Treatment agents for a low-dielectric, electronic-grade glass fiber fabric and manufacturing processes for it

Abstract

Treatment agent for a low-dielectric, electronic-grade glass fiber fabric comprising the following starting materials in weight percent: 0.6% to 1.2% of a coupling agent A, 0.3% to 0.8% of a coupling agent B, 0.01% to 1.5% of a coupling agent additive, 0.1% to 0.5% of an alcohol, 0.1% to 0.5% of an acid, and water for the remainder, wherein the ratio of coupling agent A to coupling agent B is (1.2-2.3):1; wherein the coupling agent A is a vinyl-containing coupling agent; the coupling agent B is a vinylbenzyl-containing coupling agent; and the coupling agent additive is a salt of a maleic anhydride (MA)-grafted copolymer; where a general structural formula of the coupling agent A CH2=CH(CH2) n SiX3 is where n is an integer between 0 and 3, and X is methoxy-, ethoxy-, methoxyethoxy- or acetoxy-; where a general structural formula of the coupling agent B CH2=CH(C6H4)CH2(CH2) n SiX3 is where n is an integer between 0 and 3, and X is methoxy, ethoxy, methoxyethoxy or Acetoxy- is; wherein the coupling agent additive is one or more of a sodium salt of a butadiene-MA copolymer, an ammonium salt of a butadiene-MA copolymer, a sodium salt of a dimethyldiallyl-MA copolymer and an amine salt of a dimethyldiallyl-MA copolymer.

Description

TECHNICAL AREA

[0001] The present invention belongs to the technical field of glass fiber treatment agents and relates in particular to a treatment agent for a low-dielectric glass fiber fabric of electronic quality and a manufacturing process for it. BACKGROUND

[0002] Document US 6,270,897 B1 describes a coupling agent system for composite fibers. Document US 2009 / 0206296 A1 relates to organosilane compositions that can be used to improve the water repellency and other surface properties of fabrics, garments, textiles, and other materials, and manufacturing processes for such compositions. Document US 3,855,195 A discloses a process for producing pure m-cresol. Document WO 02 / 092903 A1 relates to a glass fabric and its applications. Document CN 112,695,520 A describes a high-temperature-resistant surface treatment agent for electronic-grade glass fabrics and a manufacturing process for it. Document CN 110,981,222 A also relates to a treatment agent, in particular an impregnating agent, for glass fibers, and a process for its manufacture and application.Document CN 1 06 543 554 A describes a glass fiber-reinforced polypropylene material with a low dielectric constant and a method for its production. Document CN 1 12 813 684 A also discloses an electronics-grade glass fiber fabric with a low dielectric constant and a method for its production. Document CN 1 06 868 866 A discloses another surface treatment agent for glass fiber fabrics and a manufacturing method for them. The surface treatment agent provided is a multifunctional silane adhesive that can achieve a high-strength bond between a glass fiber fabric and a resin, and can also improve high-temperature and weather resistance and increase mechanical strength. Document JP H11 - 236 249 A discloses a coupling agent for glass fibers and glass fiber structures bonded with the coupling agent.

[0003] With the rapid development of 5G technology, the demands on printed circuit board (PCB) materials in high-frequency and high-speed applications are constantly increasing, inevitably leading to higher demands on a treatment agent for electronic-grade glass fiber fabric as one of the input materials for copper-clad laminate (CCL). Most current PCB materials are epoxy resin systems that have relatively low requirements for dielectric constant and dielectric loss. However, for some package carrier boards for ultra-thin integrated circuits (ICs) with fabric, high-frequency and high-speed boards, or similar applications, existing treatment agent formulations cannot meet the performance requirements of low-dielectric resin systems.Therefore, developing a treatment formulation for electronics-grade, low-dielectric glass fiber fabric is of great importance. Existing treatment formulations for low-dielectric glass fiber fabrics encounter problems in application, such as long penetration times and blistering in customer products due to poor impregnation performance.

[0004] For example, patent CN 1 03 556 461 B discloses a surface treatment agent for an electronics-grade glass fiber fabric, and the treatment agent consists of a silane coupling agent (SCA) with the general formula Y(CH2) nSiX3, acetic acid, and deionized water are used to produce the fiber, where Y is an organic functional group that is vinyl, amino, epoxy, methacryloyloxy, mercapto, or carbamido; and X is a hydrolyzable group that is chlorine, methoxy, ethoxy, methoxyethoxy, or acetoxy. An electronic-grade fiberglass fabric produced using this treatment formulation in combination with a pretreatment process offers advantages such as high heat resistance, ion migration resistance, and rapid resin wettability.

[0005] Patent CN1 07 119 455 A discloses a post-treatment compound for a fiberglass fabric made from the following starting materials: vinyl-containing SCA A, epoxy-containing SCA B, a pH adjuster, a surfactant, and deionized water, wherein the SCA A content is 1.1 to 1.5 times that of the SCA B content. The post-treatment compound has excellent storage stability, strong adhesion to a resin, and a certain degree of stiffness.

[0006] Patent CN 1 05 401 423 B discloses a post-treatment agent for electronic-grade glass fiber fabric, which is produced from the following components: a pH adjuster, amino-SCA, a fluorocarbon surfactant, and deionized water. Electronic-grade glass fiber fabric treated with this agent has advantages such as high mechanical strength, excellent heat resistance, and high product yield.

[0007] The coupling agent hydrolysis processes involved in the aforementioned patents are conventional hydrolysis methods for coupling agents. The surfactant is used to reduce the surface tension of a solution and minimize bubble formation during use. However, for low-dielectric fiberglass fabrics, an added fluorocarbon or hydrocarbon surfactant will adsorb salt ions, impairing the electrical performance of the electronic fabric. Therefore, it is necessary to address the challenges of selecting and matching a treatment agent to a specific resin type, particularly the issues of treatment agent adhesion to low-dielectric resins such as polyphenylene oxide (PPO). SUMMARY

[0008] Technical problems to be solved by the present disclosure: The present disclosure provides a treatment agent for a low-dielectric, electronic-grade glass fiber fabric, wherein the treatment agent, while maintaining the low-dielectric performance, improves the bond strength of the low-dielectric glass fiber fabric to a resin and increases the mechanical performance and heat resistance of the low-dielectric glass fiber fabric; wherein the present disclosure also provides a method for producing the treatment agent. The treatment agent for a low-dielectric, electronic-grade glass fiber fabric according to the invention has the features of claim 1. Further embodiments of the treatment agent are the subject of the dependent claims.The manufacturing process according to the invention for the treatment agent for the low-dielectric glass fiber fabric in electronics quality has the features of claim 6. A further embodiment is the subject of claim 7.

[0009] The treatment composition disclosed herein for a low-dielectric, electronic-grade glass fiber fabric is prepared from the following starting materials in weight percent: a coupling agent A: 0.6% to 1.2%, a coupling agent B: 0.3% to 0.8%, a coupling agent additive: 0.01% to 1.5%, an alcohol: 0.1% to 0.5%, an acid: 0.1% to 0.5%, and water: the remainder.

[0010] The coupling agent A is a vinyl-containing coupling agent.

[0011] A general structural formula of the coupling agent A CH2=CH(CH2) n SiX3, where n is an integer between 0 and 3, and X is a hydrolyzable group and is methoxy-, ethoxy-, methoxyethoxy- or acetoxy-.

[0012] A general structural formula of the coupling agent B CH2=CH(C6H4)CH2(CH2) n SiX3, where n is an integer between 0 and 3, and X is a hydrolyzable group and is methoxy-, ethoxy-, methoxyethoxy- or acetoxy-.

[0013] Furthermore, the coupling agent A is preferably one or more of vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane and propylene trimethoxysilane.

[0014] The content of coupling agent A is 0.6% to 1.2%, and preferably 0.8% to 1.1%. If the content of coupling agent A is too low, there will be a small number of nonpolar groups, and an addition reaction with a resin will be slowed down; and if the content of coupling agent A is too high, there will be an ineffective accumulation of the coupling agent on the surface of a fiberglass fabric, and, after being deposited for a long time, the coupling agent will undergo further polycondensation, forming ineffective components and thus increasing the cost.

[0015] The coupling agent B is a vinylbenzyl-containing coupling agent.

[0016] Furthermore, the coupling agent B is preferably one or more of vinylbenzyltriethoxysilane, β-(Vinylbenzyl)propyltriethoxysilane and vinylbenzyltrimethoxysilane.

[0017] The concentration of coupling agent B is 0.3% to 0.8%, and preferably 0.4% to 0.6%. If the concentration of coupling agent B is too low, only a small number of free radicals are provided, which reduces the reaction rate between the coupling agent and a resin; and if the concentration of coupling agent B is too high, there will be an ineffective accumulation of the coupling agent on the surface of a fiberglass fabric, and, after being deposited for a long time, the coupling agent will undergo further polycondensation, forming ineffective components and thus increasing costs.

[0018] The ratio of coupling agent A to coupling agent B is (1.2-2.3):1. If the ratio of coupling agent A to coupling agent B is too high, the effect of vinylbenzyl in coupling agent B to provide stable electrons is reduced; and if the ratio of coupling agent A to coupling agent B is too low, the effect of the nonpolar groups in coupling agent A to participate in a reaction with a resin is reduced.

[0019] Coupling agent A and coupling agent B are used in combination. Coupling agent A contains nonpolar groups that can not only reduce surface tension but also undergo an addition reaction with a resin system with low dielectricity (e.g., a PPO resin). It is a low-molecular-weight, short-chain coupling agent with low molecular weight, high capillary action, and high permeability, allowing it to penetrate glass fibers well. Coupling agent B contains vinylbenzyl, which is heat-resistant, lubricious, and electronically stable. It can rapidly generate free radicals to accelerate the reaction with a low-dielectric resin while simultaneously increasing heat resistance.

[0020] The coupling agent additive is a salt of an MA-grafted copolymer.

[0021] The coupling agent additive is one or more of a sodium salt of a butadiene-MA copolymer, an ammonium salt of a butadiene-MA copolymer, a sodium salt of a dimethyldiallyl-MA copolymer and an amine salt of a dimethyldiallyl-MA copolymer.

[0022] The concentration of the coupling agent additive is 0.01% to 1.5%, and preferably 0.05% to 1.0%. If the concentration of the coupling agent additive is too high, the coupling effects of coupling agent A and coupling agent B are inhibited, and the cost of the starting materials increases; and if the concentration of the coupling agent additive is too low, the strengthening effects of the coupling agents binding to a resin are weakened.

[0023] Acidic anhydride groups in the coupling agent additive can undergo a general dehydration reaction with the polar groups (-NH2 and -OH) to form chemical bonds, so that incompatible polar and nonpolar substances are chemically coupled, further enhancing the bonding of the coupling agents to a resin.

[0024] The acid is a low-molecular-weight organic acid with 1 to 5 carbon atoms and is, for example, formic acid or acetic acid. The pH of the treatment agent is adjusted to a suitable range using the acid.

[0025] Alcohol is a low molecular weight organic alcohol with 1 to 5 carbon atoms and is, for example, methanol, ethanol or glycerin.

[0026] Compared with the conventional addition of a surfactant, the use of an alcohol as a co-solvent can increase the solubilities of the coupling agents, reduce the surface tension of a solution, and promote the bonding of the treatment agent to the glass fibers; and the alcohol can evaporate in the subsequent drying step, reducing its influence on any reaction between the coupling agents and a resin.

[0027] The manufacturing process of the treatment agent for a low-dielectric, electronic-grade glass fiber fabric according to the present invention comprises the following steps: (1) Add clean water to a preparation container and begin stirring; (2) thoroughly mixing the acid and the alcohol with a stirrer and adding the resulting mixture to the preparation container; (3) Add coupling agent A and coupling agent B successively to the preparation container and stir until a resulting aqueous solution is clear and transparent; and (4) Add the coupling agent additive to the preparation container and stir thoroughly to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric.

[0028] The treatment agent for a low-dielectric, electronic-grade glass fiber fabric has a pH of 4 to 6, and after its preparation, the treatment agent is stored under slow stirring for later use.

[0029] In comparison with the prior art, the present invention provides the following advantageous effects: (1) According to the invention, a vinyl-containing coupling agent A and a vinylbenzyl-containing coupling agent B are used in combination. Coupling agent A contains nonpolar groups that can not only reduce surface tension but also undergo an addition reaction with a low-dielectric resin system (such as a PPO resin). Coupling agent B contains vinylbenzyl, which is heat-resistant, lubricious, and electronically stable, and can rapidly form free radicals to accelerate a reaction with a low-dielectric resin while improving heat resistance. Furthermore, a low-molecular-weight, short-chain coupling agent is used in conjunction with coupling agent A, which has a low molecular weight, high capillary action, and high permeability, and can penetrate glass fibers well.During the downstream production of a customer's prepreg, a resin has a low viscosity in a low-temperature phase, which promotes the penetration of glass fibers. (2) In contrast to the conventional addition of a surfactant, the use of an alcohol as a co-solvent disclosed herein can increase the solubilities of the coupling agents, reduce the surface tension of a solution and promote the bonding of the treatment agent to glass fibers; the alcohol can evaporate in the subsequent drying step, thereby reducing its influence on a reaction between the coupling agents and a resin. (3) According to the present disclosure, a salt of an MA-grafted material is added as a coupling agent additive. Acid anhydride groups in the coupling agent additive can undergo a general dehydration reaction with the polar groups (-NH2 and -OH) to form chemical bonds, so that incompatible polar and nonpolar substances are chemically coupled, thereby further enhancing the bonding of the coupling agents to a resin. (4) According to the present disclosure, no fluorocarbon surfactants or hydrocarbon surfactants are used, which reduces bubble formation during use, avoids the addition of an ineffective defoaming agent and prevents the adsorption of salt ions, which affects the electrical performance of an electronic fabric. (5) According to the present disclosure, an alcohol is used as a solvent. The alcohol can generate a large number of hydrogen bonds, which ensure the relatively stable existence of silanol formed after hydrolysis of the coupling agents and reduce the likelihood of silanol hydroxyl undergoing a condensation reaction. DETAILED DESCRIPTION OF THE EXAMPLES OF EXECUTION

[0030] The present invention is described in more detail below with reference to examples, although the present invention is not limited to the scope of the examples described. The experimental methods in the following examples, which are not specified with particular conditions, are carried out under conventional conditions or according to the product instructions. Example 1

[0031] A treatment agent for a low-dielectric, electronic-grade glass fiber fabric was prepared from the following starting materials: vinyl triethoxysilane: 1.0%, vinyl benzyl triethoxysilane: 0.7%, a sodium salt of a butadiene-MA copolymer (a molar ratio of butadiene to MA was 6:4, and a molecular weight was 4000): 1.5%, methanol: 0.15%, acetic acid: 0.25%, and purified water: the remainder.

[0032] One manufacturing process was as follows: (1) The starting materials were weighed precisely according to the recipe. The purified water was placed in a preparation container and stirring was started. (2) The methanol and the acetic acid were thoroughly mixed using a stirrer and then added to the preparation container. (3) The vinyltriethoxysilane and the vinylbenzyltriethoxysilane were added successively to the preparation container and the resulting mixture was stirred until a clear and transparent aqueous solution was obtained. (4) The sodium salt of the butadiene-MA copolymer was added to the preparation vessel and the resulting mixture was thoroughly stirred to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric, which had a pH of 4.3 and was stored under slow stirring for later use. Example 2

[0033] A treatment agent for a low-dielectric, electronic-grade glass fiber fabric was prepared from the following starting materials: vinyltris(β-methoxyethoxy)silane: 0.65%, β-(vinylbenzyl)propyltriethoxysilane: 0.3%, an amine salt of a butadiene-MA copolymer (a molar ratio of butadiene to MA was 6:4, and a molecular weight was 7000): 0.4%, methanol: 0.10%, acetic acid: 0.50%, and purified water: the remainder.

[0034] One manufacturing process was as follows: (1) The starting materials were weighed precisely according to the recipe. The purified water was placed in a preparation container and stirring was started. (2) The methanol and the acetic acid were thoroughly mixed using a stirrer and then added to the preparation container. (3) The vinyltris(β-methoxyethoxy)silane and the β-(vinylbenzyl)propyltriethoxysilane were added successively to the preparation container and the resulting mixture was stirred until a clear and transparent aqueous solution was obtained. (4) The amine salt of the butadiene-MA copolymer was added to the preparation vessel and the resulting mixture was thoroughly stirred to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric, which had a pH of 4.6 and was stored under slow stirring for later use. Example 3

[0035] A treatment agent for a low-dielectric, electronic-grade glass fiber fabric was prepared from the following starting materials: vinyl triethoxysilane: 0.6%, vinyl benzyl triethoxysilane: 0.3%, a sodium salt of a dimethyl diallyl-MA copolymer (a molar ratio of dimethyl diallyl to MA was 6:4, and a molecular weight was 5500): 0.8%, ethanol: 0.1%, acetic acid: 0.3%, and purified water: the remainder.

[0036] One manufacturing process was as follows: (1) The starting materials were weighed precisely according to the recipe. The purified water was placed in a preparation container and stirring was started. (2) The ethanol and acetic acid were thoroughly mixed using a stirrer and then added to the preparation container. (3) The vinyltriethoxysilane and the vinylbenzyltriethoxysilane were added successively to the preparation container and the resulting mixture was stirred until a clear and transparent aqueous solution was obtained. (4) The sodium salt of the dimethyldiallyl-MA copolymer was added to the preparation container and the resulting mixture was thoroughly stirred to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric, which had a pH of 4.5 and was stored under slow stirring for later use. Example 4

[0037] A treatment agent for a low-dielectric, electronic-grade glass fiber fabric was prepared from the following starting materials: propylene trimethoxysilane: 0.8%, β-(vinylbenzyl)propyltriethoxysilane: 0.6%, an amine salt of a dimethyl diallyl-MA copolymer (a molar ratio of dimethyl diallyl to MA was 5:4, and a molecular weight was 5500): 0.01%, ethanol: 0.15%, acetic acid: 0.1%, and purified water: the remainder.

[0038] One manufacturing process was as follows: (1) The starting materials were weighed precisely according to the recipe. The purified water was placed in a preparation container and stirring was started. (2) The ethanol and acetic acid were thoroughly mixed using a stirrer and then added to the preparation container. (3) The propylene trimethoxysilane and the β-(vinylbenzyl)propyl triethoxysilane were added successively to the preparation container and the resulting mixture was stirred until a clear and transparent aqueous solution was obtained. (4) The amine salt of the dimethyldiallyl MA copolymer was added to the preparation vessel and a resulting mixture was thoroughly stirred to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric, which had a pH of 4.7 and was stored under slow stirring for later use. Example 5

[0039] A treatment agent for a low-dielectric, electronic-grade glass fiber fabric was prepared from the following starting materials: propylene trimethoxysilane: 1.2%, β-(vinylbenzyl)propyl triethoxysilane: 0.8%, an amine salt of a dimethyl diallyl-MA copolymer (a molar ratio of dimethyl diallyl to MA was 5:4, and a molecular weight was 5500): 0.05%, glycerol: 0.5%, acetic acid: 0.25%, and purified water: the remainder.

[0040] One manufacturing process was as follows: (1) The starting materials were weighed precisely according to the recipe. The purified water was placed in a preparation container and stirring was started. (2) The glycerol and the acetic acid were thoroughly mixed using a stirrer and then added to the preparation container. (3) The propylene trimethoxysilane and the β-(vinylbenzyl)propyl triethoxysilane were added successively to the preparation container and the resulting mixture was stirred until a clear and transparent aqueous solution was obtained. (4) The amine salt of the dimethyldiallyl MA copolymer was added to the preparation vessel and the resulting mixture was thoroughly stirred to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric, which had a pH of 4.8 and was stored under slow stirring for later use. Example 6

[0041] A treatment agent for a low-dielectric, electronic-grade glass fiber fabric was prepared from the following starting materials: propylene trimethoxysilane: 0.8%, β-(vinylbenzyl)propyltriethoxysilane: 0.5%, an amine salt of a dimethyl diallyl-MA copolymer (a molar ratio of dimethyl diallyl to MA was 5:4, and a molecular weight was 4500): 1.0%, ethylene glycol (EG): 0.15%, acetic acid: 0.45%, and purified water: the remainder.

[0042] One manufacturing process was as follows: (1) The starting materials were weighed precisely according to the recipe. The purified water was placed in a preparation container and stirring was started. (2) The EC and the acetic acid were thoroughly mixed using a stirrer and then added to the preparation container. (3) The propylene trimethoxysilane and the β-(vinylbenzyl)propyl triethoxysilane were added successively to the preparation container and the resulting mixture was stirred until a clear and transparent aqueous solution was obtained. (4) The amine salt of the dimethyldiallyl MA copolymer was added to the preparation vessel and a resulting mixture was thoroughly stirred to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric, which had a pH of 4.5 and was stored under slow stirring for later use. Comparative example 1

[0043] This comparative example differs from example 1 only in that a sodium salt of a butadiene-MA copolymer, a coupling agent additive, was not added. Comparative example 2

[0044] This comparative example differs from example 1 only in that vinyltriethoxysilane, a coupling agent A, was not added. Comparative example 3

[0045] This comparative example differs from example 1 only in that vinylbenzyltriethoxysilane, a coupling agent B, was not added. Comparative example 4

[0046] This comparative example differs from example 1 only in that the coupling agent B was replaced by an equal amount of the amino coupling agent Dynasylan 1161 (Evonik). Comparative example 5

[0047] This comparative example differs from example 1 only in that the methanol has been replaced by an equal amount of the surfactant CapstoneFS-63 (DuPont). Comparative example 6

[0048] This comparative example differs from example 1 only in that the percentage of coupling agent A vinyltriethoxysilane was 1.3% and the percentage of coupling agent B vinylbenzyltriethoxysilane was 1.0%. Comparative example 7

[0049] This comparative example differs from example 1 only in that the percentage of coupling agent A vinyltriethoxysilane was 0.8% and the percentage of coupling agent B vinylbenzyltriethoxysilane was 0.8%. Comparative example 8

[0050] Conventional treatment agent: Glacial acetic acid: 0.35%, Amino coupling agent Dynasylan 1161: 0.85%, Surfactant Capstone FS-63: 0.015%, and water: the remainder.

[0051] The treatment agents produced in the examples and comparative examples were each used to treat a low-dielectric, electronic-grade glass fabric (2116 fabric) as follows: the low-dielectric, electronic-grade glass fabric was first immersed in the treatment agent at a speed of 30 m / min (room temperature) and then dried at 120°C. A treated, low-dielectric, electronic-grade glass fabric was subjected to the following performance tests: (1) Testing of tensile strength: Six strip samples measuring 50 mm x 250 mm were cut from a single specimen using a sampler. The upper and lower jaws of a clamping device were loosened to a suitable width, and one end of a sample was inserted into the device such that its longitudinal centerline passed through the center of a leading edge of the clamping device. The other end of the sample was inserted in the same manner. Before the sample was fully clamped, a uniform tension was applied across its entire width, corresponding to approximately (1 ± 0.25)% of the breaking strength. A test start option was selected to initiate the test. The final test result was automatically calculated and displayed by a measuring device. (2) Thermal stress test: A sample was placed in a tin furnace at 288 °C for a heat resistance test. A stopwatch was used to time the immersion of the sample in molten tin for 10 seconds. Delamination (bubbling) of the sample was observed, and the number of times the sample was immersed in the molten tin was recorded. If delamination (bubbling) occurred, it indicated that the sample had failed. (3) Testing of heat resistance: A sample that had been boiled in a PCT autoclave for 4 hours was placed in a tin furnace at 288 °C to perform a heat resistance test. A stopwatch was started to time the immersion of the sample in molten tin for 300 seconds. Delamination (bubbling) of the sample was observed, and the number of times the sample was immersed in the molten tin was recorded. If delamination (bubbling) occurred, it indicated that the sample had failed. (4) Testing of impregnation performance: Samples were taken from a surface-treated, electronic-grade fiberglass fabric using a rotary stamping machine, with one sample each taken from the left, center, and right positions of the fabric. Each sample was placed horizontally in an adhesive with a viscosity of 20 ± 1 s (laboratory temperature: 25°C). A stopwatch was started, and the change of a white line on one surface of the electronic-grade fiberglass fabric was observed until the surface was completely impregnated with the resin. As soon as the white line disappeared, the stopwatch was stopped, and the corresponding time was recorded. (5) Testing of resin content: A sample was placed in a muffle furnace, annealed for 20 minutes at 550±50°C, and then weighed. The reduced weight of the sample was calculated. Resin content = reduced weight of a sample / original weight of the sample.

[0052] The test results are shown in Tables 1 and 2. Table 1 Test results of the examples Object Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Horizontal strength (N / 25 mm) 255 253 242 254 235 239 Longitudinal strength (N / 25 mm) 259 257 246 255 239 243 288°C thermal load (10 s / time) 16 15 13 14 13 15 after plate pressing at 288°C heat resistance test(s) 300 300 300 300 300 300 Resin penetration time (s) 565 572 553 576 551 560 Resin content (%) 45,7 44,8 46,2 45,4 47,2 45,8 Table 2 Test results of the comparison examples Object Comparison example 1 Comparison example 2 Comparison example 3 Comparison example 4 Comparison example 5 Comparison example 6 Comparison example 7 Comparison example 8 Horizontal strength (N / 25 mm) 203 198 209 210 195 200 210 201 Longitudinal strength (N / 25 mm) 207 202 213 214 199 204 214 205 288°C thermal load (10 s / time) 11 9 10 11 10 10 9 8 after plate pressing at 288°C heat resistance test(s) 15 20 22 86 53 105 46 98 Resin penetration time(s) 805 843 820 805 853 809 833 830 Resin content (%) 42,3 41,5 40,5 39,5 41,3 41,9 40,2 42,5

Claims

[1] Treatment agent for a low-dielectric, electronic-grade glass fiber fabric comprising the following starting materials in weight percent: 0.6% to 1.2% of a coupling agent A, 0.3% to 0.8% of a coupling agent B, 0.01% to 1.5% of a coupling agent additive, 0.1% to 0.5% of an alcohol, 0.1% to 0.5% of an acid, and water for the remainder, wherein the ratio of coupling agent A to coupling agent B is (1.2-2.3):1; wherein the coupling agent A is a vinyl-containing coupling agent; the coupling agent B is a vinylbenzyl-containing coupling agent; and the coupling agent additive is a salt of a maleic anhydride (MA)-grafted copolymer; where a general structural formula of the coupling agent A CH2=CH(CH2) n SiX3 is where n is an integer between 0 and 3, and X is methoxy-, ethoxy-, methoxyethoxy- or acetoxy-; where a general structural formula of the coupling agent B CH2=CH(C6H4)CH2(CH2) n SiX3 is where n is an integer between 0 and 3, and X is methoxy, ethoxy, methoxyethoxy or Acetoxy- is; wherein the coupling agent additive is one or more of a sodium salt of a butadiene-MA copolymer, an ammonium salt of a butadiene-MA copolymer, a sodium salt of a dimethyldiallyl-MA copolymer and an amine salt of a dimethyldiallyl-MA copolymer. [2] Treatment agent for the low-dielectric glass fiber fabric of electronic quality according to claim 1, wherein the coupling agent A is one or more of vinyltriethoxysilane, vinyltris(β-methoxyethoxy)silane and propylene trimethoxysilane. [3] Treatment agent for the low-dielectric glass fiber fabric of electronic quality according to claim 1, wherein the coupling agent B is one or more of vinylbenzyltriethoxysilane, β-(Vinylbenzyl)propyltriethoxysilane and vinylbenzyltrimethoxysilane. [4] Treatment agent for the low-dielectric glass fiber fabric of electronic quality according to claim 1, wherein the acid is a low molecular weight organic acid with 1 to 5 carbon atoms. [5] Treatment agent for the low-dielectric glass fiber fabric of electronic quality according to claim 1, wherein the alcohol is a low molecular weight organic alcohol with 1 to 5 carbon atoms. [6] Manufacturing process of the treatment agent for the low-dielectric glass fiber fabric of electronic grade according to any one of claims 1 to 5, comprising the following steps: (1) Add clean water to a preparation container and begin stirring; (2) thoroughly mixing the acid and the alcohol with a stirrer and adding the resulting mixture to the preparation container; (3) Add coupling agent A and coupling agent B successively to the preparation container and stir until a resulting aqueous solution is clear and transparent; and (4) Add the coupling agent additive to the preparation container and stir thoroughly to obtain the treatment agent for a low-dielectric, electronic-grade glass fiber fabric. [7] Manufacturing process of the treatment agent for the low-dielectric glass fiber fabric of electronic quality according to claim 6, wherein the treatment agent obtained in step (4) has a pH of 4 to 6, and the treatment agent is stored for later use after its manufacture under stirring at low speed.