Glass fiber wetting agent and its manufacturing method, glass fiber products and applications

Abstract

The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0%-6.0%, and the active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, an antifoaming agent, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is 6%-26% for the silane coupling agent, 45%-78% for the film-forming agent, 5%-15% for the lubricant, 1%-6% for the surfactant, 1%-5% for the leveling agent, 1%-6% for the interface enhancer, 1%-5% for the wetting agent, 1%-5% for the antifoaming agent, and 1%-7% for the pH adjuster. The glass fiber yarn produced by the wetting agent has high bundling ability, flexibility and high dispersibility after receiving a certain tension, fast penetration speed in epoxy resin, good penetration effect, high interfacial compatibility between glass fiber and resin, and suitable for knitting process. It is particularly suitable for producing thick wind blade fabrics, and composite materials made by vacuum infusing the fabric with epoxy resin have high static mechanics and fatigue resistance.

Description

[Technical field]

[0001] This invention claims priority to a Chinese patent application filed with the State Intellectual Property Office of the People's Republic of China on April 20, 2022, bearing application number 202210415238.5 and entitled "Glass fiber wetting agent and its manufacturing method, glass fiber products and applications", the entire contents of which are incorporated herein by reference.

[0002] Technical Field The present invention relates to the technical field of glass fiber wetting agents, and in particular to a glass fiber wetting agent and its manufacturing method, glass fiber products and applications. [Background technology]

[0003] After wind power enters the price parity stage, market competition will become more and more fierce, and all finished product manufacturers and blade manufacturers will reduce costs and improve efficiency in various ways to maintain the healthy and stable development of the industry. The mainstream cost reduction measures for wind blades mainly include two routes: the first route is to reduce the costs of raw materials including resin, glass fiber, and core material, and the second route is to improve the overall manufacturing efficiency and reduce unit manufacturing costs.

[0004] In this context, some finished product manufacturers at the forefront of industry research have put forward a comprehensive solution called thick woven fabric. The use of thick woven fabric has two advantages: (1) it improves laying efficiency, reducing the number of main beams of the same thickness by 1 / 3 to 1 / 2, significantly shortening the laying time and reducing the cost of labor and mold use; (2) it significantly improves the glass fiber content, effectively reducing the amount of resin used, making the arrangement between the thick woven fabric fibers more dense, and reducing the amount of resin used after injection by 2 to 3%.

[0005] Thick fabric has very prominent cost and efficiency advantages, but it requires very high technical capabilities. These requirements are mainly for the glass fiber infiltrator. First, the fiber arrangement of thick fabric is denser, and after the laying is completed, it has a negative effect on the resin injection speed, and the injection flow path is less. This leads to longer injection time, insufficient injection and other problems. This requires that the glass fiber infiltrator and the epoxy resin have higher compatibility, increase the overall injection speed, and ensure that the main beam can be fully infiltrated without negatively affecting the overall injection time. Secondly, the glass fiber content of thick fabric increases after injection, which directly affects the fatigue property of the main beam. Generally speaking, within a certain range, the higher the glass fiber content, the lower the fatigue property, which requires the glass fiber infiltrator to be redesigned to ensure the fatigue property of the blade.

[0006] At present, there is no specialized wetting agent for thick glass fiber fabrics on the market. Downstream customers are eager to develop a professional solution for thick wind power fabrics to meet the needs of the industry's development. Therefore, the design of glass fiber suitable for thick wind power fabrics has a significant improvement and promotion effect on the overall development of the wind power industry, and also has a profound impact and significant significance on the research of the cutting-edge field of new composite materials. Summary of the Invention

[0007] The object of the present invention is to provide a glass fiber wetting agent, which is applied to the glass fiber yarn produced, which has high bundling ability, flexibility and high dispersibility after being subjected to a certain tension, fast permeation speed of epoxy resin, good permeation effect, high interfacial compatibility between glass fiber and resin, and is suitable for knitting process, especially for the production of thick wind blade fabric, and the composite material formed by vacuum infusing the fabric with epoxy resin has high static dynamics and fatigue resistance.

[0008] According to one aspect of the present invention, there is provided a glass fiber wetting agent containing active ingredients and water, and having a solid content of 4.0 to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interfacial enhancer, a wetting agent, an antifoaming agent, and a pH adjuster, and the percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is as follows: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster: 1% to 7%.

[0009] In some embodiments, the percentage of the solid mass of each active ingredient in the wetting agent relative to the total solid mass of the wetting agent is: Silane coupling agent 7%~25%, Film-forming agent 50%~75%, Lubricants 7%~14%, Surfactant 1% to 5%, Leveling agent 1%~4%, Interface enhancer 1%~5%, Wetting agent 1%~4%, Antifoaming agent 2%~4%, pH adjuster: 2% to 6%.

[0010] In some embodiments, the percentage of the solid mass of each active ingredient in the wetting agent relative to the total solid mass of the wetting agent is: Silane coupling agent 9%~21%, Film-forming agent 52%~73%, Lubricants 7%~13%, Surfactant 2%~5%, Leveling agent 2%~4%, Interfacial enhancer 2%~5%, Wetting agent 2%~4%, Antifoaming agent 2%~3%, pH adjuster: 2% to 6%.

[0011] In some embodiments, the silane coupling agent is a mixture of a first silane coupling agent that is an amino silane coupling agent and a second silane coupling agent that is an epoxy silane coupling agent.

[0012] In some embodiments, the mass ratio C1 of the first silane coupling agent to the second silane coupling agent is 1:5 to 1:3.

[0013] In some embodiments, the first silane coupling agent is aminopropyltriethoxysilane and / or gamma-aminopropyltrimethoxysilane.

[0014] In some embodiments, the second silane coupling agent is gamma-glycidoxypropyltrimethoxysilane.

[0015] In some embodiments, the film former is a mixture of a first film former that is a bisphenol A type epoxy resin and a second film former that is a polyurethane resin.

[0016] In some embodiments, the mass ratio C2 of the first film-forming agent to the second film-forming agent is 1:1 to 2:1.

[0017] In some embodiments, the first film-forming agent is a bisphenol A type epoxy resin having a molecular weight of 2000-3000.

[0018] In some embodiments, the second film-forming agent is a polyurethane resin having a molecular weight of 200-400.

[0019] In some embodiments, the first film-forming agent is a bisphenol A type epoxy resin having a molecular weight of 2300-2700.

[0020] In some embodiments, the second film former is a polyurethane resin having a molecular weight of 250-350.

[0021] In some embodiments, the lubricant is a polyethyleneimine-based lubricant and / or fatty acid amides and their derivatives.

[0022] In some embodiments, the surfactant is a pyrrolidone and its derivatives and / or a pyridinium salt and its derivatives.

[0023] In some embodiments, the antifoam agent is an organosilicone composite and / or a polyether based antifoam agent.

[0024] In some embodiments, the leveling agent is a modified polyacrylate and / or a modified organosiloxane.

[0025] In some embodiments, the interfacial enhancer is silica nanoparticles and / or alumina nanoparticles.

[0026] In some embodiments, the humectant is an acetylene glycol based humectant and / or a modified polyoxyethylene derivative.

[0027] In some embodiments, the pH adjuster is glacial acetic acid and / or citric acid.

[0028] In some embodiments, the percentage of the solid mass of each active ingredient in the wetting agent relative to the total solid mass of the wetting agent is: Silane coupling agent 10%~16%, Film-forming agent 55%~72%, Lubricant 7%~12%, Surfactant 2%~4%, Leveling agent 2%~4%, Interfacial enhancer 2%~4%, Wetting agent 2%~3%, Antifoaming agent 2%~3%, pH adjuster 2% to 5% Among them, the silane coupling agent is a mixture of a first silane coupling agent using an amino silane coupling agent and a second silane coupling agent using an epoxy silane coupling agent, the film forming agent is a mixture of a first film forming agent using a bisphenol A type epoxy resin and a second film forming agent using a polyurethane resin, the lubricant is a polyethyleneimine-based lubricant and / or a fatty acid amide and its derivatives, the surfactant is pyrrolidone and its derivatives and / or pyridinium salt and its derivatives, the leveling agent is a modified polyacrylate and / or a modified organosiloxane, the interface enhancer is silica nanoparticles and / or alumina nanoparticles, the wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative, the defoamer is an organic silicone complex and / or a polyether-based defoamer, and the pH adjuster is citric acid and / or glacial acetic acid.

[0029] In some embodiments, the water in the wetting agent of the present invention is deionized water. The function of the water in the wetting agent of the present invention is to act as a dispersed phase of each component.

[0030] According to a second aspect of the present invention, A silane coupling agent pre-dispersion step in which 30% to 45% of the total mass of the wetting agent is added to the container, and then a pH adjuster and a silane coupling agent are added in sequence to pre-disperse the silane coupling agent, and the solution is stirred until it becomes clear to obtain a silane coupling agent pre-dispersion liquid; a dilution step of the film-forming agent, the lubricant, the surfactant, the leveling agent, the interfacial enhancing agent, the wetting agent and the defoaming agent, respectively, with water; and adding the diluted film-forming agent, lubricant, surfactant, leveling agent, interfacial enhancer, wetting agent and defoamer solution to the silane coupling agent pre-dispersion, and then supplementing the remaining amount of water and stirring uniformly.

[0031] In some embodiments, the film-forming agent is diluted with 3 to 4 times its weight in water, the interfacial enhancer is dispersed in 5 to 8 times its weight in water, and the antifoam agent is diluted with 3 to 5 times its weight in water.

[0032] In some embodiments, the lubricant is diluted with 5-6 times its mass of hot water having a temperature of 45-60° C., the surfactant is diluted with 4-6 times its mass of hot water having a temperature of 45-60° C., the interfacial enhancer is diluted with 4-6 times its mass of hot water having a temperature of 45-60° C., and the wetting agent is diluted with 5-6 times its mass of hot water having a temperature of 45-60° C.

[0033] Among them, the pre-dispersion of the silane coupling agent and the dilution of the film-forming agent, the lubricant, the surfactant, the leveling agent, the interface enhancer, the wetting agent and the defoaming agent can be performed in any order. The silane coupling agent can be pre-dispersed first, and the film-forming agent, the lubricant, the surfactant, the leveling agent, the interface enhancer, the wetting agent and the defoaming agent can be diluted first, or they can be performed simultaneously.

[0034] According to a third aspect of the present invention, there is provided a glass fiber product produced by applying the above-mentioned glass fiber wetting agent.

[0035] According to a fourth aspect of the present invention, there is provided the use of a glass fibre product produced by application of the glass fibre wetting agent as described above in an epoxy resin composite material.

[0036] According to a fifth aspect of the present invention, there is provided the use of an epoxy resin composite material as described above in the field of wind power generation. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0037] In order to clarify the purpose, technical solution and advantages of the embodiments of the present invention, the following embodiments of the present invention are combined to clearly and completely describe the technical solution of the present invention. It is clear that the described embodiments are only some of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present invention. Furthermore, unless contradictory, the embodiments of the present invention and the features of the embodiments can be arbitrarily combined with each other.

[0038] The glass fiber wetting agent provided by some embodiments of the present invention comprises an active ingredient and water, the active ingredients including a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, an antifoaming agent and a pH adjusting agent, among which the solid content of the wetting agent is 4.0%-6.0%, and the percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is as follows: silane coupling agent 6%-26%, film-forming agent 45%-78%, lubricant 5%-15%, surfactant 1%-6%, leveling agent 1%-5%, interface enhancer 1%-6%, wetting agent 1%-5%, antifoaming agent 1%-5%, pH adjusting agent 1%-7%.

[0039] Silane coupling agents are one of the raw materials with the highest reaction activity in the wetting agent system, and the activity of the silicone hydroxyl groups formed after its hydrolysis is high, which can react with the silicone hydroxyl groups on the surface of the glass fiber to form Si-O-Si bonds. In the glass fiber wetting agent system, the coupling agent mainly plays the following roles (1) and (2). (1) In the process of drawing and molding the glass fiber, due to the fast drawing speed, the glass fiber forms surface microcracks in the process of rapidly transforming from a liquid state to a solid state, and the silicone hydroxyl groups of the silane coupling agent can well compensate for these microcracks by reacting with the silicone hydroxyl groups on the surface of the glass fiber to ensure the normal drawing process of the glass fiber; (2) It is a "bridge" action between the glass fiber and the resin, and the R group of the silane coupling agent can react with the functional group on the matrix resin, and the silicone hydroxyl group can bond with the silicone hydroxyl group on the glass fiber, which is one of the important factors that determine the strength of the glass steel product. By selecting an appropriate silane coupling agent, it can not only improve the performance of the glass fiber itself and the mechanical properties of the glass steel product produced later, but also reduce the production cost of the glass fiber. When blending a glass fiber wetting agent, it is necessary to control the amount of silane coupling agent used within a certain range. If the amount of silane coupling agent used is too small, the active group is insufficient, which adversely affects the glass fiber drawing process and the performance of the composite material, and if the amount used is too large, a part of the silane coupling agent is wasted, which increases the cost. In some embodiments, the percentage of the solid mass of the silane coupling agent relative to the total solid mass of the wetting agent may be 6% to 26%, 7% to 25%, 9% to 21%, or 10% to 16%.

[0040] In some embodiments, the silane coupling agent may be a mixture of a first silane coupling agent, which may be an amino silane coupling agent, and a second silane coupling agent, which may be an epoxy silane coupling agent. The amino silane coupling agent contains an amine group and has a very high reaction activity, which can not only react with the film-forming agent during the baking process to ensure the overall bundling of the glass fibers, but also react quickly with the epoxy resin in the subsequent processing to form a very stable chemical bond, thereby strengthening the interface bond between the glass fibers and the epoxy resin and improving the mechanical properties of the composite material. The R group in the epoxy silane coupling agent is an epoxy group, which can ensure that the glass fibers can be rapidly infiltrated into the epoxy resin in the subsequent composite material manufacturing process according to the principle of "like dissolves well with like". In the present invention, when the first silane coupling agent is an amino silane coupling agent and the second silane coupling agent is an epoxy silane coupling agent, the proportional relationship between the amino silane coupling agent and the epoxy silane coupling agent can also affect the performance of the glass fiber. If there is too much amino silane coupling agent, the glass fiber will have too good bundling ability and become hard, which is unfavorable to penetration. If there is too much epoxy silane coupling agent, it is favorable for the penetration of epoxy resin into the glass fiber, but if there is too little amino silane coupling agent, not only will the bundling ability of the yarn be insufficient and the yarn will be easily spread, but also will have a negative effect on the mechanical properties of the composite material. In some embodiments, the mass ratio C1 of the amino silane coupling agent to the epoxy silane coupling agent may be controlled to 1:5 to 1:3, or 1:4.3 to 1:3.7. Specifically, when the mass ratio C1 of the amino silane coupling agent to the epoxy silane coupling agent is 1:4, the performances of the glass fiber manufactured with the infiltrating agent manufactured by blending with other components can all meet the requirements.

[0041] In some embodiments, the first silane coupling agent may be aminopropyltriethoxysilane and / or gamma-aminopropyltrimethoxysilane. In some embodiments, the second silane coupling agent may be gamma-glycidoxypropyltrimethoxysilane.

[0042] The film former is the most important and largest component in the wetting agent. It can not only determine the molding process, bundling, flexibility and wear resistance of glass fiber, but also affect the dispersion and process smoothness of the subsequent processing, and is also one of the important factors of the interface bonding between glass fiber and matrix resin. In the actual production of glass fiber, the amount of film former should be controlled within an appropriate range. Research has shown that if the content of film former is insufficient, problems will occur in the application of the wetting agent, and the wetting agent cannot ensure effective protection of the glass fiber, thereby adversely affecting the use process performance and mechanical properties of the glass fiber. If the content of film former is too high, the bundling of the yarn will be too good, difficult to spread, and more fluff will be produced, which is also unfavorable to the penetration of the resin. In some embodiments, the percentage of the solid mass of the film-forming agent relative to the total solid mass of the wetting agent may be controlled to 45% to 78%, 50% to 75%, 52% to 73%, or even 55% to 72%. Within the above range, the film-forming agent can ensure that the glass fiber has good dispersibility and flexibility, as well as the processability of the glass fiber, the compatibility with the matrix resin, and the mechanical properties of the composite material.

[0043] In some embodiments, the film-forming agent may be a mixture of a first film-forming agent and a second film-forming agent. The first film-forming agent may be a bisphenol A type epoxy resin, and the second film-forming agent may be a polyurethane resin. In some embodiments, the first film-forming agent may be a bisphenol A type epoxy resin with a large molecular weight, specifically, a bisphenol A type epoxy resin with a molecular weight of 2000-3000, or a bisphenol A type epoxy resin with a molecular weight of 2300-2700. The epoxy resin with a large molecular weight can ensure the film-forming property of the wetting agent. In some embodiments, the second film-forming agent may be a polyurethane resin with a small molecular weight, specifically, a polyurethane resin with a molecular weight of 200-400, or a polyurethane resin with a molecular weight of 250-400, or even a polyurethane resin with a molecular weight of 250-350. The polyurethane resin with a small molecular weight is very easy to disperse after the glass fiber is subjected to tension, and can ensure the permeability and interface bonding action. At the same time, the amount of the two kinds of film-forming agents must be strictly controlled. If the amount of the first film-forming agent is too much, the bundling property will be too good, and the yarn will not be easily permeated by the resin. If the amount of the second film-forming agent is too much, the yarn will be too soft and easy to spread, which will have a negative impact on the processability of subsequent use. In some embodiments, the mass ratio C2 of the first film-forming agent to the second film-forming agent can be controlled to 1:1 to 2:1. When the mass ratio C2 of the first film-forming agent to the second film-forming agent in the present invention is 1:1 to 2:1, each performance of the produced glass fiber can reach an excellent level.

[0044] In some embodiments, the mass ratio of the silane coupling agent to the film-forming agent is 1:3 to 1:6, which not only ensures the film formation and coating uniformity of the wetting agent, but also provides sufficient reaction activity between the wetting agent and the glass skeleton and matrix resin.

[0045] The lubricant is one of the main components of the glass fiber wetting agent, mainly to improve the wear resistance of the glass fiber and ensure smoothness during the drawing process and use process. The lubricant of the present invention may be a polyethyleneimine-based lubricant and / or a fatty acid amide and its derivatives. Such a lubricant has very good dispersibility in water, has a remarkable lubricating effect, and can effectively reduce the generation of fluff. Among them, the fatty acid amide and its derivatives may include one or two of alkoxy-modified fatty acid amides and quaternized fatty acid amides. The amount of lubricant used in the production of glass fiber must also be strictly controlled. If the amount of lubricant used is too small, it will adversely affect the smoothness of the drawing and use process, and it is easy to cause problems such as yarn breakage during the drawing process and subsequent interrupted yarn use, but if the amount of lubricant is too large, not only will it increase the cost, but the excess lubricant will easily stick to the surface of the tensioning device during the use of the glass fiber, and as the amount of lubricant that sticks increases, the adhesion will increase, causing situations such as yarn adhesion and yarn breakage, which will also adversely affect the processability of using the glass fiber. In some embodiments, the percentage of the solid mass of the lubricant relative to the total solid mass of the wetting agent may be controlled to 5% to 15%, 7% to 14%, 7% to 13%, or even 7% to 12%.

[0046] The surfactant has amphiphilicity, so it mainly plays a role in stabilizing each component of the wetting agent. The components of the wetting agent are complex, and the problem of aggregation or precipitation after mixing of different components is easy to occur, which adversely affects the normal drawing process and the uniformity of application by the wetting agent. Adding an appropriate amount of surfactant can effectively solve the related problems. The surfactant of the present invention can be pyrrolidone and its derivatives and / or pyridinium salt and its derivatives, which has very good amphiphilicity, is the most common surfactant in the industry, and can well guarantee the stability of the wetting agent system. At the same time, if the amount of surfactant used in the wetting agent is too small, the problem of the wetting agent settling and the surface application becoming uneven will occur, which will ultimately have an adverse effect on the performance of the glass fiber; if the amount used is too large, after reaching the "saturation concentration", the excess part will not function, which indirectly increases the production cost; and many surfactants have charges, but the matrix resin will not be charged, and the concentration of too much charge will have an adverse effect on the penetration of the resin into the glass fiber, so there is a certain requirement on the amount of surfactant used. In some embodiments, the percentage of the solid mass of the surfactant relative to the total solid mass of the wetting agent may be controlled to 1% to 6%, 1% to 5%, 2% to 5%, or even 2% to 4%.

[0047] The leveling agent can effectively reduce the surface tension and improve the permeability of the entire wetting agent, thereby increasing the rate at which the epoxy resin permeates into the glass fiber. The leveling agent can also improve the covering ability of the wetting agent, thereby forming a flat, smooth and uniform coating film during the film formation process by the wetting agent, thereby indirectly enhancing the interfacial bonding action between the glass fiber and the epoxy resin. The leveling agent selected in the present invention can be a polyacrylate and / or an organosiloxane leveling agent, and these two types of leveling agents can not only promote the flow and leveling of the coating film, but also have no adverse effect on the interlayer adhesion of the coating film and have a partial defoaming effect. Among them, the polyacrylate can include one or two of epoxy-modified polyacrylate and amino-modified polyacrylate, and the organosiloxane leveling agent can include one or two of epoxy and polyether-modified copolymer and epoxy and polyester-modified copolymer. At the same time, the amount of the leveling agent used must be strictly controlled, and too much or too little of the leveling agent will have a negative impact. If the amount of the leveling agent used is too much and exceeds the saturation concentration, the cost of the wetting agent will increase, and if the amount of the leveling agent used is too little, the surface tension cannot be effectively reduced, and the coating uniformity of the wetting agent cannot be guaranteed, which will fundamentally have a negative impact on the permeability of the glass fiber. In some embodiments, the percentage of the solid mass of the leveling agent in the total solid mass of the wetting agent may be controlled to 1% to 5%, may be controlled to 1% to 4%, or may even be controlled to 2% to 4%.

[0048] In the present invention, the use of the interface enhancer is also one of the important technical points. Thick fabrics often have a high content of glass fiber after injection, which significantly reduces the fatigue resistance of the composite material, so it is necessary to introduce an auxiliary agent to improve the interface bonding to improve the fatigue resistance, and the interface enhancer can play a similar role. The interface enhancer in the present invention can select silica nanoparticles and / or alumina nanoparticles, specifically, the interface enhancer in the present invention is a nanoscale silica particle, and there are a large number of silicone hydroxyl groups on the surface of the silica, which can react with the silicone hydroxyl groups in the glass fiber and the silane coupling agent, while also participating in the reaction between the epoxy resin and the amine curing agent, and play a very good connecting role. In addition, the attachment of nanoscale silica can increase the specific surface area of ​​the glass fiber, increase the bonding sites between the glass fiber and the epoxy resin, and improve the interface bonding role and the mechanical properties and fatigue resistance of the final composite material. Nanoscale silica has very good dispersibility in water due to its small size and does not require additional treatment. The amount of silica interfacial enhancer used must be controlled within a certain range; if the amount used is too small, the increase in specific surface area and bonding sites is small, and the enhancement of the interfacial bond between the reinforcing glass fiber and the resin is not significant; if the amount used is too large, the glass fiber surface will have too many "protrusions", which will adversely affect the wear resistance of the glass fiber, cause problems such as an unsmooth drawing process, increased fluff, etc. In some embodiments, the percentage of the solid mass of the interfacial enhancer relative to the total mass of the solid components of the wetting agent may be controlled to 1%-6%, 1%-5%, 2%-5%, or even 2%-4%.

[0049] Another key point of the present invention is the use of a wetting agent, which can significantly reduce the surface tension of the wetting agent, increase the penetration rate of the epoxy resin into the glass fiber to enhance the effect, and enhance the interfacial bonding between the glass fiber and the matrix resin, thereby improving the mechanical properties of the composite material. The wetting agent of the present invention may be an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative. Specifically, the wetting agent of the present invention is an acetylene glycol-based wetting agent. The acetylene glycol-based wetting agent has very good dispersibility, can reduce the surface tension, and can enhance the adhesion between the glass fiber and the epoxy resin, and has low foaming / defoaming function, and can effectively ensure the penetration state of the glass fiber in the epoxy resin. At the same time, it is necessary to control the amount of wetting agent used, and if too much wetting agent is used, the wetting effect will be saturated, which will cause high costs and high costs of the wetting agent, and if too little is used, it will have a negative effect on the wetting effect, thereby adversely affecting the penetration rate and penetration effect of the glass fiber into the epoxy resin. In some embodiments, the percentage of the solid mass of the wetting agent relative to the total mass of the solid components of the wetting agent may be controlled to 1% to 5%, 1% to 4%, 2% to 4%, or even 2% to 3%.

[0050] The defoaming agent is mainly used to remove bubbles generated during the preparation and circulation of the glass fiber wetting agent. During the preparation and circulation of the glass fiber wetting agent, a large amount of bubbles will be generated due to the presence of emulsifiers and surfactants, and these bubbles will have a negative effect on the distribution of the wetting agent on the oil application roller, and will further negatively affect the application uniformity and normal production process. The defoaming agent can effectively avoid the generation of bubbles and ensure the normal production of glass fiber. The defoaming agent of the present invention may be an organic silicone compound and / or a polyether-based defoaming agent, specifically, the defoaming agent is an organic silicone compound. In addition, the amount of the defoaming agent used must be controlled within a certain range. If the amount of the defoaming agent used is too large, the defoaming effect will be saturated, and the excess will increase the cost; if the amount used is too small, the defoaming effect will not be significant, which will have a negative effect on the penetration effect of the glass fiber and the epoxy resin. In some embodiments, the percentage of the solid mass of the defoamer relative to the total mass of the solid components of the wetting agent may be controlled to 1% to 5%, may be controlled to 2% to 4%, or may even be controlled to 2% to 3%.

[0051] Through experiments, the inventors have found that a glass fiber yarn product produced by blending the film-forming agent, lubricant, surfactant, leveling agent, interfacial enhancer, wetting agent, defoamer and silane coupling agent of the present invention in an appropriate content ratio has high bundling ability, is flexible and highly dispersible after being subjected to a certain tension, has a fast penetration speed and good penetration effect with epoxy resin, and has high interfacial compatibility between glass fiber and resin, which is suitable for weaving process, especially for producing thick wind blade fabric, and a composite material formed by vacuum injecting the fabric with epoxy resin has high static mechanics and fatigue resistance.

[0052] The pH adjuster of the present invention is mainly used for hydrolysis of the silane coupling agent and adjustment of the pH value of the wetting agent so as to control the pH value of the wetting agent within the range of 6 to 7. The pH adjuster in the present invention may be glacial acetic acid and / or citric acid, specifically, glacial acetic acid. In some embodiments, the percentage of the solid mass of the pH adjuster relative to the total mass of the solid components of the wetting agent may be controlled to 1% to 7%, may be controlled to 2% to 6%, or may even be controlled to 2% to 5%.

[0053] In some embodiments, the percentage by mass of solids of each active ingredient in the wetting agent relative to the total mass of solids of the wetting agent is as follows: silane coupling agent 7%-25%, film-forming agent 50%-75%, lubricant 7%-14%, surfactant 1%-5%, leveling agent 1%-4%, interfacial enhancer 1%-5%, wetting agent 1%-4%, defoamer 2%-4%, and pH adjuster 2%-6%.

[0054] In some embodiments, the percentage by mass of solids of each active ingredient in the wetting agent relative to the total mass of solids of the wetting agent is as follows: silane coupling agent 9%-21%, film forming agent 52%-73%, lubricant 7%-13%, surfactant 2%-5%, leveling agent 2%-4%, interfacial enhancer 2%-5%, wetting agent 2%-4%, defoamer 2%-3%, and pH adjuster 2%-6%.

[0055] In some embodiments, the percentage by mass of solids of each active ingredient in the wetting agent relative to the total mass of solids of the wetting agent is as follows: silane coupling agent 10%-16%, film forming agent 55%-72%, lubricant 7%-12%, surfactant 2%-4%, leveling agent 2%-4%, interfacial enhancer 2%-4%, wetting agent 2%-3%, defoamer 2%-3%, and pH adjuster 2%-5%.

[0056] The beneficial effects of selecting the above ranges of the content of each component in the glass fiber wetting agent provided by the present invention will be explained with reference to specific experimental data in the examples.

[0057] The following are examples of preferred ranges of values ​​for each component contained in the glass fiber wetting agent according to the present invention. EXAMPLES

[0058] Preferred example 1 The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster 1% to 7% Among them, the silane coupling agent is characterized in that it is a mixture of a first silane coupling agent which is an amino silane coupling agent and a second silane coupling agent which is an epoxy silane coupling agent.

[0059] Preferred example 2 The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster 1% to 7% The film-forming agent is characterized in that it is a mixture of a first film-forming agent, which is a bisphenol A type epoxy resin, and a second film-forming agent, which is a polyurethane resin.

[0060] Preferred example 3 The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster 1% to 7% Among them, the silane coupling agent is a mixture of a first silane coupling agent which is an amino silane coupling agent and a second silane coupling agent which is an epoxy silane coupling agent, and the film forming agent is a mixture of a first film forming agent which is a bisphenol A type epoxy resin and a second film forming agent which is a polyurethane resin.

[0061] Preferred example 4 The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster 1% to 7% The lubricant is a polyethyleneimine-based lubricant, the surfactant is a polypyrrolidone-based surfactant, the leveling agent is a modified polyacrylate, the interfacial enhancer is silica nanoparticles, the wetting agent is an acetylene glycol-based wetting agent, the defoaming agent is an organic silicone complex, and the pH adjuster is acetic acid and / or citric acid.

[0062] Preferred example 5 The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster 1% to 7% Among them, the silane coupling agent is a mixture of a first silane coupling agent which is an amino silane coupling agent and a second silane coupling agent which is an epoxy silane coupling agent; the film-forming agent is a mixture of a first film-forming agent which is a bisphenol A type epoxy resin and a second film-forming agent which is a polyurethane resin; the lubricant is a polyethyleneimine-based lubricant and / or a fatty acid amide and its derivatives; the surfactant is pyrrolidone and its derivatives and / or pyridinium salt and its derivatives; the leveling agent is a modified polyacrylate and / or a modified organosiloxane; the interface enhancer is silica nanoparticles and / or alumina nanoparticles; the wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative; the defoaming agent is an organic silicone complex and / or a polyether-based defoaming agent; and the pH adjuster is citric acid and / or glacial acetic acid.

[0063] Preferred example 6 The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster 1% to 7% Among them, the silane coupling agent is a mixture of a first silane coupling agent which is an amino silane coupling agent and a second silane coupling agent which is an epoxy silane coupling agent, the film forming agent is a mixture of a first film forming agent which is a bisphenol A type epoxy resin and a second film forming agent which is a polyurethane resin, and the mass ratio C1 of the first silane coupling agent to the second silane coupling agent is 1:5 to 1:3, and the mass ratio C2 of the first film forming agent to the second film forming agent is 1:1 to 2:1.

[0064] Preferred example 7 The glass fiber wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interface enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6%~26%, Film-forming agent 45%~78%, Lubricant 5%~15%, Surfactant 1% to 6%, Leveling agent 1%~5%, Interfacial enhancer 1%~6%, Wetting agent 1%~5%, Antifoaming agent 1%~5%, pH adjuster 1% to 7% The silane coupling agent is a mixture of a first silane coupling agent which is an amino silane coupling agent and a second silane coupling agent which is an epoxy silane coupling agent; the film forming agent is a mixture of a first film forming agent which is a bisphenol A type epoxy resin and a second film forming agent which is a polyurethane resin; the mass ratio C1 of the first silane coupling agent to the second silane coupling agent is 1:5 to 1:3, the mass ratio C2 of the first film forming agent to the second film forming agent is 1:1 to 2:1; and the lubricant is polyethyleneimine. the surfactant is a modified polyacrylate and / or a modified organosiloxane; the interfacial enhancer is a silica nanoparticle and / or an alumina nanoparticle; the wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative; the defoaming agent is an organosilicon complex and / or a polyether-based defoaming agent; and the pH adjuster is citric acid and / or glacial acetic acid.

[0065] The method for producing the glass fiber wetting agent of preferred examples 1 to 7 is as follows: Step 1S of adding water of 30% to 45% of the total mass of the wetting agent to the container, then adding a pH adjuster and a silane coupling agent in order, pre-dispersing the silane coupling agent, and stirring until the solution becomes clear to obtain a silane coupling agent pre-dispersion liquid; Step 2S of diluting the film-forming agent with 3 to 4 times the mass of water, diluting the lubricant with 5 to 6 times the mass of water at 55°C, diluting the surfactant with 4 to 6 times the mass of hot water at 55°C, stirring and diluting the leveling agent with 4 to 6 times the mass of hot water at 55°C, diluting the interfacial enhancer with 5 to 8 times the mass of water, diluting the wetting agent with 5 to 6 times the mass of water at 55°C, and diluting the defoamer with 3 to 5 times the mass of water; and step 3S of mixing the silane coupling agent pre-dispersion with the diluted film-forming agent, lubricant, surfactant, leveling agent, interfacial enhancer, wetting agent and defoamer, refilling the container with the remaining amount of water, and stirring uniformly.

[0066] The specific blending ratios of some examples of the glass fiber wetting agent of the present invention are as shown in Table 1. The solid content of Examples 1 to 4 is 5.0%, the solid content of Examples 5 to 8 is 4.0%, the solid content of Examples 9 to 12 is 6.0%, the solid content of Example 13 is 4.5%, and the solid content of Example 14 is 5.5%. The values ​​in Table 1 are the percentages of the solid mass of each active ingredient in the total solid mass of the wetting agent, and the C1 value and C2 value are the ratio values ​​of the percentages of the solid mass of the corresponding active ingredients.

[0067] [Table 1-1]

[0068] [Table 1-2]

[0069] [Table 1-3]

[0070] Furthermore, a comparative example is given in this specification to illustrate the technical solution of the present invention.

[0071] Comparative Example 1 The solid content of the wetting agent is 5.5%. The percentage of the mass of each solid component in the total mass of the solid components is: Amidosilane coupling agent 15.0%, Film former (epoxy resin) 60.0%, Lubricant (fatty acid amide lubricant) 8.0%, Surfactant (quaternary ammonium salt surfactant) 3.0%, Defoamer (organic silicone compound) 6.0%, pH adjuster (citric acid) 8.0%.

[0072] The manufacturing method of Comparative Example 1 is as follows: (1) adding 30% to 45% of the total amount of water to a container containing a variable speed mixer, adding a pH adjuster and an amidosilane coupling agent in turn, and stirring until the solution becomes clear; (2) diluting the film-forming agent with 3 to 5 times its mass of water and then placing it in a container; (3) diluting the lubricant with 4 to 6 times its mass with water at 55°C and then placing it in a container; (4) diluting the surfactant with 4 to 5 times its mass of water and then placing it in a container; (5) diluting the defoamer with 3 to 5 times its mass of water and then placing it in a container; Finally, the remaining amount of water is added to the container, and the mixture is stirred uniformly to obtain the product (6).

[0073] Table 2 records the performance test results of the glass fiber wetting agents of Examples 1-18 of the present invention and Comparative Example 1.

[0074] [Table 2-1]

[0075] [Table 2-2]

[0076] [Table 2-3]

[0077] As can be seen from the above examples, by selecting the type and content design of each component of the wetting agent, a wetting agent mixing ratio that meets the requirements can be obtained. Compared with Comparative Example 1, the glass fiber produced in Examples 1-18 of the present invention has good performance, the glass fiber has less fluff, the yarn does not fray after being subjected to tension, the yarn quality is flexible, the penetration speed of epoxy resin is fast, and the interfacial bonding effect is good. The produced composite material has excellent mechanical properties and fatigue resistance.

[0078] As can be seen from the above, the glass fiber yarn produced by applying the wetting agent is flexible, disperses very well after being subjected to a certain tension, penetrates into epoxy resin quickly and completely, has very high interfacial compatibility, and is suitable for knitting process, especially for manufacturing thick wind blade substrate, which can effectively solve the problem of slow resin penetration into thick fabric and low fatigue resistance. The composite material produced by vacuum infusing the fabric produced using the wetting agent with epoxy resin has very high mechanical properties and fatigue resistance.

[0079] In the present invention, the solid content mass of each active ingredient refers to the mass of non-moisture substances in each active ingredient, and is not limited to the solid components.

[0080] Finally, it should be noted that, as used herein, the terms "comprise," "contain," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or facility that includes a set of elements not only includes those elements, but also includes other elements not expressly listed or that are inherent to such process, method, article, or facility. Unless otherwise limited, an element qualified by the phrase "comprises a..." does not exclude the presence of additional identical elements in the process, method, article, or facility that includes the recited element.

[0081] The above embodiments are merely for illustrating the technical solutions of the present invention, and are not intended to limit the same. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art may make modifications to the technical solutions described in the above embodiments, or make equivalent substitutions for some technical features therein, but it should be understood that these modifications or substitutions do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application.

[0082] Industrial Applicability The present invention provides a glass fiber wetting agent. The glass fiber yarn produced by using the wetting agent of the present invention has good bundling ability, is flexible and highly dispersible after being subjected to a certain tension, has a very fast permeation speed with epoxy resin, has good permeation effect, and has high interfacial compatibility between glass fiber and resin, and is suitable for knitting process, especially for producing thick wind blade fabric. The composite material formed by vacuum infusing the fabric with epoxy resin has high static mechanics and fatigue resistance.

Claims

1. The wetting agent contains an active ingredient and water, and the solid content is 4.0% to 6.0%. The active ingredients include a silane coupling agent, a film-forming agent, a lubricant, a surfactant, a leveling agent, an interfacial enhancer, a wetting agent, a defoamer, and a pH adjuster. The percentage of the solid mass of each active ingredient in the total solid mass of the wetting agent is: Silane coupling agent 6% to 26%, Film-forming agent 45% to 78%, Lubricant 5% to 15%, Surfactant 1% to 6%, Leveling agent 1% to 5%, Interfacial enhancer 1% to 6%, Wetting agent 1% to 5%, Defoamer 1% to 5%, pH adjuster 1% to 7% A glass fiber infiltrating agent,

2. The percentage of the solid mass of each active ingredient in the wetting agent to the total solid mass of the wetting agent is Silane coupling agent 7% to 25%, Film-forming agent 50% to 75%, Lubricant 7% to 14%, Surfactant 1% to 5%, Leveling agent 1% to 4%, Interface enhancer 1% to 5%, Wetting agent 1% to 4%, Defoamer 2% to 4%, pH adjuster 2% to 6% 2. The glass fiber infiltrating agent according to claim 1, characterized in that:

3. 2. The glass fiber wetting agent according to claim 1, characterized in that the silane coupling agent is a mixture of a first silane coupling agent which is an amino silane coupling agent and a second silane coupling agent which is an epoxy silane coupling agent.

4. The glass fiber wetting agent according to claim 3, wherein the mass ratio C1 of the first silane coupling agent to the second silane coupling agent is 1:5 to 1:

3.

5. The glass fiber infiltration agent according to claim 3, characterized in that the first silane coupling agent is aminopropyltriethoxysilane and / or γ-aminopropyltrimethoxysilane, and the second silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

6. 2. The glass fiber wetting agent according to claim 1, characterized in that the film former is a mixture of a first film former which is a bisphenol A type epoxy resin and a second film former which is a polyurethane resin.

7. The glass fiber infiltrating agent according to claim 6, characterized in that the mass ratio C2 of the first film-forming agent to the second film-forming agent is 1:1 to 2:

1.

8. 2. The glass fiber wetting agent according to claim 1, wherein the lubricant is a polyethyleneimine-based lubricant and / or a fatty acid amide and its derivative, and the surfactant is pyrrolidone and its derivative and / or a pyridinium salt and its derivative.

9. The glass fiber infiltrating agent according to claim 1, characterized in that the defoaming agent is an organosilicon composite and / or a polyether-based defoaming agent, and the leveling agent is a modified polyacrylate and / or a modified organosiloxane.

10. The glass fiber infiltrating agent according to claim 1, characterized in that the interfacial enhancing agent is silica nanoparticles and / or alumina nanoparticles.

11. The glass fiber wetting agent according to claim 1, characterized in that the wetting agent is an acetylene glycol-based wetting agent and / or a modified polyoxyethylene derivative.

12. A method for producing the glass fiber infiltrating agent according to any one of claims 1 to 11, comprising the steps of: A pre-dispersion step of adding water of 30% to 45% of the total mass of the wetting agent to a container, then adding a pH adjuster and a silane coupling agent in order to pre-disperse the silane coupling agent, and stirring the solution until it becomes clear to obtain a pre-dispersion liquid of the silane coupling agent; a dilution step of the film-forming agent, the lubricant, the surfactant, the leveling agent, the interfacial enhancing agent, the wetting agent and the defoaming agent, respectively, with water; Add the diluted film-forming agent, lubricant, surfactant, leveling agent, interface enhancer, wetting agent and defoamer to the silane coupling agent pre-dispersion, and add the remaining amount of water, and stir uniformly to obtain a glass fiber wetting agent; A manufacturing method comprising the steps of:

13. A glass fiber product produced by applying the glass fiber wetting agent according to any one of claims 1 to 11.

14. Use of the glass fiber product according to claim 13 in an epoxy resin composite material.

15. Use of the epoxy resin composite material according to claim 14 in the field of wind power generation.

Images