An electronic glass fiber cloth based on an impregnating agent and a preparation process thereof

Abstract

The application discloses electronic glass fiber cloth based on impregnating treating agent and a preparation process thereof, and relates to the technical field of electronic glass fiber cloth; and specifically comprises the following preparation steps: uniformly winding the sized glass fiber yarn on a warp beam to obtain glass fiber gray cloth through sizing weaving; performing heat desizing on the glass fiber gray cloth to obtain sized glass fiber cloth after cooling; sequentially performing water opening treatment, drying, impregnating treatment and drying on the sized glass fiber cloth to obtain the electronic glass fiber cloth; the impregnating treatment adopts an impregnating treating agent; the impregnating treating agent comprises the following raw materials: 1-3% functionalized silane, 0.5-0.8% polymer modified silane, 0.3-0.5% pH regulator, 0.05-0.08% surfactant, 0.04-0.07% defoaming agent and the balance of deionized water in percentage by mass; and the prepared impregnating treating agent effectively improves the high-temperature resistance and mechanical properties of the electronic glass fiber cloth.

Description

Technical Field

[0001] This invention relates to the field of electronic glass fiber cloth technology, specifically to an electronic glass fiber cloth based on an impregnation agent and its preparation process. Background Technology

[0002] Electronic fiberglass cloth is the core reinforcing material for manufacturing copper-clad laminates (CCLs), which in turn are the basic substrate for printed circuit boards (PCBs). With the rapid development of 5G communications, artificial intelligence (AI) servers, automotive electronics, aerospace, and other fields, electronic products are continuously evolving towards high frequency, high speed, high density interconnection, and high reliability. This trend places extremely stringent requirements on the heat resistance and long-term reliability of CCLs, and the achievement of these properties largely depends on the quality of the interfacial bonding between the electronic fiberglass cloth and the matrix resins such as epoxy resin. The conventional processing of electronic glass fiber cloth typically includes three core steps: desizing, fiber opening, and surface chemical modification. This surface chemical treatment is a crucial step in determining the interfacial properties of the final product. Currently, most methods employ traditional coupling agents as the main impregnating agent to achieve surface chemical modification of glass fiber cloth. However, while traditional coupling agents such as KH550 and KH560 can provide some chemical bonding for electronic glass fiber cloth, they struggle to balance toughness and heat resistance, resulting in a relatively simple interfacial structure. Therefore, there is an urgent need to develop an impregnating agent that can construct a multi-layered composite interfacial layer on the surface of electronic glass fiber cloth to improve its mechanical and heat resistance properties. Summary of the Invention

[0003] The purpose of this invention is to provide an electronic glass fiber cloth based on an impregnation agent and its preparation process, so as to solve the problems mentioned in the background art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A process for preparing electronic glass fiber cloth based on an impregnation agent includes the following preparation steps: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, and then weave the sized fabric to obtain the glass fiber fabric. Step 2: Perform hot desizing on the glass fiber fabric and cool it to obtain the desizing glass fiber fabric; Step 3: The desized glass fiber cloth is subjected to water splitting treatment, drying, impregnation treatment, drying, and then wound up to obtain the electronic glass fiber cloth; The impregnation treatment involves treating with an impregnation agent for 8-12 minutes. Preferably, the impregnation treatment agent comprises the following raw materials: by mass percentage, 1-3% functionalized silane, 0.5-0.8% polymer-modified silane, 0.3-0.5% pH adjuster, 0.05-0.08% surfactant, 0.04-0.07% defoamer, and the balance being deionized water; Preferably, the preparation steps of functionalized silane are as follows: γ-chloropropyltriethoxysilane, 4,4'-diaminodiphenyl sulfide, base and catalyst are placed in anhydrous toluene, heated to 85-100℃ for 16-20h under nitrogen atmosphere, anhydrous ethanol is added, filtered, rotary evaporated, dried and placed in anhydrous toluene, heated to 40-50℃, stirred and a mixed solution of p-chloromethylstyrene and polymerization inhibitor is added dropwise, heated to 60℃ and stirred for 4h, heated to 75-85℃ and an acid-binding agent is added dropwise, kept warm and stirred for 1-2h, filtered and rotary evaporated to obtain functionalized silane; Preferably, the mass ratio of γ-chloropropyltriethoxysilane, 4,4'-diaminodiphenyl sulfide and p-chloromethylstyrene is 1:(1.2-1.5):(0.5-0.7).

[0005] Preferably, the polymer-modified silane is obtained by compounding polyetheramine-modified silane and polyimide-modified silane in a mass ratio of 1:(2-4); More preferably, the polyetheramine-modified silane is obtained by reacting polyetheramine and silane coupling agent KH560 at 45-50℃ for 20-24h; More preferably, the preparation steps of polyimide-modified silane are as follows: under a nitrogen atmosphere, diaminodiphenyl ether is added to N,N-dimethylacetamide and stirred to dissolve. Then, 4,4'-biphenyl ether dianhydride is added and N,N-dimethylacetamide is added to stir and react for 3-5 hours. Then, 2-aminopyridine is added and the reaction continues for 2-3 hours. Then, acetic anhydride and triethylamine are added and the reaction is stirred for 20-24 hours. Then, ethanol is added to precipitate the solid, which is filtered and dried. Then, it is placed in N,N-dimethylacetamide, 3-aminopropyltriethoxysilane is added, and the reaction is carried out at 140°C for 24 hours. Then, ethanol is added, filtered and washed, and dried to obtain polyimide-modified silane. Preferably, the molar ratio of 4,4'-biphenyl ether dianhydride, diaminodiphenyl ether, and 2-aminopyridine is (3.6-4.2):3:1; Preferably, the preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polymer-modified silane, surfactant and defoamer, and stir at a stirring speed of 80-100 r / min for 50-60 min. Preferably, a starch-based sizing agent with a concentration of 8.5-9.5% is used for sizing; Preferably, the process parameters for hot annealing are: temperature 380-410℃, time 30-40min; An electronic glass fiber cloth based on an impregnation agent is prepared by the above-described preparation process.

[0006] Compared with the prior art, the beneficial effects achieved by the present invention are: The impregnation agent prepared in this invention is a compound combination of functionalized silane as the main component and polymer-modified silane as the auxiliary component, formulated with the addition of surfactants and defoamers. The functionalized silane uses an aromatic diamine (4,4'-diaminodiphenyl sulfide) as the core skeleton. The first reaction grafts γ-chloropropyltriethoxysilane, introducing thioether bonds into the conventional silane coupling agent to improve its thermal stability. The second reaction introduces styrene groups; the double bonds can subsequently crosslink with copper-clad laminate resins (such as epoxy resins) through free radical reactions, improving interfacial bonding while retaining the secondary amine and epoxy groups. The open-ring reaction capability between the molecules further enhances interfacial bonding and improves the bonding anchoring effect. Polymer-modified silanes are selected from a combination of polyetheramine-modified silanes and polyimide-modified silanes. Polyetheramine segments provide toughening but reduce the material's thermal stability, while polyimide has good heat resistance but is more brittle. The two modifications are mixed in a certain proportion to achieve a balance between heat resistance and toughness. Furthermore, the long chains of the polymer-modified silanes enhance the physical entanglement of the electronic glass fiber cloth in the resin matrix, forming an inter-transmission network structure with the functionalized silanes, thus improving the adhesion and anchoring of the impregnation agent to the glass fiber cloth. This invention starts with yarn sizing and performs a series of processes, including desizing, fiber opening, and impregnation. The sizing process uses a starch-based sizing agent, which balances the sizing effect with the subsequent heat desizing performance. The desizing effect affects the subsequent water opening and fiber bundle dispersion. Each step is seamlessly connected to optimize the product quality as much as possible. Detailed Implementation

[0007] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0008] It should be noted that the following quantities are by weight, and there are no special restrictions on the suppliers of all raw materials involved in this invention. Exemplary examples include: The pH adjuster is glacial acetic acid; the surfactant is polyether-modified trisiloxane, purchased from Anhui Aiyota Silicon Oil Co., Ltd.; the defoamer is BYK-024. The polyetheramine-modified silane was obtained by reacting polyetheramine and silane coupling agent KH560 in a methanol aqueous solution at 45°C for 24 hours and then distilling under reduced pressure; the polyetheramine was M-2070; the molar ratio of polyetheramine to silane coupling agent KH560 was 1:1. The preparation steps of polyimide-modified silane are as follows: Under a nitrogen atmosphere, diaminodiphenyl ether is added to N,N-dimethylacetamide and stirred until dissolved. Then, 4,4'-biphenyl ether dianhydride is added and N,N-dimethylacetamide is added, and the mixture is stirred for 4 hours. 2-aminopyridine is added and the reaction continues for 2 hours. Acetic anhydride and triethylamine are then added, and the mixture is stirred for 24 hours. Ethanol is added to precipitate the solid, which is then filtered, dried, and placed in N,N-dimethylacetamide. 3-aminopropyltriethoxysilane is added, and the mixture is reacted at 140°C for 24 hours. Ethanol is added, and the mixture is filtered and washed to obtain polyimide-modified silane. The molar ratio of 4,4'-biphenyl ether dianhydride, diaminodiphenyl ether, 2-aminopyridine, and 3-aminopropyltriethoxysilane is 3.8:3:1:4. The glass fiber warp and weft yarns in the glass fiber fabric are of ECG75 1 / 0 specification; the sizing is done with a starch-based sizing agent; the starch-based sizing agent includes: 20 parts starch, 13.5 parts PVA0588, 13.5 parts PEG4000, and 480 parts deionized water; In the following embodiments, all of the above-mentioned and other raw materials used but not mentioned are commercially available.

[0009] Example 1: This example provides a preparation process for electronic glass fiber cloth based on an impregnation agent, including the following steps: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, sizing and weaving it according to a warp and weft density of 24×24 threads / inch to obtain glass fiber fabric; Step 2: Desizing the glass fiber fabric by treating it at 400℃ for 35 minutes and then cooling it to obtain the desized glass fiber fabric; Step 3: The desized fiberglass cloth is then subjected to water-based fiber opening treatment, using a nozzle orifice diameter of 0.2 mm and a pressure of 10 kg / cm². 2 After high-pressure jetting and drying, the electronic glass fiber cloth is immersed in an impregnation agent for 10 minutes, then dried and wound up. The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polymer-modified silane, surfactant and defoamer, and stir at a stirring speed of 80 r / min for 60 min. The impregnation treatment agent comprises the following raw materials by mass percentage: 1.5% functionalized silane, 0.8% polymer-modified silane, 0.4% pH adjuster, 0.06% surfactant, 0.05% defoamer, and the balance being deionized water; The preparation steps of functionalized silane are as follows: 14.45 g of γ-chloropropyltriethoxysilane, 17.88 g of 4,4'-diaminodiphenyl sulfide, 20 g of potassium tert-butoxide and 0.2 g of palladium catalyst are placed in 100 mL of anhydrous toluene. Under a nitrogen atmosphere, the mixture is heated to 85 °C and reacted for 20 h. After adding anhydrous ethanol, the mixture is filtered, rotary evaporated, dried, and placed in 50 mL of anhydrous toluene. The mixture is heated to 40 °C, stirred, and a mixed solution of 7.63 g of p-chloromethylstyrene and 0.02 g of hydroquinone is added dropwise. The mixture is then heated to 60 °C and stirred for 4 h. After heating to 80 °C, 5.9 g of triethylamine is added dropwise. The mixture is kept at this temperature and stirred for 1 h. After filtration and rotary evaporation, the functionalized silane is obtained. The polymer-modified silane is obtained by compounding polyetheramine-modified silane and polyimide-modified silane in a mass ratio of 1:3.

[0010] Example 2: This example provides a preparation process for electronic glass fiber cloth based on an impregnation agent, including the following steps: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, sizing and weaving it according to a warp and weft density of 24×24 threads / inch to obtain glass fiber fabric; Step 2: Desizing the glass fiber fabric by treating it at 380℃ for 35 minutes and then cooling it to obtain the desized glass fiber fabric; Step 3: The desized fiberglass cloth is then subjected to water-based fiber opening treatment, using a nozzle orifice diameter of 0.2 mm and a pressure of 10 kg / cm². 2 After high-pressure jetting and drying, the electronic glass fiber cloth is immersed in an impregnation agent for 10 minutes, then dried and wound up. The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polymer-modified silane, surfactant and defoamer, and stir at a stirring speed of 85 r / min for 60 min. The impregnation treatment agent comprises the following raw materials: by mass percentage, 1% functionalized silane, 0.6% polymer-modified silane, 0.3% pH adjuster, 0.08% surfactant, 0.04% defoamer, and the balance being deionized water; The preparation steps of functionalized silane are as follows: 14.45 g of γ-chloropropyltriethoxysilane, 17.88 g of 4,4'-diaminodiphenyl sulfide, 20 g of potassium tert-butoxide and 0.2 g of palladium catalyst are placed in 100 mL of anhydrous toluene. Under a nitrogen atmosphere, the mixture is heated to 95 °C and reacted for 18 h. After adding anhydrous ethanol, the mixture is filtered, rotary evaporated, dried, and placed in 50 mL of anhydrous toluene. The mixture is heated to 45 °C, stirred, and a mixed solution of 7.23 g of p-chloromethylstyrene and 0.02 g of hydroquinone is added dropwise. The mixture is then heated to 60 °C and stirred for 4 h. After heating to 85 °C, 6.0 g of triethylamine is added dropwise. The mixture is kept at this temperature and stirred for 2 h. After filtration and rotary evaporation, the functionalized silane is obtained. The polymer-modified silane is obtained by compounding polyetheramine-modified silane and polyimide-modified silane in a mass ratio of 1:2.

[0011] Example 3: This example provides a preparation process for electronic glass fiber cloth based on an impregnation agent, including the following steps: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, sizing and weaving it according to a warp and weft density of 24×24 threads / inch to obtain glass fiber fabric; Step 2: Desizing the glass fiber fabric by treating it at 410℃ for 40 minutes and then cooling it to obtain the desized glass fiber fabric; Step 3: The desized fiberglass cloth is then subjected to water-based fiber opening treatment, using a nozzle orifice diameter of 0.2mm and a pressure of 10kg / cm². 2 After high-pressure jetting and drying, the cloth is immersed in an impregnation agent for 8 minutes, then dried and wound up to obtain electronic glass fiber cloth. The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polymer-modified silane, surfactant and defoamer, and stir at a stirring speed of 100 r / min for 50 min. The impregnation treatment agent comprises the following raw materials by mass percentage: 3% functionalized silane, 0.8% polymer-modified silane, 0.5% pH adjuster, 0.08% surfactant, 0.07% defoamer, and the balance being deionized water; The preparation steps of functionalized silane are as follows: 14.45 g of γ-chloropropyltriethoxysilane, 17.88 g of 4,4'-diaminodiphenyl sulfide, 20 g of potassium tert-butoxide and 0.2 g of palladium catalyst are placed in 100 mL of anhydrous toluene. Under a nitrogen atmosphere, the mixture is heated to 100 °C and reacted for 20 h. After adding anhydrous ethanol, the mixture is filtered, rotary evaporated, dried, and placed in 50 mL of anhydrous toluene. The mixture is heated to 50 °C, stirred, and a mixed solution of 9.63 g of p-chloromethylstyrene and 0.02 g of hydroquinone is added dropwise. The mixture is then heated to 60 °C and stirred for 4 h. After heating to 85 °C, 6.2 g of triethylamine is added dropwise. The mixture is kept at this temperature and stirred for 1-2 h. After filtration and rotary evaporation, the functionalized silane is obtained. The polymer-modified silane is obtained by compounding polyetheramine-modified silane and polyimide-modified silane in a mass ratio of 1:4.

[0012] Comparative Example 1: As a control experiment for Example 1, no polymer-modified silane was added, and the following preparation steps were included: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, sizing and weaving it according to a warp and weft density of 24×24 threads / inch to obtain glass fiber fabric; Step 2: Desizing the glass fiber fabric by treating it at 400℃ for 35 minutes and then cooling it to obtain the desized glass fiber fabric; Step 3: The desized fiberglass cloth is then subjected to water-based fiber opening treatment, using a nozzle orifice diameter of 0.2mm and a pressure of 10kg / cm². 2 After high-pressure jetting and drying, the electronic glass fiber cloth is immersed in an impregnation agent for 10 minutes, then dried and wound up. The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polymer-modified silane, surfactant and defoamer, and stir at a stirring speed of 80 r / min for 60 min. The impregnation treatment agent comprises the following raw materials: by mass percentage, 1.5% functionalized silane, 0.4% pH adjuster, 0.06% surfactant, 0.05% defoamer, and the balance being deionized water; The preparation steps of functionalized silane are as follows: 14.45 g of γ-chloropropyltriethoxysilane, 17.88 g of 4,4'-diaminodiphenyl sulfide, 20 g of potassium tert-butoxide and 0.2 g of palladium catalyst were placed in 100 mL of anhydrous toluene. Under a nitrogen atmosphere, the mixture was heated to 85 °C and reacted for 20 h. After adding anhydrous ethanol, the mixture was filtered, rotary evaporated, dried, and placed in 50 mL of anhydrous toluene. The mixture was heated to 40 °C, stirred, and a mixed solution of 7.63 g of p-chloromethylstyrene and 0.02 g of hydroquinone was added dropwise. The mixture was then heated to 60 °C and stirred for 4 h. After heating to 80 °C, 5.9 g of triethylamine was added dropwise. The mixture was kept at this temperature and stirred for 1 h. After filtration and rotary evaporation, the functionalized silane was obtained.

[0013] Comparative Example 2: As a control experiment for Example 1, the polymer-modified silane was a single-component polyetheramine-modified silane, comprising the following steps: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, sizing and weaving it according to a warp and weft density of 24×24 threads / inch to obtain glass fiber fabric; Step 2: Desizing the glass fiber fabric by treating it at 400℃ for 35 minutes and then cooling it to obtain the desized glass fiber fabric; Step 3: The desized fiberglass cloth is then subjected to water-based fiber opening treatment, using a nozzle orifice diameter of 0.2mm and a pressure of 10kg / cm². 2 After high-pressure jetting and drying, the electronic glass fiber cloth is immersed in an impregnation agent for 10 minutes, then dried and wound up. The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polyetheramine modified silane, surfactant and defoamer, and stir at a stirring speed of 80 r / min for 60 min. The impregnation treatment agent comprises the following raw materials by mass percentage: 1.5% functionalized silane, 0.8% polyetheramine modified silane, 0.4% pH adjuster, 0.06% surfactant, 0.05% defoamer, and the balance being deionized water; The preparation steps of functionalized silane are as follows: 14.45 g of γ-chloropropyltriethoxysilane, 17.88 g of 4,4'-diaminodiphenyl sulfide, 20 g of potassium tert-butoxide and 0.2 g of palladium catalyst were placed in 100 mL of anhydrous toluene. Under a nitrogen atmosphere, the mixture was heated to 85 °C and reacted for 20 h. After adding anhydrous ethanol, the mixture was filtered, rotary evaporated, dried, and placed in 50 mL of anhydrous toluene. The mixture was heated to 40 °C, stirred, and a mixed solution of 7.63 g of p-chloromethylstyrene and 0.02 g of hydroquinone was added dropwise. The mixture was then heated to 60 °C and stirred for 4 h. After heating to 80 °C, 5.9 g of triethylamine was added dropwise. The mixture was kept at this temperature and stirred for 1 h. After filtration and rotary evaporation, the functionalized silane was obtained.

[0014] Comparative Example 3: As a control experiment for Example 1, the polymer-modified silane was a single-component polyimide-modified silane, comprising the following steps: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, sizing and weaving it according to a warp and weft density of 24×24 threads / inch to obtain glass fiber fabric; Step 2: Desizing the glass fiber fabric by treating it at 400℃ for 35 minutes and then cooling it to obtain the desized glass fiber fabric; Step 3: The desized fiberglass cloth is then subjected to water-based fiber opening treatment, using a nozzle orifice diameter of 0.2mm and a pressure of 10kg / cm². 2 After high-pressure jetting and drying, the electronic glass fiber cloth is immersed in an impregnation agent for 10 minutes, then dried and wound up. The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polyimide modified silane, surfactant and defoamer, and stir at a stirring speed of 80 r / min for 60 min. The impregnation treatment agent comprises the following raw materials by mass percentage: 1.5% functionalized silane, 0.8% polyimide-modified silane, 0.4% pH adjuster, 0.06% surfactant, 0.05% defoamer, and the balance being deionized water; The preparation steps of functionalized silane are as follows: 14.45 g of γ-chloropropyltriethoxysilane, 17.88 g of 4,4'-diaminodiphenyl sulfide, 20 g of potassium tert-butoxide and 0.2 g of palladium catalyst were placed in 100 mL of anhydrous toluene. Under a nitrogen atmosphere, the mixture was heated to 85 °C and reacted for 20 h. After adding anhydrous ethanol, the mixture was filtered, rotary evaporated, dried, and placed in 50 mL of anhydrous toluene. The mixture was heated to 40 °C, stirred, and a mixed solution of 7.63 g of p-chloromethylstyrene and 0.02 g of hydroquinone was added dropwise. The mixture was then heated to 60 °C and stirred for 4 h. After heating to 80 °C, 5.9 g of triethylamine was added dropwise. The mixture was kept at this temperature and stirred for 1 h. After filtration and rotary evaporation, the functionalized silane was obtained.

[0015] Comparative Example 4: As a control experiment for Example 1, the functionalized silane did not introduce styrene groups, and included the following steps: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, sizing and weaving it according to a warp and weft density of 24×24 threads / inch to obtain glass fiber fabric; Step 2: Desizing the glass fiber fabric by treating it at 400℃ for 35 minutes and then cooling it to obtain the desized glass fiber fabric; Step 3: The desized fiberglass cloth is then subjected to water-based fiber opening treatment, using a nozzle orifice diameter of 0.2mm and a pressure of 10kg / cm². 2 After high-pressure jetting and drying, the electronic glass fiber cloth is immersed in an impregnation agent for 10 minutes, then dried and wound up. The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polymer-modified silane, surfactant and defoamer, and stir at a stirring speed of 80 r / min for 60 min. The impregnation treatment agent comprises the following raw materials by mass percentage: 1.5% functionalized silane, 0.8% polymer-modified silane, 0.4% pH adjuster, 0.06% surfactant, 0.05% defoamer, and the balance being deionized water; The preparation steps of functionalized silane are as follows: 14.45 g of γ-chloropropyltriethoxysilane, 17.88 g of 4,4'-diaminodiphenyl sulfide, 20 g of potassium tert-butoxide and 0.2 g of palladium catalyst are placed in 100 mL of anhydrous toluene, heated to 85 °C for 20 h under nitrogen atmosphere, anhydrous ethanol is added, and the mixture is filtered, rotary evaporated and dried to obtain functionalized silane. The polymer-modified silane is obtained by compounding polyetheramine-modified silane and polyimide-modified silane in a mass ratio of 1:3.

[0016] Performance testing: 1. Referring to GB / T 7689.5, the tensile strength and elongation at break of the electronic glass fiber cloths prepared in Examples 1-3 and Comparative Examples 1-4 were tested using a tensile testing machine. The tensile speed during the test was 100 mm / min.

[0017] 2. Copper-clad laminates were prepared using the electronic glass fiber cloths prepared in Examples 1-3 and Comparative Examples 1-4. The heat resistance was tested. After being cooked in a PCT high-pressure cooker for 4 hours, the samples were immersed in a tin furnace at a temperature of 288°C for 300 seconds. The samples were observed to see if they burst or bubbled. Table 1

[0018] Conclusion: Example 1 exhibits the best tensile strength and elongation at break test performance compared to the other examples; Comparative Example 1, serving as a control experiment for Example 1, does not contain polymer-modified silane, resulting in a significant decrease in tensile strength and elongation at break, and severe plate bursting; Comparative Example 2, serving as a control experiment for Example 1, does not contain polyimide-modified silane, showing good elongation at break, but with a significant decrease in tensile strength and heat resistance; Comparative Example 3, without polyetheramine, shows good tensile strength, but is brittle and has insufficient heat resistance; Comparative Example 4, lacking styrene, shows a slight decrease in performance.

[0019] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A preparation process for electronic glass fiber cloth based on an impregnation agent, characterized in that, The preparation steps include the following: Step 1: Evenly wind the sized glass fiber yarn onto the warp beam, and then weave the sized fabric to obtain the glass fiber fabric. Step 2: Perform hot desizing on the glass fiber fabric and cool it to obtain the desizing glass fiber fabric; Step 3: The desized glass fiber cloth is subjected to water splitting treatment, drying, impregnation treatment, drying, and then wound up to obtain the electronic glass fiber cloth; The impregnation treatment involves treating with an impregnation agent for 8-12 minutes. The impregnation agent comprises the following raw materials by mass percentage: 1-3% functionalized silane, 0.5-0.8% polymer-modified silane, 0.3-0.5% pH adjuster, 0.05-0.08% surfactant, 0.04-0.07% defoamer, and the balance being deionized water. The polymer-modified silane is obtained by compounding polyetheramine-modified silane and polyimide-modified silane in a mass ratio of 1:(2-4); The functionalized silane is prepared by reacting γ-chloropropyltriethoxysilane, 4,4'-diaminodiphenyl sulfide and p-chloromethylstyrene.

2. The preparation process of electronic glass fiber cloth based on impregnation agent according to claim 1, characterized in that, The preparation steps of the functionalized silane are as follows: γ-chloropropyltriethoxysilane, 4,4'-diaminodiphenyl sulfide, base and catalyst are placed in anhydrous toluene and reacted at 85-100℃ for 16-20h under a nitrogen atmosphere. After adding anhydrous ethanol, the mixture is filtered, rotary evaporated, dried, and placed in anhydrous toluene. The mixture is heated to 40-50℃, stirred and a mixed solution of p-chloromethylstyrene and polymerization inhibitor is added dropwise. The mixture is then heated to 60℃ and stirred for 4h. After heating to 75-85℃ and adding an acid-binding agent, the mixture is kept at this temperature and stirred for 1-2h. The mixture is then filtered and rotary evaporated to obtain the functionalized silane.

3. The preparation process of electronic glass fiber cloth based on impregnation agent according to claim 2, characterized in that, The mass ratio of γ-chloropropyltriethoxysilane, 4,4'-diaminodiphenyl sulfide and p-chloromethylstyrene is 1:(1.2-1.5):(0.5-0.7).

4. The preparation process of electronic glass fiber cloth based on impregnation agent according to claim 1, characterized in that, The polyetheramine-modified silane is obtained by reacting polyetheramine and silane coupling agent KH560 at 45-50℃ for 20-24 hours.

5. The preparation process of electronic glass fiber cloth based on impregnation agent according to claim 1, characterized in that, The preparation steps of the polyimide-modified silane are as follows: Under a nitrogen atmosphere, diaminodiphenyl ether is added to N,N-dimethylacetamide and stirred to dissolve. Then, 4,4'-biphenyl ether dianhydride is added and N,N-dimethylacetamide is added to stir and react for 3-5 hours. Then, 2-aminopyridine is added and the reaction continues for 2-3 hours. Then, acetic anhydride and triethylamine are added and the reaction is stirred for 20-24 hours. Then, ethanol is added to precipitate the solid, which is filtered and dried. Then, it is placed in N,N-dimethylacetamide and 3-aminopropyltriethoxysilane is added. After reacting at 140°C for 24 hours, ethanol is added, filtered and washed, and dried to obtain the polyimide-modified silane.

6. The preparation process of electronic glass fiber cloth based on impregnation agent according to claim 5, characterized in that, The molar ratio of 4,4'-biphenyl ether dianhydride, diaminodiphenyl ether, and 2-aminopyridine is (3.6-4.2):3:

1.

7. The preparation process of electronic glass fiber cloth based on impregnation agent according to claim 1, characterized in that, The preparation steps of the impregnation treatment agent are as follows: after adding a pH adjuster to deionized water, add functionalized silane, polymer-modified silane, surfactant and defoamer, and stir at a stirring speed of 80-100 r / min for 50-60 min.

8. The preparation process of electronic glass fiber cloth based on impregnation agent according to claim 1, characterized in that, The sizing process uses a starch-based sizing agent with a concentration of 8.5-9.5%; the process parameters for the heat annealing are: temperature 380-410℃ and time 30-40min.

9. An electronic glass fiber cloth based on an impregnation agent prepared by the preparation process according to any one of claims 1-8.

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