - 11 of the glass fiber sizing agent of the present application are listed herein. Among them, the specific formulations of the components of the glass fiber sizing agent in Examples 1 - 11 of the present application are shown in Table 1, and the values in Table 1 are the mass percentages of the components in the total mass of the sizing agent. It should be noted that the specific types, contents and combinations of the components selected in Table 1 do not limit the protection scope of the present application.

[0077] Table 1 Specific formulations of components of sizing agent examples

[0078]

[0079] Table 1 (continued) Specific formulations of components of sizing agent examples

[0080]

[0081] In addition, to better explain the beneficial effects of the present application, a commonly used sizing agent for SMC is selected as a comparative example to facilitate the explanation of the technical solution of the present application. The contents of the components in the sizing agent of this comparative example are expressed as mass percentages as follows:

[0082] Coupling agent: 0.4% of γ-aminopropyltriethoxysilane,

[0083] Film-forming agent 1: 6.0% of crosslinked polyvinyl acetate,

[0084] Film-forming agent 2: 3.0% of high molecular epoxy emulsion,

[0085] Film-forming agent 3: 3.5% of unsaturated polyester emulsion,

[0086] Lubricant: 0.1% of polyethylene oxide ether,

[0087] pH regulator: 0.2% of acetic acid,

[0088] Deionized water: 86.8%.

[0089] The sizing agents of the above examples and comparative examples were respectively applied to the production of glass fibers, and the corresponding glass fibers were applied to the preparation of glass fiber composites. The mechanical properties, as well as the boiling water resistance and appearance properties of the final SMC materials for integral bathroom, were tested. The results are as follows:

[0090] Table 2 Test results of the properties of glass fibers produced by applying sizing agents of examples and comparative examples

[0091]

[0092] Table 2 (continued) Test results of the properties of glass fibers produced by applying sizing agents of examples and comparative examples

[0093]

[0094] Note: The boiling water resistance test was carried out in a constant temperature water bath at a water temperature of 95°C, and the test sample was an SMC flat plate of 200*200*4 mm.

[0095] It can be seen from the test results of the properties of glass fibers produced by applying sizing agents of examples and comparative examples in Table 2 that the glass fiber composites produced by applying the sizing agents provided in Examples 1 to 11 of the present application have better properties, specifically reflected in the static electricity qualification rate and hairiness of the glass fibers, as well as the boiling water resistance and appearance properties of the final product SMC materials for integral bathroom:

[0096] In terms of the static electricity test, the average static electricity qualification rate of Examples 1 to 11 is 99.86%. Compared with the static electricity qualification rate of 95.50% in the comparative example, the static electricity qualification rate of the glass fiber composites coated with the glass fiber sizing agent of the present application has increased by more than 4 percentage points, indicating that the sizing agent further improves the antistatic performance of the glass fibers.

[0097] In terms of the measurement of hairiness, the average hairiness of Examples 1 to 11 is 12.62 mg / kg. Compared with the hairiness of 23.59 mg / kg in the comparative example, the hairiness of the glass fiber composite material coated with the sizing agent of the present application is reduced by 46.5%, indicating that the sizing agent greatly improves the bundling property of the glass fiber.

[0098] In terms of the boiling water resistance test of the SMC material for the final product of integral bathroom, Examples 1 to 11 did not foam when boiled in a constant temperature water bath at 95 °C for 300 h, and at most 2 bubbles appeared at 500 h. The best Example 2 did not even foam at 800 h, indicating that the boiling water resistance of the SMC material for integral bathroom finally prepared with the sizing agent of the present application is significantly better than that of the comparative example.

[0099] In terms of the appearance of the SMC material for the final product of integral bathroom, it was observed that there was material shortage at the edge of the product in the comparative example, and some glass fibers were exposed on the surface of the product. Even local glass fiber agglomeration and uneven glass fiber distribution occurred. Compared with the comparative example, the SMC material for integral bathroom finally prepared with the sizing agent of the present application has a complete edge, a smooth surface, and uniform glass fiber distribution. Only a few glass fiber traces are contained in some examples, and the overall appearance performance is excellent.

[0100] In summary, the sizing agent of the present application has the following beneficial effects:

[0101] First, the film-forming agent of the present application includes unsaturated polyester emulsion, polyurethane emulsion, and epoxy emulsion. By controlling the mass percentages of the above three in the total mass of the sizing agent within appropriate ranges, the fluidity, fiber opening property, and bundling property of the glass fiber can be significantly improved, and thus the surface performance of the glass fiber product is better;

[0102] Second, the silane coupling agent with a specific composition and ratio in the present application cooperates with the film-forming agent of the present application, which can improve the bundling property of the glass fiber and effectively improve the compatibility between the glass fiber and the matrix resin, and thus significantly enhance the boiling water resistance of the SMC material;

[0103] Third, the sizing agent of the present application also selects appropriate defoaming agents, lubricants, antistatic agents, and pH regulators, and controls the mass percentages of the above components in the total mass of the sizing agent within appropriate ranges. The glass fiber product coated and produced by this sizing agent has good bundling property, few surface defects, less hairiness and static electricity during short cutting, and uniform dispersion, and has excellent use performance; during the molding process, the glass fibers are evenly distributed, and the compatibility with the matrix resin is good. The products prepared have excellent appearance effects and boiling water resistance. Therefore, it can be applied to the field of SMC materials for home building materials such as integral bathrooms.

[0104] Finally, it should be noted that in this text, the term "including", "comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "comprising an..." does not exclude the existence of additional identical elements in the process, method, article or device comprising said element.

[0105] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A glass fiber sizing agent, characterized in that the sizing agent comprises a silane coupling agent, a lubricant, a film-forming agent, an antifoaming agent, an antistatic agent, a pH regulator and water; the mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows: wherein, the film-forming agent comprises an unsaturated polyester emulsion, a polyurethane emulsion and an epoxy emulsion; the mass of the unsaturated polyester emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 8.0% of the total mass of the sizing agent; the silane coupling agent is a mixture of γ-glycidoxypropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and the mass ratio of γ-glycidoxypropyltrimethoxysilane to γ-aminopropyltriethoxysilane is 4:1 - 2:

1.

2. The glass fiber sizing agent according to claim 1, characterized in that the mass percentages of the components of the sizing agent in the total mass of the sizing agent are as follows: wherein, the mass of the unsaturated polyester emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, the mass of the polyurethane emulsion accounts for 2.0 - 6.0% of the total mass of the sizing agent, and the mass of the epoxy emulsion accounts for 2.0 - 8.0% of the total mass of the sizing agent.

3. The glass fiber sizing agent according to claim 1 or 2, characterized in that the unsaturated polyester emulsion is an isophthalic unsaturated polyester emulsion; the polyurethane emulsion is an aqueous polyurethane emulsion; the epoxy emulsion is a bisphenol A epoxy resin emulsion.

4. The glass fiber sizing agent according to claim 1 or 2, characterized in that the antifoaming agent is a polyether antifoaming agent; wherein, the polyether antifoaming agent is at least one of polyaliphatic ether, polyaryl ether and polyether ketone.

5. The glass fiber sizing agent according to claim 1 or 2, characterized in that the lubricant is a mixture of a polyethyleneimine polyamide salt lubricant and a silicone oil lubricant, and the mass ratio of the polyethyleneimine polyamide salt lubricant to the silicone oil lubricant is 2:1 - 1:

1.

6. The glass fiber sizing agent according to claim 1 or 2, characterized in that the antistatic agent is a mixture of a quaternary ammonium salt and a nitrate, and the mass ratio of the quaternary ammonium salt to the nitrate is 5:1 - 2:1; the pH regulator is an acidic regulator.

7. A glass fiber product produced by coating with the glass fiber sizing agent according to any one of claims 1 - 6.

8. An application of the glass fiber product according to claim 7 in the field of manufacturing sheet molding compounds for integral bathroom.

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