Treating agent for electronic-grade glass fiber cloth as well as preparation method and application of treating agent

Abstract

The invention discloses a treating agent for electronic-grade glass fiber cloth as well as a preparation method and application thereof, and belongs to the field of glass fiber cloth treating agents. The treating agent for the electronic-grade glass fiber cloth is prepared from the following components in percentage by weight: 0.5 to 1.5 percent of compound coupling agent, 0.2 to 0.4 percent of modified halloysite nanotube, 0.2 to 0.6 percent of alcohol, 2 to 3 percent of acidity regulator and the balance of 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. According to the treating agent for the electronic-grade glass fiber cloth, the bonding performance of the electronic-grade glass fiber cloth and resin can be improved, and meanwhile the impregnation property and the heat resistance of the electronic-grade glass fiber cloth are improved.

Description

Technical Field

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

[0002] A glass fiber cloth is a cloth woven from glass fibers, which usually has excellent insulation properties, electrical properties, weather resistance, chemical corrosion resistance, and dimensional stability, and is widely used in printed circuit boards for insulation and reinforcement. However, since glass fiber is an inorganic material and resin is an organic material, a treating agent is required for their effective combination. 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, thus affecting the insulation reliability of the printed circuit board. In addition, due to the development of electronic products towards smaller, lighter, and thinner directions, the substrates of printed circuit boards are also required to be high-density and multi-layered, which puts higher requirements on the performance of electronic-grade glass fiber cloth, requiring faster and more uniform impregnation of the electronic-grade glass fiber cloth with resin.

[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 insufficient uniformity of the treating agent in wetting 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, the purpose 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 impregnation property and heat resistance of the electronic-grade glass fiber cloth.

[0005] To achieve the above purpose, 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 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 being water; 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.

[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 comprises 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 with a certain strength, 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 treating 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-phenylethynyl phthalic anhydride. Preferably, the halloysite nanotubes have 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 interlocking 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-phenylethynyl phthalic 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 interlocking, thereby strengthening the interfacial bonding strength between the glass fiber cloth and the resin matrix.

[0011] In the present invention, in the treating agent for the electronic-grade glass fiber cloth, the weight percentage of the acidic 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 acidic regulator is glacial acetic acid.

[0012] In the present invention, in the treating 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-mentioned treating agent for the electronic-grade glass fiber cloth, and the method includes the following steps: (1) Add the acidity regulator and the alcohol to water and stir evenly to obtain a mixed aqueous solution; (2) Mix the amino silane coupling agent and the imide ring-modified silane coupling agent in proportion to obtain the composite coupling agent; (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; (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.

[0014] 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.

[0015] In the present invention, in step (2), mix the amino-functional 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 under 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).

[0016] 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.

[0017] 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.

[0018] According to another aspect of the present invention, there is also provided an application of the above treatment agent or the treatment agent prepared according to the above method in an electronic grade fiberglass cloth.

[0019] Compared with the prior art, the beneficial effects of the present invention are as follows: (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 agent has appropriate activity. 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 interact with the glass fiber cloth with a certain strength, 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.

[0020] (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.

[0021] (3) The present invention also provides a preparation method for the 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

[0022] 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 expressions mentioned in the specification and claims. Unless otherwise specified, all technical and scientific terms used herein shall have the ordinary meanings understood by those skilled in the art regarding the present invention. In case of conflict, the definitions in this specification shall prevail.

[0023] The theories or mechanisms described and disclosed herein, whether correct or incorrect, shall not limit the scope of the present invention in any way, that is, the content of the present invention can be implemented without being limited by any specific theory or mechanism.

[0024] In this text, when describing embodiments or examples, it should be understood that it is 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.

[0025] In this text, for the sake of brevity of description, not all possible combinations of all technical features in each embodiment or example are 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 to be within the scope described in this specification.

[0026] 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 alcohol, 2 - 3% of an acidic regulator, and the balance is 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.

[0027] In some embodiments, the amino-silane coupling agent is selected from at least one of γ-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.

[0028] In some embodiments, the imide-ring modified silane coupling agent is a phthalic anhydride modified silane coupling agent.

[0029] In some embodiments, the modified halloysite nanotubes are halloysite nanotubes modified with 4-phenylethynylphthalic anhydride.

[0030] In some embodiments, the acidic regulator is glacial acetic acid.

[0031] In some embodiments, the alcohol comprises one or more of methanol, ethanol, or glycerol.

[0032] 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: (1) Add the acidity regulator and alcohol to water, and stir evenly to obtain a mixed aqueous solution; (2) Mix the amino-silane coupling agent and the imide-ring modified silane coupling agent in proportion to obtain the compound coupling agent; (3) Add halloysite nanotubes, 4-phenylethynylphthalic anhydride, and γ-aminopropyltriethoxysilane to an N,N-dimethylacetamide solution, ultrasonic at 50 - 60 °C for 12 - 16 h, wash and dry to obtain the modified halloysite nanotubes; (4) Add the complex coupling agent and the modified halloysite nanotubes into the mixed aqueous solution, and stir evenly to obtain the treating agent for the electronic grade fiberglass cloth.

[0033] In some embodiments, the preparation method of the imide ring modified silane coupling agent comprises 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, and add to clear water after cooling to room temperature 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.

[0034] 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.

[0035] The present invention also provides an application of the above treating agent or the treating agent prepared according to the above method in an electronic grade fiberglass cloth.

[0036] 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.

[0037] Example 1 is the best example.

[0038] The chemical auxiliaries used in the examples and comparative examples of the present invention are all commercially available, and the specific information is as follows: 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.

[0039] Example 1 The treating agent for the electronic grade fiberglass cloth described in this example, by weight percentage, comprises the following components: complex coupling agent 1.4%, 4-phenylethynylphthalic anhydride modified halloysite nanotubes 0.3%, methanol 0.5%, glacial acetic acid 2%, and the balance is water; The complex coupling agent comprises γ-aminopropyltriethoxysilane and phthalic anhydride modified silane coupling agent with a mass ratio of 3.5:1.

[0040] The preparation method of the treating agent for electronic glass fiber cloth in this embodiment includes the following steps: (1) Add the glacial acetic acid and methanol into water, and stir evenly to obtain a mixed aqueous solution; (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 1 h, heat 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; (3) Add 2 g of halloysite nanotubes, 2.2 g of 4-phenylethynylphthalic anhydride and 2 g of γ-aminopropyltriethoxysilane into 20 mL of N,N-dimethylacetamide solution, ultrasonically treat at 50 °C for 12 h, wash and dry to obtain the modified halloysite nanotubes; (4) Add the compound coupling agent and the modified halloysite nanotubes into the mixed aqueous solution, and stir evenly to obtain the treating agent for electronic glass fiber cloth.

[0041] Example 2 The treating agent for electronic glass fiber cloth in this embodiment, by weight percentage, includes the following components: 1.5% of compound coupling agent, 0.4% of halloysite nanotubes modified by 4-phenylethynylphthalic anhydride, 0.6% of ethanol, 3% of glacial acetic acid, and the balance is water; the compound coupling agent includes γ-aminopropyltriethoxysilane and phthalic anhydride modified silane coupling agent with a mass ratio of 3:1.

[0042] The preparation method of the treating agent for electronic glass fiber cloth in this embodiment includes the following steps: (1) Add the glacial acetic acid and ethanol into water, and stir evenly to obtain a mixed aqueous solution; (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 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; (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; (4) Add the complex coupling agent and the modified halloysite nanotubes to the mixed aqueous solution, stir evenly to obtain the treating agent for the electronic-grade fiberglass cloth.

[0043] Example 3 A treating agent for an electronic-grade fiberglass cloth according to this example, by weight percentage, comprises the following components: 0.5% of a complex 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 complex coupling agent comprises 3-aminopropyltrimethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 4:1.

[0044] The preparation method of the treating agent for the electronic-grade fiberglass cloth according to this example, the method comprises the following steps: (1) Add the glacial acetic acid and methanol to water, stir evenly to obtain a mixed aqueous solution; (2) Mix 3-aminopropyltrimethoxysilane and phthalic anhydride-modified silane coupling agent in proportion to obtain the complex coupling agent; wherein, the preparation method of the imide ring-modified silane coupling agent comprises 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; (3) Add 2 g of halloysite nanotubes, 3 g of 4-phenylethynylphthalic 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; (4) Add the complex coupling agent and the modified halloysite nanotubes to the mixed aqueous solution, stir evenly to obtain the treating agent for the electronic-grade fiberglass cloth.

[0045] Comparative Example 1 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, the only difference being that the complex silane coupling agent is γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 1:1.

[0046] Comparative Example 2 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 compounded silane coupling agent is γ-aminopropyltriethoxysilane and phthalic anhydride-modified silane coupling agent with a mass ratio of 6:1.

[0047] Comparative Example 3 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 compounded coupling agent includes γ-aminopropyltriethoxysilane and styrene amino trimethoxysilane with a mass ratio of 3.5:1.

[0048] Comparative Example 4 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 4-phenylethynylphthalic anhydride-modified halloysite nanotubes are replaced with an equal amount of unmodified halloysite nanotubes.

[0049] Comparative Example 5 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 weight percentage of the 4-phenylethynylphthalic anhydride-modified halloysite nanotubes is 0.8%.

[0050] Comparative Example 6 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.

[0051] Performance Test 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.

[0052] (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, and 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.

[0053] (2)Adhesion test of electronic glass fiber cloth and resin matrix: The peel strength test was carried out in accordance with the detection standard GB / T36476-2018.

[0054] (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, start the stopwatch and soak continuously in the molten tin for 300 s. Observe whether the samples are delaminated (bubbled). If there is delamination (bubbling), it indicates that the board has delaminated and failed.

[0055] Table 1 Performance data of Examples 1-3 and Comparative Examples 1-6 。

[0056] As can be seen from Table 1, the impregnation time of the electronic-grade 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-grade glass fiber cloth and the resin. The glass fiber cloth treated with the treating agent of Examples 1-3 was subjected to a heat resistance test 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-grade glass fiber cloth. By comparing Example 1 with Comparative Example 1, it can be seen that the content of the 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 higher 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-grade glass fiber cloth and the resin, and at the same time improve the impregnability and heat resistance of the electronic-grade glass fiber cloth.

[0057] 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, the appropriate activity of the compound coupling agent is ensured. 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, 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. 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 with a certain strength, 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 then 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 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.

[0058] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limiting the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or variations can be made on the basis of the above description. It is impossible to enumerate all the implementation manners here. Any obvious changes or variations derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A treatment agent for electronic grade glass fiber cloth, characterized in that: The invention comprises the following components by weight percentage: 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 of water; the complex coupling agent comprises an amino silane coupling agent and an imide ring modified silane coupling agent in a mass ratio of 3-4:

1.

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

3. The electronic grade glass fiber cloth treating agent according to claim 1, characterized in that: The imide ring modified silane coupling agent is a phthalic anhydride modified silane coupling agent.

4. The electronic grade glass fiber cloth treating agent according to claim 1, characterized in that: The modified halloysite nanotube is a halloysite nanotube modified with 4-phenylethynylphthalic anhydride.

5. The electronic grade glass fiber cloth treating agent according to claim 1, characterized in that: The acidity regulator is glacial acetic acid.

6. The electronic grade glass fiber cloth treating agent according to claim 1, characterized in that: The alcohol includes one or more of methanol, ethanol or glycerol.

7. The method for preparing a treatment agent for electronic grade glass fiber cloth according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: (1) adding an acidity regulator and alcohol into water and stirring uniformly to obtain a mixed aqueous solution; (2) mixing an amino silane coupling agent and an imide ring modified silane coupling agent in a certain proportion to obtain the complex coupling agent; (3) adding halloysite nanotubes, 4-phenylethynylphthalic anhydride and γ-aminopropyltriethoxysilane to N,N-dimethylacetamide solution, ultrasonicating at 50-60° C. for 12-16 hours, washing and drying to obtain the modified halloysite nanotubes; (4) Adding the complex coupling agent and the modified halloysite nanotubes into the mixed aqueous solution and stirring evenly to obtain the electronic grade glass fiber cloth treating agent.

8. The method for preparing a treatment agent for electronic grade glass fiber cloth according to claim 7, 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 hours, heating and reflux for 4-5 hours, cooling to room temperature and adding to clean water to obtain a white solid; dissolving a certain amount of the white solid in THF, adding chloroplatinic acid solution, dripping triethoxysilane, reacting at 60-65° C. for 8-10 hours, and obtaining the imide ring modified silane coupling agent.

9. The method for preparing a treatment agent for electronic grade glass fiber cloth according to claim 7, 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.

10. Use of the treatment agent according to any one of claims 1 to 6 or the treatment agent prepared according to the method according to any one of claims 7 to 9 in electronic grade glass fiber cloth.