A treating agent for electronic-grade glass fiber cloth, its preparation method and application

Abstract

A treating agent for electronic-grade glass fiber cloth, its preparation method and application belong to the field of treating agents for glass fiber cloth. The treating agent for electronic-grade glass fiber cloth includes the following components by weight percentage: 0.5-1.5% of a composite coupling agent, 0.2-0.4% of modified halloysite nanotubes, 0.2-0.6% of alcohol, 2-3% of an acidic regulator, and the balance is water; the composite coupling agent includes an amino silane coupling agent and an imide ring-modified silane coupling agent with a mass ratio of 3-4:1. The treating agent for electronic-grade glass fiber cloth of the present invention can improve the bonding performance between the electronic-grade glass fiber cloth and the resin, and at the same time enhance the impregnation property and heat resistance of the electronic-grade glass fiber cloth.

Description

Technical Field

[0001] The present invention belongs to the field of treating agents for glass fiber cloth, and particularly relates to a treating agent for electronic-grade glass fiber cloth, a preparation method thereof, and an application thereof. Background Art

[0002] Glass fiber cloth is a kind of cloth woven from glass fibers, usually having excellent insulation properties, electrical properties, weather resistance, chemical corrosion resistance, and dimensional stability, and is widely used in printed circuit boards that play an insulating and strengthening role. However, since glass fiber is an inorganic material and resin is an organic material, an effective combination between the two requires a treating agent. The formulation of the treating agent directly determines the bonding strength at the interface between the resin and the glass fiber. Once the bonding force is insufficient and delamination occurs between the resin and the glass fiber, the printed circuit board will experience board explosion or ion migration, thereby affecting the insulation reliability of the printed circuit board. In addition, due to the development of electronic products towards smaller, lighter, and thinner, the printed circuit board substrates are also required to be of high density and multi-layered, which puts forward higher requirements for the performance of electronic-grade glass fiber cloth, requiring that the electronic-grade glass fiber cloth be impregnated with resin faster and more evenly.

[0003] Patent application CN103422356A discloses a surface treating agent for electronic-grade glass fiber cloth, including 0.3%-0.9% of silane coupling agent, 0.3-0.8% of acidic regulator, 0.1%-0.5% of surfactant, and the balance being deionized water, all of which are mass fractions. Although the surface treating agent for electronic-grade glass fiber cloth can be applicable to the fields of high-density, high-uniformity, and high-performance printed circuits, it does not investigate the stability of the treating agent. In addition, the surfactant added therein does not effectively improve the surface tension of the treating agent, resulting in a lack of uniformity in the treating agent's wetting of the electronic-grade glass fiber cloth, and further limiting the effective spreading of the coupling agent on the glass fiber cloth surface. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, an object of the present invention is to provide a treating agent for electronic-grade glass fiber cloth, a preparation method thereof, and an application thereof. The treating agent for electronic-grade glass fiber cloth can improve the bonding performance between the electronic-grade glass fiber cloth and the resin, and at the same time enhance the impregnability and heat resistance of the electronic-grade glass fiber cloth.

[0005] To achieve the above object, according to one aspect of the present invention, there is provided a treating agent for electronic-grade glass fiber cloth, which, by weight percentage, includes the following components: 0.5-1.5% of a complex coupling agent, 0.2-0.4% of modified halloysite nanotubes, 0.2-0.6% of alcohol, 2-3% of an acidic regulator, and the balance being water; the complex coupling agent includes an amino silane coupling agent and an imide ring-modified silane coupling agent in a mass ratio of 3-4:1.

[0006] In the present invention, in the treating agent for the electronic-grade glass fiber cloth, the weight percentage of the compound coupling agent is 0.5-1.5%. It can be understood that the weight percentage can be any specific value among 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5% or any value within the range of 0.5-1.5%. In the present invention, the compound coupling agent includes an amino-silane coupling agent and an imide-ring modified silane coupling agent with a mass ratio of 3-4:1. It can be understood that the mass ratio of the amino-silane coupling agent and the imide-ring modified silane coupling agent can be any specific value among 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4.0:1 or any value within the range of 3-4:1. Preferably, the mass ratio of the amino-silane coupling agent and the imide-ring modified silane coupling agent is 3.5:1.

[0007] In the present invention, the amino-silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

[0008] In the present invention, the imide-ring modified silane coupling agent is a phthalic anhydride modified silane coupling agent.

[0009] The inventors found that by selecting specific amino-silane coupling agents and imide-ring modified silane coupling agents for compounding and further regulating the compounding ratio, it is ensured that the compound coupling agent has appropriate activity, and the two act synergistically, thereby improving the bonding performance between the electronic-grade glass fiber cloth and the resin, and at the same time improving the impregnation property and heat resistance of the electronic-grade glass fiber cloth. Further, the present invention uses an amino-silane coupling agent as the main coupling agent, and the amino functional group can chemically react with a resin matrix such as epoxy resin, significantly improving the interfacial bonding strength. In addition, in the present invention, by adding a certain amount of phthalic anhydride modified silane coupling agent, due to its imide ring with a planar symmetric ring structure, it has high thermal stability, and at the same time, due to the inductive effect of the carbonyl group on the imide ring, it has strong polarity and can interact with the glass fiber cloth to a certain extent, thereby improving the impregnation property of the glass fiber cloth. After the impregnation property is improved, it will further promote the chemical reaction between the amino-silane coupling agent and the resin matrix such as epoxy resin, and further improve the bonding performance between the electronic-grade glass fiber cloth and the resin.

[0010] In the present invention, in the treatment agent for the electronic-grade glass fiber cloth, the weight percentage of the modified halloysite nanotubes is 0.2 - 0.4%. It can be understood that the weight percentage can be any specific value among 0.2%, 0.3%, 0.4% or any value within the range of 0.2 - 0.4%. In the present invention, the modified halloysite nanotubes are halloysite nanotubes modified with 4-phenylethynylphthalic anhydride. Preferably, the halloysite nanotubes are of a hollow tubular structure, with an inner tube diameter of 10 - 30 nm, an outer diameter of 40 - 70 nm, and a length of 0.2 - 1 μm. By incorporating a certain amount of modified halloysite nanotubes, the present invention improves the mechanical interlock between the glass fiber cloth and the resin matrix, thereby effectively enhancing the interfacial bonding strength. If the content of the modified halloysite nanotubes is too high, agglomeration is likely to occur on the surface of the glass fiber cloth, thereby reducing the performance; if the content of the modified halloysite nanotubes is too low, the interfacial bonding strength will be correspondingly reduced, and the impregnability of the electronic-grade glass fiber cloth will also be reduced. In addition, the use of 4-phenylethynylphthalic anhydride to modify the halloysite nanotubes further improves the dispersibility and heat resistance of the halloysite nanotubes, and during the processing, the halloysite nanotubes are not easily detached from the glass fiber cloth, better playing the role of mechanical interlock, thereby strengthening the interfacial bonding strength between the glass fiber cloth and the resin matrix.

[0011] In the present invention, in the treatment agent for the electronic-grade glass fiber cloth, the weight percentage of the acid regulator is 2 - 3%. It can be understood that the weight percentage can be any specific value among 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0% or any value within the range of 2 - 3%. In the present invention, the acid regulator is glacial acetic acid.

[0012] In the present invention, in the treatment agent for the electronic-grade glass fiber cloth, the weight percentage of the alcohol is 0.2 - 0.6%. It can be understood that the weight percentage can be any specific value among 0.2%, 0.3%, 0.4%, 0.5%, 0.6% or any value within the range of 0.2 - 0.6%. In the present invention, the alcohol includes one or more of methanol, ethanol or glycerol.

[0013] According to another aspect of the present invention, there is also provided a method for preparing the above treatment agent for the electronic-grade glass fiber cloth, and the method includes the following steps:

[0014] (1) Add the acidity regulator and the alcohol to water and stir evenly to obtain a mixed aqueous solution;

[0015] (2) Mix the amino-functional silane coupling agent and the imide ring-modified silane coupling agent in proportion to obtain the compound coupling agent;

[0016] (3) Add halloysite nanotubes, 4-phenylethynylphthalic anhydride, and γ-aminopropyltriethoxysilane to an N,N-dimethylacetamide solution, ultrasonicate at 50 - 60 °C for 12 - 16 h, wash and dry to obtain the modified halloysite nanotubes;

[0017] (4) Add the complex coupling agent and the modified halloysite nanotubes to the mixed aqueous solution, stir evenly to obtain the treatment agent for the electronic grade fiberglass cloth.

[0018] In the present invention, in step (1), add an acidity regulator and an alcohol to water, stir evenly to obtain a mixed aqueous solution. Among them, the presence of the alcohol can inhibit the condensation of silanol groups, thereby ensuring the production of the maximum amount of silanol groups in the hydrolysis solution and ensuring the activity of the hydrolysis solution.

[0019] In the present invention, in step (2), mix the amino silane coupling agent and the imide ring-modified silane coupling agent in proportion to obtain the complex coupling agent. In the present invention, the preparation method of the imide ring-modified silane coupling agent includes the following steps: Stir and dissolve phthalic anhydride and glacial acetic acid, add allylamine, react at room temperature for 1 - 2 h, heat reflux for 4 - 5 h, cool to room temperature and then add to clear water to obtain a white solid; Dissolve a certain amount of the white solid in THF, add a chloroplatinic acid solution, dropwise add triethoxysilane, and react at 60 - 65 °C for 8 - 10 h to obtain the imide ring-modified silane coupling agent. In the present invention, the molar ratio of phthalic anhydride to allylamine is 1:1. In the present invention, the molar ratio of the certain amount of white solid to triethoxysilane is 1:1. In the present invention, THF (THF is tetrahydrofuran).

[0020] In the present invention, in step (3), add halloysite nanotubes, 4-phenylethynylphthalic anhydride, and γ-aminopropyltriethoxysilane to an N,N-dimethylacetamide solution, ultrasonicate at 50 - 60 °C for 12 - 16 h, wash and dry to obtain the modified halloysite nanotubes. In the present invention, in step (3), the mass ratio of the halloysite nanotubes, 4-phenylethynylphthalic anhydride, and γ-aminopropyltriethoxysilane is 1:1 - 1.5:1. It can be understood that the mass ratio can be any specific value among 1:1:1, 1:1.1:1, 1:1.2:1, 1:1.3:1, 1:1.4:1, 1:1.5:1 or any value within the range of 1:1 - 1.5:1.

[0021] In the present invention, in step (4), add the complex coupling agent and the modified halloysite nanotubes to the mixed aqueous solution, stir evenly to obtain the treatment agent for the electronic grade fiberglass cloth.

[0022] According to another aspect of the present invention, there is also provided an application of the above-mentioned treating agent or the treating agent prepared by the above method in an electronic-grade glass fiber cloth.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] (1) The present invention creatively designs a treating agent for electronic-grade glass fiber cloth. By selecting specific amino-silane coupling agents and imide-ring modified silane coupling agents for compounding and further regulating the compounding ratio, it is ensured that the compound coupling agents have appropriate activities. The two act synergistically, thereby improving the bonding performance between the electronic-grade glass fiber cloth and the resin, and at the same time improving the impregnability and heat resistance of the electronic-grade glass fiber cloth. The present invention uses an amino-silane coupling agent as the main coupling agent, and the amino functional group can chemically react with a resin matrix such as epoxy resin, significantly improving the interfacial bonding strength. In addition, by adding a certain amount of imide-ring modified silane coupling agent in the present invention, due to its imide ring with a planar symmetric ring structure, it has high thermal stability. At the same time, due to the inductive effect of the carbonyl group on the imide ring, it has strong polarity and can have a certain strength of interaction with the glass fiber cloth, thereby improving the impregnability of the glass fiber cloth. After the impregnability is improved, it will further promote the chemical reaction between the amino-silane coupling agent and the resin matrix such as epoxy resin, and further improve the bonding performance between the electronic-grade glass fiber cloth and the resin.

[0025] (2) By incorporating a certain amount of modified halloysite nanotubes in the present invention, the mechanical interlock between the glass fiber cloth and the resin matrix is improved, thereby effectively enhancing the interfacial bonding strength. Further, by modifying the halloysite nanotubes with 4-phenylethynylphthalic anhydride, the dispersibility and heat resistance of the halloysite nanotubes are improved, and during the processing, the halloysite nanotubes are not easily detached from the glass fiber cloth, better playing the role of mechanical interlock, thereby strengthening the interfacial bonding strength between the glass fiber cloth and the resin matrix.

[0026] (3) The present invention also provides a preparation method of a treating agent for electronic-grade glass fiber cloth. The method is simple and easy to operate and is suitable for large-scale production. Detailed embodiments

[0027] To enable those skilled in the art to understand the features and effects of the present invention, the following provides a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meaning understood by those skilled in the art for the present invention. In case of conflict, the definition in this specification shall prevail.

[0028] The theories or mechanisms described and disclosed herein, whether right or wrong, shall not in any way limit the scope of the present invention, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0029] In this document, when describing embodiments or examples, it should be understood that they are not used to limit the present invention to these embodiments or examples. On the contrary, all alternatives, improvements, and equivalents of the methods and materials described in the present invention can be covered within the scope defined by the claims.

[0030] In this document, for the sake of brevity, all possible combinations of all technical features in each embodiment or example are not described. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each embodiment or example can be combined arbitrarily, and all possible combinations should be considered as within the scope described in this specification.

[0031] The present invention provides a treating agent for electronic-grade glass fiber cloth, which comprises the following components by weight percentage: 0.5-1.5% of a compound coupling agent, 0.2-0.4% of modified halloysite nanotubes, 0.2-0.6% of an alcohol, 2-3% of an acidic regulator, and the balance being water; the compound coupling agent comprises an amino-silane coupling agent and an imide-ring modified silane coupling agent in a mass ratio of 3-4:1.

[0032] In some embodiments, the amino-silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

[0033] In some embodiments, the imide-ring modified silane coupling agent is a phthalic anhydride modified silane coupling agent.

[0034] In some embodiments, the modified halloysite nanotubes are 4-phenylethynylphthalic anhydride modified halloysite nanotubes.

[0035] In some embodiments, the acidic regulator is glacial acetic acid.

[0036] In some embodiments, the alcohol comprises one or more of methanol, ethanol, or glycerol.

[0037] The present invention also provides a preparation method of the above-mentioned treating agent for electronic-grade glass fiber cloth, and the method comprises the following steps:

[0038] (1) Add the acidity regulator and the alcohol to water, and stir evenly to obtain a mixed aqueous solution;

[0039] (2) Mix the amino-silane coupling agent and the imide-ring modified silane coupling agent in proportion to obtain the compound coupling agent;

[0040] (3) Add halloysite nanotubes, 4-phenylethynylphthalic anhydride, and γ-aminopropyltriethoxysilane to an N,N-dimethylacetamide solution, ultrasonicate at 50-60 °C for 12-16 h, wash and dry to obtain the modified halloysite nanotubes;

[0041] (4) Add the complex coupling agent and the modified halloysite nanotubes to the mixed aqueous solution, stir evenly to obtain the treatment agent for electronic grade fiberglass cloth.

[0042] In some embodiments, the preparation method of the imide ring-modified silane coupling agent includes the following steps: Stir and dissolve phthalic anhydride and glacial acetic acid, add allylamine, react at room temperature for 1-2 h, heat under reflux for 4-5 h, cool to room temperature and add to clear water to obtain a white solid; Dissolve a certain amount of the white solid in THF, add chloroplatinic acid solution, dropwise add triethoxysilane, and react at 60-65 °C for 8-10 h to obtain the imide ring-modified silane coupling agent.

[0043] In some embodiments, in step (3), the mass ratio of the halloysite nanotubes, 4-phenylethynylphthalic anhydride, and γ-aminopropyltriethoxysilane is 1:1-1.5:1.

[0044] The present invention also provides an application of the above treatment agent or the treatment agent prepared according to the above method in electronic grade fiberglass cloth.

[0045] The present invention will be described in detail below through examples. It should be understood that the following examples are only used to further explain and illustrate the content of the present invention by way of example, and are not used to limit the present invention.

[0046] Example 1 is the best example.

[0047] The chemical aids used in the examples and comparative examples of the present invention are all commercially available, and the specific information is as follows:

[0048] Allylamine: Purchased from Zouping Mingxing Chemical Co., Ltd.; Chloroplatinic acid solution: 8 wt% aqueous solution of chloroplatinic acid, purchased from Merck; Triethoxysilane: Silane coupling agent CG-H23, purchased from Jiangsu Bost Chemical Technology Co., Ltd.; Halloysite nanotubes: Purity 99%, purchased from Guangdong Jinna New Materials Technology Co., Ltd.; γ-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N,N-dimethylacetamide, 4-phenylethynylphthalic anhydride, phthalic anhydride, glacial acetic acid, isopropanol, methanol: Purchased from Aladdin Reagent Co., Ltd.; Water: Self-made in the laboratory.

[0049] Example 1

[0050] A treating agent for electronic-grade fiberglass cloth described in this embodiment includes the following components by weight percentage: 1.4% of a complex coupling agent, 0.3% of halloysite nanotubes modified with 4-phenylethynyl phthalic anhydride, 0.5% of methanol, 2% of glacial acetic acid, and the balance is water; the complex coupling agent includes γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 3.5:1.

[0051] The preparation method of the treating agent for electronic-grade fiberglass cloth described in this embodiment includes the following steps:

[0052] (1) Add the glacial acetic acid and methanol to water, and stir evenly to obtain a mixed aqueous solution;

[0053] (2) Mix γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent in proportion to obtain the complex coupling agent; among them, the preparation method of the imide ring-modified silane coupling agent includes the following steps: Stir and dissolve 0.1 mol of phthalic anhydride and 100 mL of glacial acetic acid, add 0.1 mol of allylamine, react at room temperature for 1 h, heat under reflux for 4 h, cool to room temperature and then add to clear water to obtain a white solid; dissolve 0.05 mol of the white solid in 100 mL of THF, add 0.55 mL of chloroplatinic acid solution, dropwise add 0.05 mol of triethoxysilane, and react at 60 °C for 10 h to obtain the imide ring-modified silane coupling agent;

[0054] (3) Add 2 g of halloysite nanotubes, 2.2 g of 4-phenylethynyl phthalic anhydride and 2 g of γ-aminopropyltriethoxysilane to 20 mL of N,N-dimethylacetamide solution, ultrasonicate at 50 °C for 12 h, wash and dry to obtain the modified halloysite nanotubes;

[0055] (4) Add the complex coupling agent and the modified halloysite nanotubes to the mixed aqueous solution, and stir evenly to obtain the treating agent for electronic-grade fiberglass cloth.

[0056] Example 2

[0057] A treating agent for electronic-grade fiberglass cloth described in this embodiment includes the following components by weight percentage: 1.5% of a complex coupling agent, 0.4% of halloysite nanotubes modified with 4-phenylethynyl phthalic anhydride, 0.6% of ethanol, 3% of glacial acetic acid, and the balance is water; the complex coupling agent includes γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 3:1.

[0058] The preparation method of the treating agent for electronic-grade fiberglass cloth described in this embodiment includes the following steps:

[0059] (1) Add the glacial acetic acid and ethanol to water, and stir evenly to obtain a mixed aqueous solution;

[0060] (2) Mix γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent in proportion to obtain the compound coupling agent; wherein, the preparation method of the imide ring-modified silane coupling agent includes the following steps: Stir and dissolve 0.1 mol of phthalic anhydride and 100 mL of glacial acetic acid, add 0.1 mol of allylamine, react at room temperature for 2 h, heat under reflux for 5 h, cool to room temperature and then add to clear water to obtain a white solid; Dissolve 0.05 mol of the white solid in 100 mL of THF, add 0.55 mL of chloroplatinic acid solution, dropwise add 0.05 mol of triethoxysilane, and react at 65 °C for 8 h to obtain the imide ring-modified silane coupling agent;

[0061] (3) Add 2 g of halloysite nanotubes, 2 g of 4-phenylethynylphthalic anhydride and 2 g of γ-aminopropyltriethoxysilane to 20 mL of N,N-dimethylacetamide solution, ultrasonicate at 60 °C for 16 h, wash and dry to obtain the modified halloysite nanotubes;

[0062] (4) Add the compound coupling agent and the modified halloysite nanotubes to the mixed aqueous solution, stir evenly to obtain the treatment agent for electronic grade fiberglass cloth.

[0063] Example 3

[0064] The treatment agent for electronic grade fiberglass cloth described in this example, by weight percentage, includes the following components: 0.5% of compound coupling agent, 0.2% of halloysite nanotubes modified with 4-phenylethynylphthalic anhydride, 0.2% of methanol, 2% of glacial acetic acid, and the balance is water; The compound coupling agent includes 3-aminopropyltrimethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 4:1.

[0065] The preparation method of the treatment agent for electronic grade fiberglass cloth described in this example, the method includes the following steps:

[0066] (1) Add the glacial acetic acid and methanol to water, stir evenly to obtain a mixed aqueous solution;

[0067] (2) Mix 3-aminopropyltrimethoxysilane and phthalic anhydride-modified silane coupling agent in proportion to obtain the compound coupling agent; wherein, the preparation method of the imide ring-modified silane coupling agent includes the following steps: Stir and dissolve 0.1 mol of phthalic anhydride and 100 mL of glacial acetic acid, add 0.1 mol of allylamine, react at room temperature for 1 h, heat under reflux for 4 h, cool to room temperature and then add to clear water to obtain a white solid; Dissolve 0.05 mol of the white solid in 100 mL of THF, add 0.55 mL of chloroplatinic acid solution, dropwise add 0.05 mol of triethoxysilane, and react at 60 °C for 10 h to obtain the imide ring-modified silane coupling agent;

[0068] (3) Add 2 g of halloysite nanotubes, 3 g of 4-phenylethynylphthalic anhydride, and 2 g of γ-aminopropyltriethoxysilane into 20 mL of N,N-dimethylacetamide solution, ultrasonicate for 12 h at 50 °C, wash and dry to obtain the modified halloysite nanotubes;

[0069] (4) Add the compound coupling agent and the modified halloysite nanotubes into the mixed aqueous solution, stir evenly to obtain the treating agent for the electronic-grade fiberglass cloth.

[0070] Comparative Example 1

[0071] The preparation method of the treating agent for the electronic-grade fiberglass cloth in this comparative example is exactly the same as that in Example 1, except that the compound silane coupling agent is γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 1:1.

[0072] Comparative Example 2

[0073] The preparation method of the treating agent for the electronic-grade fiberglass cloth in this comparative example is exactly the same as that in Example 1, except that the compound silane coupling agent is γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 6:1.

[0074] Comparative Example 3

[0075] The preparation method of the treating agent for the electronic-grade fiberglass cloth in this comparative example is exactly the same as that in Example 1, except that the compound coupling agent includes γ-aminopropyltriethoxysilane and styrylamine trimethoxysilane with a mass ratio of 3.5:1.

[0076] Comparative Example 4

[0077] The preparation method of the treating agent for the electronic-grade fiberglass cloth in this comparative example is exactly the same as that in Example 1, except that the 4-phenylethynylphthalic anhydride-modified halloysite nanotubes are replaced with an equal amount of unmodified halloysite nanotubes.

[0078] Comparative Example 5

[0079] The preparation method of the treating agent for the electronic-grade fiberglass cloth in this comparative example is exactly the same as that in Example 1, except that the weight percentage of the 4-phenylethynylphthalic anhydride-modified halloysite nanotubes is 0.8%.

[0080] Comparative Example 6

[0081] The preparation method of the treatment agent for the electronic-grade glass fiber cloth in this comparative example is exactly the same as that in Example 1, except that the halloysite nanotubes are only modified with γ-aminopropyltriethoxysilane, that is, step (3) is: adding 2 g of halloysite nanotubes and 2 g of γ-aminopropyltriethoxysilane into 20 mL of N,N-dimethylacetamide solution, ultrasonicating at 50 °C for 12 h, washing and drying to obtain the modified halloysite nanotubes.

[0082] Performance test

[0083] The treatment agents for the electronic-grade glass fiber cloth obtained in Examples 1-3 and Comparative Examples 1-6 were used to treat the 1080 electronic-grade glass fiber cloth respectively, and the method was as follows: The glass fiber cloth was first immersed in the treatment agent (at room temperature) at a speed of 30 m / min, and then dried at 120 °C. The treated electronic-grade glass fiber cloth was subjected to performance tests according to the following methods, and the specific results are shown in Table 1.

[0084] (1) Impregnability of the glass fiber cloth: The surface-treated electronic-grade glass fiber cloth was placed flat in a resin tank filled with epoxy resin of a certain viscosity, and the resin impregnation state (residual white spots, transparency) of the glass fiber cloth was observed. The time from when the glass fiber cloth was put in to when the glass fiber cloth became completely transparent was measured. The shorter the time, the better the impregnability.

[0085] (2) Adhesion test between the electronic glass fiber cloth and the resin matrix: The peel strength test was carried out according to the detection standard GB / T36476-2018.

[0086] (3) Heat resistance test: The samples that had been steamed in a PCT autoclave for 4 h were respectively put into a tin furnace at 288 °C and 300 °C for heat resistance test. At the same time, the stopwatch was started, and they were continuously immersed in the tin liquid for 300 s. Observe whether the samples burst (foam). If there is bursting (foaming), it means that the board has delaminated and failed.

[0087] Table 1 Performance data of Examples 1-3 and Comparative Examples 1-6 。

[0088] As can be seen from Table 1, the impregnation time of the electronic glass fiber cloth treated with the treating agent described in Examples 1-3 is shorter, indicating that the addition of the complex coupling agent and the modified halloysite nanotubes described in the present invention to the treating agent formulation significantly improves the impregnability of the glass fiber cloth; the peel strength of the glass fiber cloth treated with the treating agent of Examples 1-3 is higher, indicating that the treating agent described in the present invention improves the bonding performance between the electronic glass fiber cloth and the resin. The glass fiber cloth treated with the treating agent of Examples 1-3 was subjected to heat resistance tests at 288 °C and 300 °C, and no blistering or bubbling occurred in the samples, indicating that the treating agent described in the present invention improves the heat resistance of the electronic glass fiber cloth. By comparing Example 1 with Comparative Example 1, it can be seen that the content of phthalic anhydride-modified silane coupling agent in Comparative Example 1 is relatively high, and the impregnability and peel strength of the treated glass fiber cloth are both poor. By comparing Example 1 with Comparative Example 2, it can be seen that the content of γ-aminopropyltriethoxysilane in Comparative Example 2 is relatively high, and the impregnability and heat resistance of the treated glass fiber cloth are significantly reduced, indicating that the compounding ratio of the complex coupling agent has a great influence on the performance. By comparing Example 1 with Comparative Example 3, it can be seen that styrene aminotrimethoxysilane is used in Comparative Example 3, and the impregnability of the treated glass fiber cloth is significantly deteriorated, indicating that the amino silane coupling agent and the imide ring-modified silane coupling agent synergistically improve the impregnability of the glass fiber cloth. By comparing Example 1 with Comparative Example 4, it can be seen that unmodified halloysite nanotubes are used in Comparative Example 4, and the peel strength and heat resistance of the treated glass fiber cloth are reduced, indicating that 4-phenylethynylphthalic anhydride-modified halloysite nanotubes can improve the interfacial strength and heat resistance between the glass fiber cloth and the resin. By comparing Example 1 with Comparative Example 5, it can be seen that the content of the modified halloysite nanotubes in Comparative Example 5 is relatively high, and the peel strength and heat resistance of the treated glass fiber cloth are also reduced, indicating that the content of the modified halloysite nanotubes is not the more the better. By comparing Example 1 with Comparative Example 6, it can be seen that the halloysite nanotubes in Comparative Example 6 are only modified with γ-aminopropyltriethoxysilane, and the peel strength and heat resistance of the treated glass fiber cloth are significantly reduced, indicating that 4-phenylethynylphthalic anhydride-modified halloysite nanotubes can significantly improve the bonding performance between the electronic glass fiber cloth and the resin, and at the same time improve the impregnability and heat resistance of the electronic glass fiber cloth.

[0089] It can be seen that in the present invention, by selecting specific amino silane coupling agents and imide ring-modified silane coupling agents for compounding and further regulating the compounding ratio, it is ensured that the compound coupling agent has appropriate activity, and the two act synergistically, thereby improving the bonding performance between the electronic-grade glass fiber cloth and the resin, and at the same time improving the impregnation property and heat resistance of the electronic-grade glass fiber cloth. The present invention uses an amino silane coupling agent as the main coupling agent, and the amino functional group can chemically react with a resin matrix such as epoxy resin, significantly improving the interfacial bonding strength. In addition, in the present invention, by adding a certain amount of imide ring-modified silane coupling agent, due to its imide ring with a planar symmetric ring structure, it has high thermal stability, and at the same time, due to the inductive effect of the carbonyl group on the imide ring, it has strong polarity and can interact with the glass fiber cloth to a certain extent, thereby improving the impregnation property of the glass fiber cloth. After the impregnation property is improved, it will further promote the chemical reaction between the amino silane coupling agent and the resin matrix such as epoxy resin, and further improve the bonding performance between the electronic-grade glass fiber cloth and the resin. In addition, in the present invention, by incorporating a certain amount of modified halloysite nanotubes, the mechanical interlock between the glass fiber cloth and the resin matrix is improved, thereby effectively improving the interfacial bonding strength. Further, by modifying the halloysite nanotubes with 4-phenylethynylphthalic anhydride, the dispersibility and heat resistance of the halloysite nanotubes are improved, and during the processing, the halloysite nanotubes are not easily detached from the glass fiber cloth, better playing the role of mechanical interlock, thereby strengthening the interfacial bonding strength between the glass fiber cloth and the resin matrix.

[0090] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly explaining the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A treating agent for electronic-grade fiberglass cloth, characterized in that, By weight percentage, it comprises the following components: 0.5 - 1.5% of a compound coupling agent, 0.2 - 0.4% of modified halloysite nanotubes, 0.2 - 0.6% of alcohol, 2 - 3% of an acidic regulator, and the balance is water; the compound coupling agent comprises an amino - type silane coupling agent and an imide - ring - modified silane coupling agent with a mass ratio of 3 - 4:1; the preparation method of the modified halloysite nanotubes is: adding halloysite nanotubes, 4 - phenylethynylphthalic anhydride, and γ - aminopropyltriethoxysilane into an N,N - dimethylacetamide solution, ultrasonically treating at 50 - 60 °C for 12 - 16 h, washing and drying to obtain the modified halloysite nanotubes.

2. The treating agent for electronic-grade fiberglass cloth according to claim 1, characterized in that, The amino - type silane coupling agent is selected from at least one of γ - aminopropyltriethoxysilane and 3 - aminopropyltrimethoxysilane.

3. The treating agent for an electronic-grade fiberglass cloth according to claim 1, characterized in that, The acidic regulator is glacial acetic acid.

4. The treating agent for an electronic-grade fiberglass cloth according to claim 1, characterized in that, The alcohol comprises one or more of methanol, ethanol, or glycerol.

5. A method for preparing a treating agent for an electronic-grade glass fiber cloth according to any one of claims 1-4, characterized in that, The method comprises the following steps: (1) Adding the acidity regulator and alcohol into water, and stirring evenly to obtain a mixed aqueous solution; (2) Mixing the amino - type silane coupling agent and the imide - ring - modified silane coupling agent in proportion to obtain the compound coupling agent; (3) Adding halloysite nanotubes, 4 - phenylethynylphthalic anhydride, and γ - aminopropyltriethoxysilane into an N,N - dimethylacetamide solution, ultrasonically treating at 50 - 60 °C for 12 - 16 h, washing and drying to obtain the modified halloysite nanotubes; (4) Adding the compound coupling agent and the modified halloysite nanotubes into the mixed aqueous solution, and stirring evenly to obtain the treating agent for electronic - grade glass fiber cloth.

6. The preparation method of a treating agent for electronic-grade fiberglass cloth according to claim 5, characterized in that, The preparation method of the imide - ring - modified silane coupling agent comprises the following steps: stirring and dissolving phthalic anhydride and glacial acetic acid, adding allylamine, reacting at room temperature for 1 - 2 h, heating under reflux for 4 - 5 h, cooling to room temperature and then adding to clear water to obtain a white solid; dissolving a certain amount of the white solid in THF, adding a chloroplatinic acid solution, dropping triethoxysilane, and reacting at 60 - 65 °C for 8 - 10 h to obtain the imide - ring - modified silane coupling agent.

7. The preparation method of a treating agent for electronic-grade fiberglass cloth according to claim 5, characterized in that In step (3), the mass ratio of the halloysite nanotubes, 4 - phenylethynylphthalic anhydride, and γ - aminopropyltriethoxysilane is 1:1 - 1.5:

1.

8. Application of the treating agent according to any one of claims 1 - 4 or the treating agent prepared by the method according to any one of claims 5 - 7 in electronic - grade glass fiber cloth.