Fiber-reinforced waterproof material for electronic backplane and manufacturing process thereof

Abstract

The application discloses a kind of fiber reinforced waterproof material for electronic backplane and its manufacturing process, it is related to the technical field of polyester composite material.In the present application, by blending flame-retardant glass fiber with PET resin and other additives, a glass fiber / PET composite material is obtained through melting, extrusion, injection molding and other processes, then a silicon oxide target is used to deposit a silicon oxide film on the surface of the glass fiber / PET composite material through magnetron sputtering, and finally a fiber reinforced waterproof material is obtained.The flame-retardant glass fiber has polycarbonate segments on its surface, which improves the compatibility of the glass fiber and the PET resin, and also disperses the stress when the fiber reinforced waterproof material is under stress, improving the mechanical properties of the material.The silicon oxide film can effectively prevent water and water vapor from penetrating, and helps to improve the waterproofness of the material.

Description

Technical Field

[0001] This invention relates to the field of polyester composite materials technology, specifically to a fiber-reinforced waterproof material for electronic backplanes and its manufacturing process. Background Technology

[0002] Backplanes are specialized circuit boards used in the PCB manufacturing industry, primarily to support electronic components. The choice of materials directly determines the reliability and application scenarios of the equipment. As electronic products develop towards thinner and lighter designs and higher reliability, backplane materials are also transforming towards multi-performance synergy. PET composite materials, with their excellent insulation and significant cost advantages, have become the core basic material for electronic backplanes.

[0003] CN114395223A discloses a hydrolysis-resistant, weather-resistant, and high-strength glass fiber reinforced PP / PET material for photovoltaic backsheets and its preparation method. The method involves mixing PP and PET materials with compatibilizers, anti-hydrolysis agents, light stabilizers, and antioxidants to prepare a hydrolysis-resistant, weather-resistant, and high-strength composite material.

[0004] However, when electronic devices are in operation, they may generate high temperatures or open flames due to short circuits, overloads, or component failures. Therefore, this application prepares a composite PET material with waterproof and flame-retardant properties and applies it to the preparation of electronic backplanes to improve the safety and service life of electronic devices. Summary of the Invention

[0005] The purpose of this invention is to provide a fiber-reinforced waterproof material for electronic backplanes and its manufacturing process, so as to solve the problems raised in the prior art.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a manufacturing process for a fiber-reinforced waterproof material for electronic backplanes, comprising the following steps: Step 1: Mix PET resin, flame-retardant glass fiber, carbodiimide and antioxidant, heat and stir to obtain a mixture; Step 2: Feed the mixture into a twin-screw extruder, melt, extrude, granulate, inject mold, and cool to obtain a glass fiber / PET composite material; Step 3: Take the glass fiber / PET composite material, use a silicon oxide ceramic target, and deposit silicon oxide on the surface of the glass fiber / PET composite material by magnetron sputtering to form a silicon oxide film, thus obtaining a fiber-reinforced waterproof material.

[0007] Furthermore, in step 1, the mass ratio of PET resin, flame-retardant glass fiber, carbodiimide, and antioxidant is 100:(45~55):(1~3):(0.5~1.5). In step 1, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, and antioxidant 1330, or a mixture thereof.

[0008] Furthermore, in step 1, the heating and stirring process conditions are: temperature 250~270℃, stirring speed 600~800r / min, and time 90~110min.

[0009] Furthermore, in step 2, the melting temperature is 260~270℃; In step 2, the extrusion temperature is 270~280℃; In step 2, the injection temperature is 270~280℃.

[0010] Furthermore, in step 3, the magnetron sputtering process conditions are: power density 5~10 W / cm³. 2 Temperature 50~70℃, pressure 0.2~1.0Pa.

[0011] Furthermore, the working gas used in the magnetron sputtering process is argon. The argon gas flow rate is 3.5~4.5 mL / min.

[0012] Furthermore, in step 3, the thickness of the silicon oxide film is 100~500nm.

[0013] Furthermore, the flame-retardant glass fiber is obtained by the following process: S1: Mix glass fiber with hydrochloric acid aqueous solution, soak and treat, wash and dry to obtain hydroxylated glass fiber; S2: Disperse hydroxylated glass fibers in N,N-dimethylformamide, stir to form a suspension, add maleic anhydride, dicyclohexylcarbodiimide and 4-dimethylaminopyridine under nitrogen atmosphere protection, heat and stir to react, filter, wash and dry to obtain modified glass fibers; S3: Mix modified glass fiber and dimethyl sulfoxide, stir evenly, add flame-retardant polycarbonate polyol and alkaline catalyst under nitrogen atmosphere protection, heat to react, filter, wash and dry to obtain flame-retardant glass fiber.

[0014] Furthermore, in S1, the ratio of glass fiber to hydrochloric acid aqueous solution is 1g:(20~30)mL; The concentration of the hydrochloric acid aqueous solution is 1~3 mol / L.

[0015] Furthermore, in S1, the soaking treatment process conditions are: temperature 30~50℃, time 0.5~1.5h.

[0016] Furthermore, in S2, the mass ratio of hydroxylated glass fiber, N,N-dimethylformamide, maleic anhydride, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 1:(5~10):(0.45~0.55):(0.07~0.09):(0.01~0.03).

[0017] Furthermore, in S2, the process conditions for heating and stirring reaction are: temperature 60~80℃, time 3~5h, and rotation speed 100~200r / min.

[0018] Furthermore, in S3, the mass ratio of modified glass fiber, dimethyl sulfoxide, flame-retardant polycarbonate polyol, and alkaline catalyst is 1: (5~10): (1.8~2.0): (0.4~0.6). The alkaline catalyst is one or a mixture of potassium carbonate and potassium hydroxide.

[0019] Furthermore, in S3, the process conditions for the heating reaction are: temperature 70~80℃, time 4~6h.

[0020] Furthermore, in S1, S2, and S3, the drying process conditions are: temperature 60~70℃, time 30~40min.

[0021] In the above technical solution, the glass fiber is first immersed in hydrochloric acid aqueous solution for treatment, so that the surface of the glass fiber has hydroxyl groups, and hydroxylated glass fiber is obtained. Then, under the action of dicyclohexylcarbodiimide (condensing agent) and 4-dimethylaminopyridine (catalyst), the hydroxyl groups and the anhydride groups of maleic anhydride undergo a ring-opening esterification reaction. The carbonyl group of one anhydride reacts with the hydroxyl group to form an ester bond, and the carbonyl group of the other anhydride is converted into a carboxyl group, thus obtaining modified glass fiber. Finally, the carboxyl groups on the surface of the modified glass fiber and the hydroxyl groups of the flame-retardant polycarbonate polyol undergo an esterification reaction under the action of an alkaline catalyst, and the polycarbonate segments are grafted onto the surface of the glass fiber to obtain flame-retardant glass fiber. On the one hand, the polycarbonate segments in flame-retardant polycarbonate polyols have good compatibility with PET, reducing the interfacial tension between glass fiber and PET resin and preventing glass fiber agglomeration. On the other hand, polycarbonate segments are flexible segments that can disperse the stress when fiber-reinforced waterproof materials are subjected to force, transferring external force from the waterproof material to the glass fiber, thereby improving the mechanical properties of the material.

[0022] Furthermore, the preparation process of the flame-retardant polycarbonate polyol is as follows: Step A: Mix octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution, heat and stir to react, adjust pH to 6.5~7.0, remove low-boiling substances under vacuum to obtain hydroxyl-terminated aminosiloxane; Step B: Hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, and solvent are mixed and heated to obtain intermediate A containing aldehyde and hydroxyl groups. Then, it is mixed with DOPO and heated to react. After the reaction is completed, it is washed and dried to obtain DOPO derivative containing hydroxyl groups. Step C: Mix DOPO derivative, nitrogen-containing polyol, diester, and catalyst, and carry out transesterification and polycondensation reactions in sequence. After cooling, flame-retardant polycarbonate polyol is obtained.

[0023] Furthermore, in step A, the mass ratio of octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution is 10:(8.5~9.5):(0.02~0.04). The mass fraction of the potassium hydroxide aqueous solution is 8-10%.

[0024] Furthermore, in step A, the process conditions for heating and stirring the reaction are: temperature 130~140℃, time 4~6h, and rotation speed 100~200r / min.

[0025] Furthermore, in step A, the process conditions for vacuum removal of low-boiling substances are: temperature 145~155℃, time 1.5~2.0h.

[0026] Furthermore, in step B, the mass ratio of hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, DOPO, and solvent is 1:1:(0.8~1.0):(8~10). The solvent is one or a mixture of anhydrous ethanol, N,N-dimethylformamide, and dimethyl sulfoxide.

[0027] Furthermore, in step B, the process conditions for the heating reaction are: temperature 70~80℃, time 6~8h; In step B, the process conditions for the heating reaction are: temperature 80~85℃, time 4~6h; In step B, the drying process conditions are: temperature 60~70℃, time 30~50min.

[0028] Furthermore, in step C, the mass ratio of DOPO derivative, nitrogen-containing polyol, carbonate diester, and catalyst is 10:(35~40):(22~26):(0.04~0.06). The nitrogen-containing polyol is one or a mixture of two of diethanolamine and triethanolamine; The catalyst is one or a mixture of tetraethyl titanate, dibutyltin dilaurate, and dibutyltin octanoate.

[0029] Furthermore, in step C, the process conditions for the transesterification reaction are: temperature 155~160℃, time 9~10h; In step C, the process conditions for the polycondensation reaction are: temperature 155~160℃, time 40~44h, and pressure 1~3kPa.

[0030] Furthermore, in step A, the (3-aminopropyl)trimethoxysilane hydrolysate is prepared by the following process: (3-aminopropyl)trimethoxysilane was mixed with water at a mass ratio of 1:1 and heated to 75-85℃ for 1.5-2.0 h to obtain (3-aminopropyl)trimethoxysilane hydrolysate.

[0031] In the above technical solution, octamethyl silicone oil is first reacted with (3-aminopropyl)trimethoxysilane hydrolysate under the action of potassium hydroxide to obtain hydroxyl-terminated aminosiloxane. Then, the amino group on it undergoes an aldehyde-amine condensation reaction with the aldehyde group of 2,6-pyridinedicarboxaldehyde to generate intermediate A containing aldehyde and hydroxyl groups. Then, the aldehyde group reacts with the PH bond of DOPO, retaining the hydroxyl group, which is the DOPO derivative. Finally, the hydroxyl group of the DOPO derivative undergoes transesterification and polycondensation reactions with nitrogen-containing polyol and diester in sequence to obtain flame-retardant polycarbonate polyol. The DOPO derivative contains silicon, nitrogen and phosphorus elements at the same time. The three elements work synergistically to give the flame-retardant polycarbonate polyol excellent flame-retardant effect.

[0032] Compared with the prior art, the beneficial effects of the present invention are: 1. In this application, a silica target is used to deposit a dense, non-porous silica film on the surface of a glass fiber / PET composite material by magnetron sputtering, which can effectively prevent water and water vapor penetration and help improve the waterproofness of the material.

[0033] 2. In this application, hydroxyl-terminated aminosiloxane is first synthesized from octamethyl silicone oil and (3-aminopropyl)trimethoxysilane. Then, it undergoes aldehyde-amine condensation with 2,6-pyridinedicarboxaldehyde to generate intermediate A containing aldehyde and hydroxyl groups. Then, it reacts with the PH bond of DOPO to obtain a hydroxyl-containing DOPO derivative. Finally, it undergoes transesterification and polycondensation reactions with nitrogen-containing polyol and diester in sequence to obtain flame-retardant polycarbonate polyol containing nitrogen, phosphorus, and silicon. The three elements work synergistically to give the flame-retardant polycarbonate polyol excellent flame retardancy. The siloxane segment structure in the molecular structure is stable and can further improve the hydrolysis resistance of flame-retardant polycarbonate.

[0034] 3. In this application, polycarbonate segments are grafted onto the surface of glass fiber to obtain flame-retardant glass fiber. On the one hand, the polycarbonate segments in the flame-retardant polycarbonate polyol have good compatibility with PET, reducing the interfacial tension between glass fiber and PET resin and preventing glass fiber agglomeration. On the other hand, the polycarbonate segments are flexible segments, which can disperse the stress when the fiber-reinforced waterproof material is subjected to force, transfer the external force from the waterproof material to the glass fiber, and improve the mechanical properties of the material. Detailed Implementation

[0035] 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.

[0036] In the following specific implementation, PET resin, grade 70G43L; Silica sputtering target, purity 99.99%; The antioxidant is antioxidant 1010; Fiberglass, grade 8025; The alkaline catalyst is potassium carbonate; The solvent is anhydrous ethanol; The nitrogen-containing polyol is triethanolamine; The catalyst is tetraethyl titanate; Polycarbonate diol, model number RAYNOL PS-3152.

[0037] Example 1: A manufacturing process for a fiber-reinforced waterproof material for electronic backplanes, comprising the following steps: (1) Preparation of flame-retardant polycarbonate polyols: (3-aminopropyl)trimethoxysilane was mixed with water at a mass ratio of 1:1 and heated to 85°C for 2.0 h to obtain (3-aminopropyl)trimethoxysilane hydrolysate; Step A: Mix octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution, heat and stir to react, adjust pH to 7.0, remove low-boiling substances under vacuum to obtain hydroxyl-terminated aminosiloxane; Step B: Mix hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, and solvent, heat to react to obtain intermediate A containing aldehyde and hydroxyl groups, then mix with DOPO, heat to react, wash and dry after reaction to obtain DOPO derivative containing hydroxyl groups; Step C: Mix DOPO derivative, nitrogen-containing polyol, diester, and catalyst, and carry out transesterification and polycondensation reactions sequentially, cool to obtain flame-retardant polycarbonate polyol; In Step A, the mass ratio of octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution is 10:9.5:0.04; the mass fraction of potassium hydroxide aqueous solution is 10%; In Step A, the heating and stirring reaction... The process conditions are as follows: temperature 140℃, time 6h, rotation speed 200r / min; in step A, the vacuum removal of low-boiling substances is performed at a temperature of 155℃ for 2.0h; in step B, the mass ratio of hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, DOPO, and solvent is 1:1:1.0:10; in step B, the heating reaction is performed at a temperature of 80℃ for 8h; in step B, the temperature rise reaction is performed at a temperature of 85℃ for 6h; in step B, the drying is performed at a temperature of 70℃ for 50min; in step C, the mass ratio of DOPO derivative, nitrogen-containing polyol, diester, and catalyst is 10:40:26:0.06; in step C, the transesterification reaction is performed at a temperature of 160℃ for 10h; in step C, the polycondensation reaction is performed at a temperature of 160℃ for 44h and a pressure of 3kPa. (2) Preparation of flame-retardant glass fiber: S1: Glass fiber is mixed with hydrochloric acid aqueous solution, soaked, washed, and dried to obtain hydroxylated glass fiber; S2: Hydroxylated glass fiber is dispersed in N,N-dimethylformamide, stirred to form a suspension, and maleic anhydride, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine are added under nitrogen atmosphere protection. The mixture is heated and stirred to react, filtered, washed, and dried to obtain modified glass fiber; S3: Modified glass fiber and dimethyl sulfoxide are mixed and stirred evenly. Flame-retardant polycarbonate polyol and an alkaline catalyst are added under nitrogen atmosphere protection. The mixture is heated to react, filtered, washed, and dried to obtain flame-retardant glass fiber; In S1, the ratio of glass fiber to hydrochloric acid aqueous solution is 1g:30mL; the concentration of hydrochloric acid aqueous solution is 3mol / L; In S1, the soaking treatment conditions are: temperature 50℃, time 1.5h; in S2, the mass ratio of hydroxylated glass fiber, N,N-dimethylformamide, maleic anhydride, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 1:10:0.55:0.09:0.03; in S2, the heating and stirring reaction conditions are: temperature 80℃, time 5h, rotation speed 200r / min; in S3, the mass ratio of modified glass fiber, dimethyl sulfoxide, flame-retardant polycarbonate polyol, and alkaline catalyst is 1:10:2.0:0.6; in S3, the heating reaction conditions are: temperature 80℃, time 6h; in S1, S2, and S3, the drying conditions are: temperature 70℃, time 40min. (3) Preparation of fiber-reinforced waterproof materials: Step 1: Mix PET resin, flame-retardant glass fiber, carbodiimide, and antioxidant, and heat and stir to obtain a mixture. Step 2: Feed the mixture into a twin-screw extruder, melt, extrude, granulate, inject mold, and cool to obtain a glass fiber / PET composite material. Step 3: Take the glass fiber / PET composite material, use a silica ceramic target, and deposit silica on the surface of the glass fiber / PET composite material by magnetron sputtering to form a silica film, obtaining a fiber-reinforced waterproof material. In Step 1, the mass ratio of PET resin, flame-retardant glass fiber, carbodiimide, and antioxidant is 100:55:3:1.5. In Step 1, the heating and stirring process conditions are: temperature 270℃, stirring speed 800 r / min, time 110 min. In Step 2, the melting temperature is 270℃. In Step 2, the extrusion temperature is 280℃. In Step 2, the injection molding temperature is 280℃. In Step 3, the magnetron sputtering process conditions are: power density 10 W / cm³. 2 The temperature was 70℃ and the pressure was 1.0Pa. The working gas used in the magnetron sputtering process was argon. The argon gas flow rate was 4.5mL / min. In step 3, the thickness of the silicon oxide film was 500nm.

[0038] Example 2: A manufacturing process for a fiber-reinforced waterproof material for electronic backplanes, comprising the following steps: (1) Preparation of flame-retardant polycarbonate polyols: (3-aminopropyl)trimethoxysilane was mixed with water at a mass ratio of 1:1 and heated to 80°C for 1.8 h to obtain (3-aminopropyl)trimethoxysilane hydrolysate; Step A: Mix octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution, heat and stir to react, adjust pH to 7.0, remove low-boiling substances under vacuum to obtain hydroxyl-terminated aminosiloxane; Step B: Mix hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, and solvent, heat to react to obtain intermediate A containing aldehyde and hydroxyl groups, then mix with DOPO, heat to react, wash and dry after reaction to obtain DOPO derivative containing hydroxyl groups; Step C: Mix DOPO derivative, nitrogen-containing polyol, diester, and catalyst, and carry out transesterification and polycondensation reactions sequentially, cool to obtain flame-retardant polycarbonate polyol; In Step A, the mass ratio of octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution is 10:9.0:0.03; the mass fraction of potassium hydroxide aqueous solution is 9%; In Step A, the heating and stirring reaction... The process conditions are as follows: temperature 135℃, time 5h, rotation speed 150r / min; in step A, the vacuum removal of low-boiling substances is performed at a temperature of 150℃ for 1.8h; in step B, the mass ratio of hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, DOPO, and solvent is 1:1:0.9:9; in step B, the heating reaction is performed at a temperature of 75℃ for 7h; in step B, the temperature rise reaction is performed at a temperature of 82℃ for 5h; in step B, the drying is performed at a temperature of 65℃ for 40min; in step C, the mass ratio of DOPO derivative, nitrogen-containing polyol, carbonate diester, and catalyst is 10:38:24:0.05; in step C, the transesterification reaction is performed at a temperature of 158℃ for 9.5h; in step C, the polycondensation reaction is performed at a temperature of 158℃ for 42h and a pressure of 2kPa. (2) Preparation of flame-retardant glass fiber: S1: Glass fiber is mixed with hydrochloric acid aqueous solution, soaked, washed, and dried to obtain hydroxylated glass fiber; S2: Hydroxylated glass fiber is dispersed in N,N-dimethylformamide, stirred to form a suspension, and maleic anhydride, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine are added under nitrogen atmosphere. The mixture is heated and stirred to react, filtered, washed, and dried to obtain modified glass fiber; S3: Modified glass fiber and dimethyl sulfoxide are mixed and stirred evenly. Flame-retardant polycarbonate polyol and an alkaline catalyst are added under nitrogen atmosphere. The mixture is heated to react, filtered, washed, and dried to obtain flame-retardant glass fiber; In S1, the ratio of glass fiber to hydrochloric acid aqueous solution is 1 g: 25 mL; the concentration of hydrochloric acid aqueous solution is 2 mol / L. In S1, the soaking treatment conditions are: temperature 40℃, time 1.0h; in S2, the mass ratio of hydroxylated glass fiber, N,N-dimethylformamide, maleic anhydride, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 1:8:0.50:0.08:0.02; in S2, the heating and stirring reaction conditions are: temperature 70℃, time 4h, rotation speed 150r / min; in S3, the mass ratio of modified glass fiber, dimethyl sulfoxide, flame-retardant polycarbonate polyol, and alkaline catalyst is 1:8:1.9:0.5; in S3, the heating reaction conditions are: temperature 75℃, time 5h; in S1, S2, and S3, the drying conditions are: temperature 65℃, time 35min. (3) Preparation of fiber-reinforced waterproof materials: Step 1: Mix PET resin, flame-retardant glass fiber, carbodiimide, and antioxidant, and heat and stir to obtain a mixture. Step 2: Feed the mixture into a twin-screw extruder, melt, extrude, granulate, inject mold, and cool to obtain a glass fiber / PET composite material. Step 3: Take the glass fiber / PET composite material, use a silica ceramic target, and deposit silica on the surface of the glass fiber / PET composite material by magnetron sputtering to form a silica film, obtaining a fiber-reinforced waterproof material. In Step 1, the mass ratio of PET resin, flame-retardant glass fiber, carbodiimide, and antioxidant is 100:50:2:1.0. In Step 1, the heating and stirring process conditions are: temperature 260℃, stirring speed 700 r / min, time 100 min. In Step 2, the melting temperature is 265℃. In Step 2, the extrusion temperature is 275℃. In Step 2, the injection molding temperature is 275℃. In Step 3, the magnetron sputtering process conditions are: power density 810 W / cm³. 2 The temperature was 60℃ and the pressure was 0.8Pa. The working gas used in the magnetron sputtering process was argon. The argon gas flow rate was 4.0mL / min. In step 3, the thickness of the silicon oxide film was 300nm.

[0039] Example 3: A manufacturing process for a fiber-reinforced waterproof material for electronic backplanes, comprising the following steps: (1) Preparation of flame-retardant polycarbonate polyols: (3-aminopropyl)trimethoxysilane was mixed with water at a mass ratio of 1:1 and heated to 75°C for 1.5 h to obtain (3-aminopropyl)trimethoxysilane hydrolysate. Step A: Mix octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution, heat and stir to react, adjust pH to 6.5, remove low-boiling substances under vacuum to obtain hydroxyl-terminated aminosiloxane; Step B: Mix hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, and solvent, heat to react to obtain intermediate A containing aldehyde and hydroxyl groups, then mix with DOPO, heat to react, wash and dry after reaction to obtain DOPO derivative containing hydroxyl groups; Step C: Mix DOPO derivative, nitrogen-containing polyol, diester, and catalyst, and carry out transesterification and polycondensation reactions sequentially, cool to obtain flame-retardant polycarbonate polyol; In Step A, the mass ratio of octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution is 10:8.5:0.02; the mass fraction of potassium hydroxide aqueous solution is 8%; In Step A, the reaction is heated and stirred. The process conditions are as follows: temperature 130℃, time 4h, rotation speed 100r / min; in step A, the vacuum removal of low-boiling substances is performed at a temperature of 145℃ for 1.5h; in step B, the mass ratio of hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, DOPO, and solvent is 1:1:0.8:8; in step B, the heating reaction is performed at a temperature of 70℃ for 6h; in step B, the temperature rise reaction is performed at a temperature of 80℃ for 4h; in step B, the drying is performed at a temperature of 60℃ for 30min; in step C, the mass ratio of DOPO derivative, nitrogen-containing polyol, diester, and catalyst is 10:35:22:0.04; in step C, the transesterification reaction is performed at a temperature of 155℃ for 9h; in step C, the polycondensation reaction is performed at a temperature of 155℃ for 40h and a pressure of 1kPa. (2) Preparation of flame-retardant glass fiber: S1: Glass fiber is mixed with hydrochloric acid aqueous solution, soaked, washed, and dried to obtain hydroxylated glass fiber; S2: Hydroxylated glass fiber is dispersed in N,N-dimethylformamide, stirred to form a suspension, and maleic anhydride, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine are added under nitrogen atmosphere. The mixture is heated and stirred to react, filtered, washed, and dried to obtain modified glass fiber; S3: Modified glass fiber and dimethyl sulfoxide are mixed and stirred evenly. Flame-retardant polycarbonate polyol and an alkaline catalyst are added under nitrogen atmosphere. The mixture is heated to react, filtered, washed, and dried to obtain flame-retardant glass fiber; In S1, the ratio of glass fiber to hydrochloric acid aqueous solution is 1g:20mL; the concentration of hydrochloric acid aqueous solution is 1mol / L. In S1, the soaking treatment conditions are: temperature 30℃, time 0.5h; in S2, the mass ratio of hydroxylated glass fiber, N,N-dimethylformamide, maleic anhydride, dicyclohexylcarbodiimide, and 4-dimethylaminopyridine is 1:5:0.45:0.07:0.01; in S2, the heating and stirring reaction conditions are: temperature 60℃, time 3h, rotation speed 100r / min; in S3, the mass ratio of modified glass fiber, dimethyl sulfoxide, flame-retardant polycarbonate polyol, and alkaline catalyst is 1:5:1.8:0.4; in S3, the heating reaction conditions are: temperature 70℃, time 4h; in S1, S2, and S3, the drying process conditions are: temperature 60℃, time 30min. (3) Preparation of fiber-reinforced waterproof materials: Step 1: Mix PET resin, flame-retardant glass fiber, carbodiimide, and antioxidant, and heat and stir to obtain a mixture; Step 2: Feed the mixture into a twin-screw extruder, melt, extrude, granulate, inject mold, and cool to obtain a glass fiber / PET composite material; Step 3: Take the glass fiber / PET composite material, use a silica ceramic target, and deposit silica on the surface of the glass fiber / PET composite material by magnetron sputtering to form a silica film, obtaining a fiber-reinforced waterproof material; In Step 1, the mass ratio of PET resin, flame-retardant glass fiber, carbodiimide, and antioxidant is 100:45:1:0.5; In Step 1, the heating and stirring process conditions are: temperature 250℃, stirring speed 600 r / min, time 90 min; In Step 2, the melting temperature is 260℃; In Step 2, the extrusion temperature is 270℃; In Step 2, the injection molding temperature is 270℃; In Step 3, the magnetron sputtering process conditions are: power density 5 W / cm³. 2 The temperature was 50℃ and the pressure was 0.2Pa. The working gas used in the magnetron sputtering process was argon. The argon gas flow rate was 3.5mL / min. In step 3, the thickness of the silicon oxide film was 100nm.

[0040] Comparative Example 1: Compared with Example 1, the flame-retardant polycarbonate polyol was replaced with polycarbonate diol, and the mass ratio of modified glass fiber, dimethyl sulfoxide, polycarbonate diol and alkaline catalyst was adjusted to 1:10:2.2:0.6, while the other conditions remained unchanged.

[0041] Comparative Example 2: Compared with Example 1, no silicon oxide film was deposited on the surface of the glass fiber / PET composite material, while other conditions remained unchanged.

[0042] Comparative Example 3: Compared with Example 1, the glass fiber was not modified and all other conditions remained unchanged.

[0043] Comparative Example 4: Compared with Example 1, no silicon oxide film was deposited on the surface of the glass fiber / PET composite material, and the glass fiber was not modified, while other conditions remained unchanged.

[0044] Experiment: The fiber-reinforced waterproof materials obtained in the examples and comparative examples were tested for various properties; Water resistance test: The water contact angle of the obtained fiber-reinforced waterproof material was tested according to GB / T 30693-2014 to characterize its water resistance. Flame retardancy test: The oxygen index of the obtained fiber-reinforced waterproof material was tested according to GB / T2406.2-2009 to characterize its flame retardancy; Hydrolysis degree test: Take the obtained fiber-reinforced waterproof material and place it in a constant temperature and humidity test chamber for hydrolysis treatment. Set the temperature to 85℃, humidity to 85%, and test time to 1000h. Then test the waterproofness and flame retardancy. Based on the data in Table 1, the following conclusions can be drawn: Compared to Example 1, the oxygen index of the fiber-reinforced waterproof material obtained in Comparative Example 1 decreased, while the water contact angle did not change significantly. This is because commercially available polycarbonate diol does not contain nitrogen, phosphorus, or silicon elements, and therefore does not possess flame retardancy. However, the material surface still has a silica film, so the change in waterproofness is not significant. The water contact angle of the fiber-reinforced waterproof materials obtained in Comparative Examples 2 and 3 did not change much, but the oxygen index in Comparative Example 3 decreased more significantly. This is because the silica film can effectively prevent water and water vapor penetration, and the siloxane chain structure in the flame-retardant polycarbonate molecule is stable and also has a certain degree of waterproofness. However, Comparative Example 3 does not contain flame-retardant elements, so the flame retardancy decreased more significantly. In Comparative Example 4, both flame retardancy and waterproofness decreased significantly. It is understood that the preparation of the deposited silica film and flame-retardant polycarbonate polyol in this application can promote the improvement of the waterproof and flame-retardant properties of the fiber-reinforced waterproof material.

[0045] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

Claims

1. A manufacturing process for a fiber-reinforced waterproof material for electronic backplanes, characterized in that: Includes the following steps: Step 1: Mix PET resin, flame-retardant glass fiber, carbodiimide and antioxidant, heat and stir to obtain a mixture; Step 2: Feed the mixture into a twin-screw extruder, melt, extrude, granulate, inject mold, and cool to obtain a glass fiber / PET composite material; Step 3: Take the glass fiber / PET composite material, use a silicon oxide ceramic target, and deposit silicon oxide on the surface of the glass fiber / PET composite material by magnetron sputtering to form a silicon oxide film, thus obtaining a fiber-reinforced waterproof material.

2. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 1, characterized in that: The flame-retardant glass fiber is obtained by the following process: S1: Mix glass fiber with hydrochloric acid aqueous solution, soak and treat, wash and dry to obtain hydroxylated glass fiber; S2: Disperse hydroxylated glass fibers in N,N-dimethylformamide, stir to form a suspension, add maleic anhydride, dicyclohexylcarbodiimide and 4-dimethylaminopyridine under nitrogen atmosphere protection, heat and stir to react, filter, wash and dry to obtain modified glass fibers; S3: Mix modified glass fiber and dimethyl sulfoxide, stir evenly, add flame-retardant polycarbonate polyol and alkaline catalyst under nitrogen atmosphere protection, heat to react, filter, wash and dry to obtain flame-retardant glass fiber.

3. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 2, characterized in that: The preparation process of the flame-retardant polycarbonate polyol is as follows: Step A: Mix octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution, heat and stir to react, adjust pH to 6.5~7.0, remove low-boiling substances under vacuum to obtain hydroxyl-terminated aminosiloxane; Step B: Hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, and solvent are mixed and heated to obtain intermediate A containing aldehyde and hydroxyl groups. Then, it is mixed with DOPO and heated to react. After the reaction is completed, it is washed and dried to obtain DOPO derivative containing hydroxyl groups. Step C: Mix DOPO derivative, nitrogen-containing polyol, diester, and catalyst, and carry out transesterification and polycondensation reactions in sequence. After cooling, flame-retardant polycarbonate polyol is obtained.

4. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 2, characterized in that: In S2, the mass ratio of hydroxylated glass fiber, N,N-dimethylformamide, maleic anhydride, dicyclohexylcarbodiimide and 4-dimethylaminopyridine is 1:(5~10):(0.45~0.55):(0.07~0.09):(0.01~0.03).

5. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 2, characterized in that: In S3, the mass ratio of modified glass fiber, dimethyl sulfoxide, flame-retardant polycarbonate polyol, and alkaline catalyst is 1: (5~10): (1.8~2.0): (0.4~0.6). The alkaline catalyst is one or a mixture of potassium carbonate and potassium hydroxide.

6. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 3, characterized in that: In step A, the mass ratio of octamethyl silicone oil, (3-aminopropyl)trimethoxysilane hydrolysate, and potassium hydroxide aqueous solution is 10:(8.5~9.5):(0.02~0.04). The mass fraction of the potassium hydroxide aqueous solution is 8-10%.

7. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 3, characterized in that: In step B, the mass ratio of hydroxyl-terminated aminosiloxane, 2,6-pyridinedicarboxaldehyde, DOPO, and solvent is 1:1:(0.8~1.0):(8~10). The solvent is one or a mixture of anhydrous ethanol, N,N-dimethylformamide, and dimethyl sulfoxide.

8. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 3, characterized in that: In step C, the mass ratio of DOPO derivative, nitrogen-containing polyol, carbonate diester, and catalyst is 10:(35~40):(22~26):(0.04~0.06). The nitrogen-containing polyol is one or a mixture of two of diethanolamine and triethanolamine; The catalyst is one or a mixture of tetraethyl titanate, dibutyltin dilaurate, and dibutyltin octanoate.

9. The manufacturing process of a fiber-reinforced waterproof material for electronic backplanes according to claim 3, characterized in that: In step A, the (3-aminopropyl)trimethoxysilane hydrolysate is prepared by the following process: (3-aminopropyl)trimethoxysilane was mixed with water at a mass ratio of 1:1 and heated to 75-85℃ for 1.5-2.0 h to obtain (3-aminopropyl)trimethoxysilane hydrolysate.

10. A fiber-reinforced waterproof material for electronic backplanes, characterized in that: The product is obtained using the manufacturing process described in any one of claims 1 to 9.

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