Glass fiber direct yarn sizing agent and method for preparing the same

Abstract

The application discloses a glass fiber direct yarn impregnant and a preparation method thereof. The glass fiber direct yarn impregnant comprises effective components and water; the solid content of the impregnant is 5-12%, the effective components comprise a silane coupling agent, a film forming agent A, a film forming agent B and a lubricant, and the percentage of the solid mass of each effective component of the impregnant in the total mass of the solid of the impregnant is shown as follows: the silane coupling agent is 20-30%, the film forming agent A is 31-40%, the film forming agent B is 24-35%, the film forming agent A+the film forming agent B is 55-75%, and the lubricant is 5-15%; wherein the silane coupling agent is a bisamino silane oligomer, the film forming agent A is an isocyanate polymer, and the film forming agent B is an amide polymer. The glass fiber untwisted roving treated by the impregnant has stronger applicability of the glass fiber reinforced material for battery protection plates, the impact performance of the product is obviously improved, the bending performance is outstanding, and the market and application requirements are met.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass fiber production and manufacturing, in particular to a glass fiber direct yarn sizing agent and a preparation method thereof, and especially to a sizing agent for a glass fiber direct yarn for a battery protection plate. BACKGROUND

[0002] In recent years, in response to the call of the country, the energy industry chain is actively changing from traditional energy to green new energy to promote carbon peak and carbon comprehensive and realize the grand goal of long-term circular green economy. In particular, new energy vehicles represented by battery energy storage and motor power driving are developing rapidly, which has extremely important strategic significance for China to achieve a breakthrough in the automobile industry. As the core of China's new energy vehicle development, the safety research and development of batteries have always been considered a top priority by automobile manufacturers. In order to achieve better safety of the battery pack, the overall rigidity strength is required to be high, and the impact resistance and bending resistance are particularly important. At the same time, in order to better realize lightweighting, which helps to further improve the battery's mileage, new material technologies represented by continuous fiber prepreg tapes are widely used.

[0003] The present application is a continuous glass fiber treatment agent technology more suitable for the application field of battery protection plates to meet the target requirements of automobile manufacturers for new high-strength protection plates. SUMMARY

[0004] The present application aims to provide a glass fiber direct yarn sizing agent and a preparation method thereof. The glass fiber direct yarn sizing agent of the present application is suitable for continuous glass fiber reinforced PA, PET and other general-purpose prepreg tape materials, can meet the higher impact resistance requirements of the prepreg tape material, has high bending resistance, and meets the market and application requirements.

[0005] According to a first aspect of the present application, a glass fiber direct yarn sizing agent is provided, the sizing agent comprising effective components and water; the solid content of the sizing agent is 5-12%, and the effective components comprise a silane coupling agent, a film former A, a film former B and a lubricant, and the solid mass percentage of each effective component of the sizing agent in the total mass of the sizing agent is as follows:

[0006]

[0007] Among them, the silane coupling agent is a diamino silane oligomer, the film former A is an isocyanate polymer; and the film former B is an amide polymer.

[0008] Further, the diamino silane oligomer is one or both of an aminoalkyl modified organosilicon and an aminoalkyl containing alkyl siloxane.

[0009] Further, the molecular weight of the bisaminosilane oligomer is less than or equal to 1500.

[0010] Further, the ratio of the solid mass of the film-forming agent A to the solid mass of the film-forming agent B is 1:1 to 2:1.

[0011] Further, the isocyanate-based polymer is one or both of hydrogenated phenylmethane diisocyanate-based polymer and isophorone diisocyanate-based polymer; and the amide-based polymer is polyvinylpyrrolidone.

[0012] Further, the molecular weight of the isocyanate-based polymer is 1000 to 8000; and the molecular weight of the polyvinylpyrrolidone is 7000 to 11000.

[0013] Further, the lubricant is one or both of aliphatic lubricant and paraffin wax.

[0014] According to a second aspect of the present application, a preparation method of the aforementioned glass fiber direct yarn impregnant is provided, comprising: mixing the film-forming agent A diluted with water, the film-forming agent B diluted with water, the lubricant diluted with water, and the hydrolyzed silane coupling agent, stirring uniformly, and adding the rest of water to obtain the glass fiber direct yarn impregnant.

[0015] According to a third aspect of the present application, a glass fiber product coated by the aforementioned impregnant is provided.

[0016] According to a fourth aspect of the present application, the aforementioned glass fiber product is applied in a fiber-reinforced general-purpose polar resin prepreg process.

[0017] Compared with the prior art, the glass fiber roving treated by the impregnant of the present application has stronger applicability of the battery backsheet glass fiber reinforced material, the impact performance of the product is obviously improved, the bending performance is outstanding, and the market and application requirements are met. DETAILED DESCRIPTION

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present application clearer, the technical solutions of the present application will be described clearly and completely below with reference to the specific embodiments of the present application. Obviously, the described embodiments are some of the embodiments of the present application, but not all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the scope of protection of the present application. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other arbitrarily without conflict.

[0019] In some alternative embodiments, a glass fiber direct yarn sizing agent is provided, comprising effective components and water; the solid content of the sizing agent is 5-12%, the effective components comprise silane coupling agent, film forming agent A, film forming agent B and lubricant, the percentage of the solid mass of each effective component of the sizing agent in the total mass of the sizing agent is shown as follows:

[0020]

[0021]

[0022] wherein the silane coupling agent is a bisamino silane oligomer, the film forming agent A is an isocyanate polymer; the film forming agent B is an amide polymer.

[0023] In some alternative embodiments, a glass fiber direct yarn sizing agent is provided, comprising effective components and water; the solid content of the sizing agent is 5-12%, the effective components comprise silane coupling agent, film forming agent A, film forming agent B and lubricant, the percentage of the solid mass of each effective component of the sizing agent in the total mass of the sizing agent is shown as follows:

[0024]

[0025] wherein the silane coupling agent is a bisamino silane oligomer, the film forming agent A is an isocyanate polymer; the film forming agent B is an amide polymer.

[0026] In some alternative embodiments, a glass fiber direct yarn sizing agent is provided, comprising effective components and water; the solid content of the sizing agent is 5-12%, the effective components comprise silane coupling agent, film forming agent A, film forming agent B and lubricant, the percentage of the solid mass of each effective component of the sizing agent in the total mass of the sizing agent is shown as follows:

[0027]

[0028] wherein the silane coupling agent is a bisamino silane oligomer, the film forming agent A is an isocyanate polymer; the film forming agent B is an amide polymer.

[0029] In some alternative embodiments, a glass fiber direct yarn sizing agent is provided, comprising effective components and water; the solid content of the sizing agent is 5-12%, the effective components comprise silane coupling agent, film forming agent A, film forming agent B and lubricant, the percentage of the solid mass of each effective component of the sizing agent in the total mass of the sizing agent is shown as follows:

[0030]

[0031]

[0032] Among them, the silane coupling agent is a diaminosilane oligomer, film-forming agent A is an isocyanate polymer, and film-forming agent B is an amide polymer.

[0033] Silane coupling agents are substances with two functional groups possessing different properties. Their molecular structure is characterized by two chemically distinct groups: one is an inorganic-loving group that readily reacts with inorganic surfaces; the other is an organic-loving group that reacts with synthetic resins or other polymers or forms hydrogen bonds, dissolving within them. Therefore, coupling agents are called "molecular bridges" to improve the interfacial interaction between inorganic and organic materials, thereby significantly enhancing the performance of composite materials. The silane coupling agent used in this application is a diaminosilane oligomer. The diaminosilane oligomer has a functional group containing two amino groups. Due to its unique oligomer structure, it exhibits excellent wettability and chemical bonding on the glass fiber substrate surface, effectively protecting the integrity of the glass fiber during the drawing process. Simultaneously, the diamino properties maintain the treatment agent's excellent chemical activity, providing reaction sites for the resin group, thus improving the bonding ability with the resin. The coupled glass fiber product exhibits significantly improved impact resistance and rigidity. In this application, the amount of silane coupling agent must be controlled within a certain range. In actual use, the coupling agent often forms a deposition layer on the surface, but only a monolayer is truly effective. Therefore, the amount of coupling agent should not be excessive. If the content of silane coupling agent is too high, it will lead to self-polymerization on the glass fiber surface, causing some coupling agent to fail and also causing the glass fiber surface to become brittle, thus affecting the glass fiber performance. Conversely, if the content is too low, it will lead to a reduction in interfacial reaction sites, thereby affecting the reaction effect of the film-forming agent and failing to meet the target requirements for the protection of the glass fiber, thus affecting the mechanical and processing properties. Therefore, this application controls the percentage of the solid mass of the silane coupling agent to the solid mass of the wetting agent to be 20-30%, preferably 21-28%, more preferably 22-26%, and even more preferably 23-25%.

[0034] The film-forming agent of the present application is the main component of the infiltrating agent, and its main function is to protect the fibers. According to its source and properties, it can be divided into polyolefin film-forming agents, epoxy film-forming agents, polyurethane film-forming agents, PVAC film-forming agents, etc. Generally, a certain type of film-forming agent does not have all the properties required by the infiltrating agent, so two or three film-forming agents are often mixed and used in practice to make up for each other's shortcomings. The present application preferably uses two different types of film-forming agents to improve the dispersion and bonding of glass fibers, thereby improving the impact resistance and bending resistance of the reinforcing material. Specifically, the film-forming agent of the present application is a mixture of film-forming agent A and film-forming agent B, wherein film-forming agent A is an isocyanate polymer, and film-forming agent B is an amide polymer. The use of these two film-forming agents together can serve as a bridge to improve the adhesion and compatibility of polar materials and non-polar materials. Among them, the cyanate polymer (film-forming agent A) has good bonding with polar resins as a crosslinking agent, and its use amount and resin infiltration have a positive correlation within a certain range. Appropriately increasing the use amount can greatly improve the affinity and dispersibility of glass fibers and film-forming agent A, so as to effectively enhance the infiltration effect of glass fibers in polar resins (PA, PET, etc.), thereby improving the bending and impact strength of the filled film-forming agent A. In addition, the glass fibers have good dispersibility, can achieve good single fiberization in the pre-impregnation process, spread more evenly, and are beneficial to accelerating the reaction space with the resin in a shorter time, which can further improve the dispersion and bonding of the glass fibers. The present application needs to reasonably control the solid mass of film-forming agent A and film-forming agent B, film-forming agent A is 31-40%, and film-forming agent B is 24-35%; preferably, film-forming agent A is 32-38%, and film-forming agent B is 26-33%; more preferably, film-forming agent A is 34-37%, and film-forming agent B is 28-32%; further preferably, film-forming agent A is 35-37%, and film-forming agent B is 29-31%.

[0035] In the present application, the lubricant is a kind of additive for improving the internal friction of the material during use, especially the flowability and demouldability of the thermoplastic material during processing. In the glass fiber industry, the addition of the lubricant can effectively reduce the frictional resistance and the wear of the glass fiber during production and use. The present application relates to a special prepreg process, and the integrity of the glass fiber is extremely high during the drawing process and use. Excellent wet-based lubrication effect can ensure that the glass fiber has lower drawing tension during the production process, reduces wear, and achieves high integrity to retain the good bundling forming ability of the raw material. The preferred lubricant type in the present application is mineral oil lubricant. In addition to good lubricity, this kind of lubricant has high thermal stability (high temperature resistance and not easy to decompose), does not damage the physical properties of the final product, and does not affect the final product color. Combined with the strength and process characteristics of the product, the proportion of the lubricant should be within a certain range. If the content is too high, it will affect the combination of glass fiber and matrix resin, thereby affecting the mechanical properties. If it is too low, it cannot achieve the effect of lubricating the glass fiber, thereby causing the problem of increasing hairiness during production and processing. Therefore, the present application controls the solid mass of the lubricant to account for 5-15% of the total solid mass of the impregnant, preferably 8-14%, more preferably 9-12%, and further preferably 9-11%.

[0036] In some alternative embodiments, the bisamino silane oligomer is one or both of an aminoalkyl-modified silicone and an aminoalkyl-containing alkyl siloxane.

[0037] In some alternative embodiments, the bisamino silane oligomer has a molecular weight less than or equal to 1500. When the bisamino silane oligomer has a molecular weight less than or equal to 1500, it has strong bond energy, good heat resistance and yellowing resistance due to its containing two amino functional groups, containing a silicon-nitrogen bond, and having a small molecular weight.

[0038] In some alternative embodiments, the ratio of the solid mass of the film-forming agent A to the solid mass of the film-forming agent B is 1:1 to 2:1.

[0039] Due to the special process characteristics of the prepreg tape, the glass fiber needs to have good dispersibility and certain process smoothness. Therefore, the amount ratio of the film-forming agent A and the film-forming agent B should be fully considered to avoid excessive imbalance in the proportioning process, which may cause too much film-forming agent B and easily cause process problems such as hairiness and broken filaments, thereby causing problems such as broken yarns and skeins in the subsequent processing production process. If the film-forming agent B is too little, it will affect the dispersion of the glass fiber and the uniformity of the spreading in the subsequent processing process, thereby affecting the yield of the appearance. The inventors have found that when the solid mass of the film-forming agent A and the solid mass of the film-forming agent B are in the ratio of 1:1 to 2:1, the glass fiber has excellent dispersibility and process smoothness. The solid mass of the film-forming agent A and the solid mass of the film-forming agent B can also be in the ratio of 1.1:1 to 1.3:1. For example, the solid mass of the film-forming agent A and the solid mass of the film-forming agent B can also be in the ratio of 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.6:1, 1.8:1, 2:1

[0040] In some optional embodiments, the isocyanate-based polymer is one or both of hydrogenated phenylmethane diisocyanate-based polymer and isophorone diisocyanate-based polymer; the amide-based polymer is polyvinylpyrrolidone.

[0041] In the present application, the isocyanate-based polymer is selected from one or both of hydrogenated phenylmethane diisocyanate-based polymer and isophorone diisocyanate-based polymer. Both of these two polymers belong to non-yellowing isocyanate-based polymers, have strong ultraviolet resistance and oxidation resistance, so as to better improve the interfacial bonding capacity, and consider the good appearance characteristics of the tape to meet the requirements of yellowing resistance. The amide-based polymer is selected from polyvinylpyrrolidone, which can make the glass fiber disperse rapidly in a short time and retain excellent interfacial bonding capacity with the resin. The use of the isocyanate-based polymer in combination with the amide-based polymer can give the glass fiber good protection. The more sufficient the dispersion of the glass fiber, the better the appearance performance of the product, the better the impregnation effect of the resin, and the better the impact and bending resistance.

[0042] In some optional embodiments, the molecular weight of the isocyanate-based polymer is 1000-8000, and the molecular weight of the polyvinylpyrrolidone is 7000-11000. The isocyanate-based polymer and the polyvinylpyrrolidone in this molecular weight range have moderate viscosity, that is, they will not easily settle due to too high viscosity, affecting the dispersion effect of the impregnant, nor will they affect the coating effect of the impregnant due to too low viscosity.

[0043] In some alternative embodiments, the emulsion particle size of the film-forming agent A is 0.1-1.0 microns; the emulsion particle size of the film-forming agent B is 0.1-1.0 microns. The emulsion component has strong swelling performance and complexing ability with multiple substances. As a synthetic water-soluble polymer compound, it has the general properties of water-soluble polymer compounds, has colloidal protection, film-forming property, adhesion, hygroscopicity, solubilization or condensation, and in this patent, as a good dispersant, it enables the glass fiber to be uniformly dispersed and has good infiltration and binding capacity with the matrix resin. The film-forming agent A and the film-forming agent B with the above parameters have smaller particle sizes and higher stability, so that the infiltration agent has better stability,

[0044] In some alternative embodiments, the lubricant is one or both of an aliphatic lubricant and a paraffin.

[0045] The mineral oil lubricant in the present application can be selected from paraffin emulsion or aliphatic lubricant. On the one hand, paraffin itself is an excellent dry lubricant, which has strong effect on lubricating glass fiber. On the other hand, during the drying process of the coating film, the paraffin emulsion can migrate to the surface of the coating to form a protective film, thereby producing good anti-sticking effect and reducing the interlayer adhesion between fibers, so that the degradation tension is reduced and the smoothness is improved during use. The aliphatic lubricant, especially the high molecular weight linear aliphatic lubricant, also has good dry base lubrication effect, and can play a good protection and lubrication effect when matched with the film-forming agent.

[0046] It should be noted that in the present application, the solid mass of each effective component refers to the mass of the non-water component in the corresponding effective component.

[0047] In some alternative embodiments, a preparation method of the glass fiber direct yarn infiltration agent is provided, comprising:

[0048] The film-forming agent A diluted with water, the film-forming agent B diluted with water, the lubricant diluted with water, and the hydrolyzed silane coupling agent are mixed and stirred uniformly, and the remaining water is added to obtain the glass fiber direct yarn infiltration agent.

[0049] In some alternative embodiments, the preparation method of the hydrolyzed silane coupling agent comprises: adding water with a mass of 25-35 times that of the silane coupling agent in a container, slowly adding the silane coupling agent, and hydrolyzing for 30-50 minutes to obtain the hydrolyzed silane coupling agent.

[0050] The preparation method of the film-forming agent A diluted with water comprises: diluting the film-forming agent A with water with a mass of 2-4 times that of the film-forming agent A, and stirring uniformly to obtain the film-forming agent A diluted with water.

[0051] The preparation method of the water-diluted film-forming agent B comprises: diluting the film-forming agent B with water in an amount of 2-4 times the mass of the film-forming agent B, and stirring to obtain the water-diluted film-forming agent B;

[0052] The preparation method of the water-diluted lubricant comprises: diluting and dissolving the lubricant with water in an amount of 20-30 times the mass of the lubricant and at a temperature of 60-80°C, and stirring to obtain the water-diluted lubricant.

[0053] The application uses water as the dispersion phase of each component of the sizing agent, and water is more environmentally friendly and safe than a solvent dispersion phase. Preferably, the water is deionized water. Unless otherwise specified, the water refers to water at room temperature (20-30°C).

[0054] In the preparation method of the sizing agent for direct glass fiber yarn of the application, the water-diluted film-forming agent A, the water-diluted film-forming agent B, the water-diluted lubricant, and the hydrolyzed silane coupling agent should be prepared separately, and can be mixed and added after being fully hydrolyzed or stirred uniformly, so as to prevent some substances from causing uneven dispersion of the sizing agent due to hydrolysis or insufficient stirring, thereby increasing the actual measurement error of the solid content and affecting the use effect.

[0055] In some optional embodiments, a glass fiber product coated by the aforementioned sizing agent is provided.

[0056] In some optional embodiments, the use of the aforementioned glass fiber product in a fiber-reinforced general-purpose polar resin prepreg tape process is provided.

[0057] The combustible content of the glass fiber (i.e., the amount of sizing agent coated on the glass fiber accounts for the proportion of the mass of the glass fiber) of the application is generally controlled at 0.8-1.3%, and the combustible content should be appropriately higher within a certain range in the actual production process, considering economy and actual use effect. Due to the excellent dispersion effect of the film-forming system used in the patent application, appropriately increasing the combustible content can ensure excellent dispersibility of the glass fiber and significantly improve the protection and bonding of the glass fiber. However, too high a combustible content will lead to an increase in economic cost and a limitation on the performance improvement of the material itself, that is, the performance will also decrease with the increase of the content after reaching a certain level. In the actual production, a sizing agent with a higher solid content should be used to ensure that the product can obtain a relatively high combustible content. It has been proved that a relatively high combustible content can significantly improve the smoothness of the glass fiber in the production process of the product involved in the application.

[0058] In order to more clearly explain the technical solutions of the present application, the following lists partial specific examples (Examples 1-9) of the glass fiber direct yarn sizing agent of the present application, wherein the specific formulations of the partial examples of the glass fiber direct yarn sizing agent of Examples 1-9 of the present application are shown in Table 1. The values in Table 1 are the percentages of the solid mass of the effective components in the total solid mass of the sizing agent.

[0059] It should be noted that the specific types and contents of the components selected in Table 1 and the combinations thereof do not constitute a limitation on the scope of protection of the present application.

[0060] Table 1 is a specific formulation example and the specific test results of the 12 tex direct yarn produced according to a certain glass fiber production process. The values of the sizing agent components are the percentages of the solid mass of the components in the total solid mass of the sizing agent.

[0061] Specific formulation of the sizing agent of Examples 1-9 in Table 1

[0062]

[0063] In order to further illustrate the beneficial effects of the present application, two commonly used glass fiber direct yarn sizing agents are selected as Comparative Examples 1-2. The formulations of Comparative Examples 1-2 are shown below, wherein the amounts of the effective components are the percentages of the solid mass of the effective components in the total mass of the sizing agent.

[0064] Comparative Example 1:

[0065] Silane coupling agent: bisamino silane oligomer, proportion 25%;

[0066] Film forming agent: polyolefin modified emulsion, proportion 35%;

[0067] Film forming agent: polyvinylpyrrolidone, proportion 30%;

[0068] Lubricant: paraffin emulsion, proportion 10%.

[0069] Comparative Example 2:

[0070] Silane coupling agent: bisamino silane oligomer, proportion 25%;

[0071] Film forming agent: IPDI isocyanate, proportion 35%;

[0072] Film forming agent: water-based polyurethane emulsion, proportion 30%;

[0073] Lubricant: paraffin emulsion, proportion 10%.

[0074] From the actual measurement of the comparative examples, the actual measurement of the hairiness is 200-300 mg, the hairiness amount is greatly increased, the dispersibility is poor, there are many white strips and cracks in the produced sheet, and the appearance of the product is poor.

[0075] Test results:

[0076] Impact resistance test results

[0077] Under the conditions of the prepreg process, 65% glass fiber (GF) content, and through hot roller molding into a sheet, 0° and 90° crosswise and longitudinal molding composite profiles were formed, and the notched impact performance (method standard: ASTM D256) and the bending performance (method standard: ASTM D790) were measured, wherein the performance test results are shown in Table 2.

[0078] Table 2

[0079]

[0080] *Notched impact strength standard: ≥ 280 KJ / m2

[0081] *Bending strength standard: ≥ 250 Mpa

[0082] As can be seen from Table 2, by selecting the types of components of the sizing agent and controlling the content, we can obtain a sizing agent formula that meets the requirements, among which the glass fiber prepared in Example 3 has the best comprehensive performance, can achieve excellent appearance performance, has the best process state, and has good impact resistance and bending performance, meeting the customer's requirements for processing and forming battery guard plates. The impact resistance and bending performance of Comparative Example 1 and Comparative Example 2 are significantly lower, both below the standard line, not meeting the industry standard, and the appearance state and processing performance are not good, not meeting the design requirements.

[0083] In summary, the glass fiber untwisted roving treated by the sizing agent of the present application has strong applicability as a material for processing prepreg strips into guard plate profiles, has high impact resistance and bending performance, good appearance performance, and good processing smoothness, meeting most prepreg process systems, especially in the field of new energy vehicles, and is more suitable for customer groups with high impact resistance and bending performance requirements.

[0084] Finally, it should be noted that in this document, the terms "comprise", "comprise" or any other variant thereof are intended to cover non-exclusive inclusion, so that processes, methods, articles or equipment containing a series of elements not only include those elements, but also include other elements not explicitly listed, or include elements inherent to such processes, methods, articles or equipment. Without more limitations, the element defined by the statement "comprises one" does not exclude the presence of another identical element in the process, method, article or equipment that includes the element.

[0085] The above examples are only used to illustrate the technical solutions of the present application, but not to limit it. Although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those skilled in the art that the technical solutions recorded in the foregoing embodiments can be modified, or some technical features can be replaced by equivalent ones, and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A glass fiber direct yarn size, characterized by, The infiltrant comprises effective components and water; the solid content of the infiltrant is 5-12%, the effective components comprise silane coupling agent, film forming agent A, film forming agent B and lubricant, and the percentage of the solid mass of each effective component of the infiltrant in the total mass of the solid of the infiltrant is shown as follows: The silane coupling agent is a diamino silane oligomer, and the film forming agent A is an isocyanate polymer; the film forming agent B is an amide polymer.

2. The sizing agent according to claim 1, characterized in that, The diamino silane oligomer is one or both of aminoalkyl modified silicone and aminoalkyl containing alkyl siloxane.

3. The sizing agent of claim 1, wherein The molecular weight of the diamino silane oligomer is less than or equal to 1500.

4. The sizing agent of claim 1, wherein The ratio of the solid mass of the film forming agent A to the solid mass of the film forming agent B is 1:1-2:

1.

5. The sizing agent of claim 1, wherein The isocyanate polymer is one or both of hydrogenated phenylmethane diisocyanate polymer and isophorone diisocyanate polymer; the amide polymer is polyvinyl pyrrolidone.

6. The impregnating agent according to claim 5, characterized in that The molecular weight of the isocyanate polymer is 1000-8000; the molecular weight of the polyvinyl pyrrolidone is 7000-11000.

7. The sizing agent of claim 1, wherein The lubricant is one or both of aliphatic lubricant and paraffin.

8. A process for the preparation of a glass fiber direct yarn size according to any one of claims 1 to 7, characterized in that The method comprises mixing the film forming agent A diluted with water, the film forming agent B diluted with water, the lubricant diluted with water and the silane coupling agent after hydrolysis, stirring uniformly, and adding the rest of water to obtain the glass fiber direct yarn infiltrant.

9. A glass fiber product coated by the infiltrant of any one of claims 1-7.

10. Use of the glass fiber product of claim 9 in a fiber reinforced general purpose polar resin prepreg tape process.

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