Textile sizing agent, method of preparation and use on electronic grade glass fiber cloth

Abstract

The application relates to the technical field of textile sizing, and discloses a textile sizing, a preparation method and application on electronic-grade glass fiber cloth. The textile sizing is prepared by mixing polyvinyl alcohol, maleic anhydride esterified starch, hyperbranched polyether, a silane coupling agent solution and a photoinitiator, the combination effect of the sizing and the glass fiber is optimized, and the crosslinking degree of the sizing on the surface of the glass fiber yarn is further improved through a photocuring crosslinking reaction. The hyperbranched polyether has the functions of compatibilization and multifunctional crosslinking points; the maleic anhydride esterified starch retains the film-forming property of the starch and introduces copolymerizable double bond sites; the silane coupling agent solution can be anchored on the surface of the glass fiber through Si-O-Si bonds; in addition, after the sizing is sized and is cured through ultraviolet light, the carbon-carbon double bonds in the components are copolymerized to form a crosslinking network, and the interface performance of the sizing film and the glass fiber is improved through chemical bonding. The prepared sizing significantly improves the sizing rate, wear resistance and breaking strength of the electronic-grade glass fiber yarn, and can meet the weaving requirements of high-quality electronic-grade glass fiber cloth.

Description

Technical Field

[0001] This invention relates to the field of textile sizing technology, specifically to a textile sizing agent, its preparation method, and its application on electronic-grade glass fiber cloth. Background Technology

[0002] Electronic-grade fiberglass cloth is one of the core reinforcing materials in the manufacture of electronic products. In the production process of electronic cloth, sizing of the fiberglass yarn is a critical step, and the quality of sizing largely determines the weaving efficiency of the electronic fiber cloth and the performance of the final product.

[0003] Glass fiber yarn has low breaking strength, and during weaving, fuzz and breakage easily occur on the fiber surface, affecting weaving efficiency and fabric quality. Therefore, glass fiber yarn must be sized before weaving to impart good bundle properties, abrasion resistance, and flexibility. However, the smooth and chemically inert surface of glass fiber yarn results in insufficient interfacial bonding between the sizing agent and the fiber, making it prone to desizing during weaving.

[0004] Currently, the sizing systems used in the production of electronic-grade glass fiber cloth are still mainly based on traditional film-forming substances such as polyvinyl alcohol (PVA). Although these traditional sizings have good film-forming properties, their bonding force with the glass fiber surface is weak, and their interfacial adhesion is limited, resulting in insufficient abrasion resistance and limited improvement in breaking strength of the sized glass fiber yarn. To improve the interfacial bonding between the sizing and glass fiber, silane coupling agents are often used in the surface modification of glass fibers. Silane coupling agents can form "molecular bridges" between the glass fiber and the sizing, thereby enhancing the bonding force between the glass fiber and the sizing. However, traditional sizing systems lack active functional groups that can react with silane coupling agents and film-forming substances, resulting in low bridging efficiency of the coupling agents and failing to fully realize their application potential in the interfacial reinforcement of glass fibers.

[0005] Therefore, developing a textile sizing agent with high bonding strength to the surface of glass fiber is of great significance for improving the weaving efficiency and product quality of electronic-grade glass fiber cloth. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a textile sizing agent, its preparation method, and its application in electronic-grade glass fiber cloth. A textile sizing agent is prepared by mixing polyvinyl alcohol, maleic anhydride esterified starch, hyperbranched polyether, silane coupling agent solution, and a photoinitiator. This optimizes the bonding effect between the sizing agent and glass fiber, while further improving the crosslinking degree of the sizing agent on the glass fiber yarn surface through a photocuring crosslinking reaction. The hyperbranched polyether acts as both a compatibilizer and a multifunctional crosslinking point; the maleic anhydride esterified starch introduces copolymerizable double bond sites while retaining the film-forming properties of starch; the silane coupling agent solution can be anchored to the glass fiber surface through Si-O-Si bonds; furthermore, after sizing, the sizing agent is cured by ultraviolet light, causing the carbon-carbon double bonds in each component to copolymerize and form a crosslinked network, improving the interfacial properties between the sizing film and the glass fiber through chemical bonding. The sizing agent prepared by this invention significantly improves the sizing rate, abrasion resistance, and breaking strength of electronic-grade glass fiber yarn, meeting the weaving requirements of electronic-grade glass fiber cloth.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: A method for preparing a textile sizing agent includes the following steps: Step (1): Mix and dissolve 3,5-dihydroxybenzoic acid, allyl glycidyl ether, tetrabutylammonium bromide and N,N-dimethylformamide, and react. After the reaction is completed, add trimethylolpropane triglycidyl ether solution and continue the reaction. After the reaction is completed, concentrate by rotary evaporation, add tetrahydrofuran to dissolve, and wash with water and ether in sequence. Dry to obtain hyperbranched polyether. Step (2): Mix and dissolve the acid-hydrolyzed starch and sodium sulfate aqueous solution to obtain a suspension. Adjust the pH value and add maleic anhydride acetone solution dropwise. After the addition is complete, react. After the reaction is complete, neutralize, filter, wash, dry, pulverize and sieve to obtain maleic anhydride esterified starch. Step (3): Mix polyvinyl alcohol (PVA), maleic anhydride esterified starch, hyperbranched polyether, and water evenly, then add silane coupling agent solution and photoinitiator, and continue to mix evenly to obtain textile sizing agent.

[0008] Preferably, in step (1), the ratio of 3,5-dihydroxybenzoic acid, allyl glycidyl ether, tetrabutylammonium bromide, N,N-dimethylformamide, and trimethylolpropane triglycidyl ether solution is 0.1 mol: 0.1 mol: 0.001-0.005 mol: 40-50 mL: 100-110 mL; the trimethylolpropane triglycidyl ether solution is prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.01-0.02 mol of tetrabutylammonium bromide, and 100-110 mL of N,N-dimethylformamide.

[0009] Preferably, in step (1), the reaction and continued reaction conditions are: reaction in a nitrogen atmosphere at a temperature of 80-95°C for 3-6 hours.

[0010] Preferably, in step (2): the concentration of sodium sulfate aqueous solution is 5-10 wt%; the content of maleic anhydride in the acetone solution is 30-50 wt%; and the ratio of acid hydrolyzed starch, 5-10 wt% sodium sulfate aqueous solution, and 30-50 wt% maleic anhydride acetone solution is 150-200 g: 400-500 g: 15-25 g.

[0011] Preferably, in step (2), the acetone solution of maleic anhydride is added under the following conditions: the acetone solution of maleic anhydride is added at 30°C for 1-2 hours, and the pH value of the system is maintained at 8-9 during the addition.

[0012] Preferably, in step (2), the reaction conditions are: reacting at 25-35℃ for 0.5-2h.

[0013] Preferably, in step (3), the mass ratio of polyvinyl alcohol, maleic anhydride esterified starch, hyperbranched polyether, water, silane coupling agent solution, and photoinitiator is 15-20:15-20:8-12:100:15-20:1-5; the silane coupling agent solution is prepared by mixing 1-9g of KH550, 1-9g of KH570, 10-20mL of water, and 80-90mL of ethanol.

[0014] Preferably, a textile sizing agent prepared by the method described above is used.

[0015] Preferably, the application of a textile sizing agent as described above on electronic-grade glass fiber cloth includes the following steps: Set the temperature of the sizing tank of the single yarn sizing machine to 60-70℃ and the drying temperature to 80-100℃. Place the textile sizing agent prepared above into the sizing tank and sizing the electronic-grade glass fiber yarn. The sizing speed is 30-50m / min, the yarn tension is 0.3-0.6kN, and after sizing, remove the yarn and perform photocuring using a photochemical reactor with a power of 0.8-1.5kW, a distance of 3-10cm, and a curing time of 20-40s. After photocuring, the sized electronic-grade glass fiber yarn is obtained. The electronic-grade glass fiber yarn is then woven to obtain electronic-grade glass fiber cloth.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention uses a mixture of polyvinyl alcohol, maleic anhydride esterified starch, hyperbranched polyether, silane coupling agent solution, and photoinitiator to prepare a textile sizing agent. Through the synergistic effect of the compounded components, the bonding effect between the sizing agent and glass fiber is optimized. Simultaneously, a photocuring crosslinking reaction further enhances the crosslinking degree of the sizing agent on the glass fiber yarn surface. Specifically, the hyperbranched polyether has active carbon-carbon double bonds at its ends, serving as both compatibilizer and multifunctional crosslinking points; the maleic anhydride esterified starch retains the film-forming properties of starch while introducing copolymerizable double bond sites; the silane coupling agent solution containing KH550 and KH570 can be anchored to the glass fiber surface through Si-O-Si bonds; furthermore, after sizing, the sizing agent is cured under ultraviolet light, causing the carbon-carbon double bonds in each component to copolymerize and form a crosslinked network, improving the interfacial properties between the sizing film and the glass fiber through chemical bonding. The sizing agent prepared by this invention significantly improves the sizing rate, abrasion resistance, and breaking strength of electronic-grade glass fiber yarn, meeting the weaving requirements of electronic-grade glass fiber cloth.

[0017] 2. This invention uses 3,5-dihydroxybenzoic acid and allyl glycidyl ether as raw materials, and utilizes the ring-opening reaction of phenolic hydroxyl groups and epoxy groups to synthesize monomers with allyl double bonds at the ends; subsequently, trimethylolpropane triglycidyl ether is added, and through further reaction of carboxyl groups and epoxy groups, a hyperbranched polyether with functional groups such as active carbon-carbon double bonds at the end and hydroxyl groups is formed. Because allyl glycidyl ether is introduced as a terminating end group in the first step of the reaction, the outer spherical surface of the resulting hyperbranched polyether is enriched with a large number of active carbon-carbon double bonds.

[0018] In the sizing system, hyperbranched polyether can reduce the viscosity of the system and, as a polymer compatibilizer, significantly improve the compatibility between PVA and maleic anhydride esterified starch, ensuring the uniformity of sizing. At the same time, the carbon-carbon double bonds in the hyperbranched polyether provide photopolymerization active sites for the sizing system. Under ultraviolet light irradiation in the presence of a photoinitiator, free radical polymerization occurs, making the hyperbranched polyether molecules act as multifunctional crosslinking points, connecting the components together to form a three-dimensional interpenetrating crosslinked network structure. This improves the crosslinking degree of the sizing film and enhances the mechanical properties of the sized glass fiber yarn.

[0019] 3. This invention utilizes maleic anhydride to esterify and modify acid-hydrolyzed starch. Under alkaline conditions, the hydroxyl groups of acid-hydrolyzed starch react with maleic anhydride, thereby introducing maleic anhydride monoester groups onto the starch molecule backbone. In the resulting maleic anhydride esterified starch, the presence of carboxyl groups enhances the dispersion stability of starch in water. Simultaneously, hydrogen bonds can form between the carboxyl groups and the hydroxyl groups of PVA, improving the compatibility between starch and PVA. Furthermore, the carbon-carbon double bonds introduced by maleic anhydride can react with the carbon-carbon double bonds of hyperbranched polyethers to copolymerize, increasing the crosslinking degree of the sizing film and improving the mechanical properties of the sized glass fiber yarn.

[0020] 4. This invention employs a coupling agent system composed of KH550 and KH570. Through the reaction of silanol groups with the silanol groups on the glass fiber surface, the coupling agent molecules are anchored to the fiber surface, thereby improving the bonding force between the sizing agent and the glass fiber yarn. Furthermore, hydrogen bonds are formed between the amino groups of KH550 and the hydroxyl groups of PVA and the carboxyl groups of maleic anhydride-esterified starch; while the methacryloyloxy group of KH570 can copolymerize with the double bonds of hyperbranched polyether and maleic anhydride-esterified starch during the photocuring stage, covalently fixing the sizing agent crosslinking network to the glass fiber surface. The two coupling agents work synergistically through different bonding mechanisms to construct a multi-anchored chemical bridge between the inorganic glass fiber and the organic sizing film, solving the problem of easy peeling and desizing of the sizing agent on the glass fiber surface. Attached Figure Description

[0021] Figure 1 This is a line graph showing the sizing rate of samples 1-7 prepared in Example 6 and Comparative Examples 3-4 of this invention during performance testing; Figure 2 This is a bar chart showing the number of friction fractures in performance testing of samples 1-7 prepared in Example 6 and Comparative Examples 3-4 of this invention; Figure 3 These are bar graphs showing the fracture strength of samples 1-7 prepared in Example 6 and Comparative Examples 3-4 of this invention during performance testing. Detailed Implementation

[0022] The present invention will be further illustrated below through specific embodiments. The following embodiments are specific implementations of the present invention, but the implementation of the present invention is not limited to the following embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and are included within the protection scope of the present invention.

[0023] Example 1 This embodiment discloses a method for preparing textile sizing agents, including the following steps: Step (1): Mix and dissolve 0.1 mol of 3,5-dihydroxybenzoic acid, 0.1 mol of allyl glycidyl ether, 0.005 mol of tetrabutylammonium bromide and 40 mL of N,N-dimethylformamide. React at 90°C for 5 h under a nitrogen atmosphere. After the reaction is complete, add trimethylolpropane triglycidyl ether solution and continue to react at 90°C under a nitrogen atmosphere for 4 h. After the reaction is complete, concentrate by rotary evaporation, dissolve in tetrahydrofuran, and wash with 80°C hot water and 0°C diethyl ether to precipitate. Take the precipitate and dry it at 40°C to obtain hyperbranched polyether. The trimethylolpropane triglycidyl ether solution was prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.015 mol of tetrabutylammonium bromide, and 100 mL of N,N-dimethylformamide. Step (2): Mix and dissolve 180g of acid-hydrolyzed starch and 450g of 5wt% sodium sulfate aqueous solution to obtain a suspension. Add 6wt% sodium carbonate aqueous solution to adjust the pH to 8. Add 20g of acetone solution containing 40wt% maleic anhydride dropwise at 30℃ for 1.5h, and maintain the pH of the system at 8 during the dropwise addition. After the dropwise addition is completed, react at 30℃ for 1h. After the reaction is completed, add 2mol / L hydrogen chloride aqueous solution to neutralize to pH 7. Filter, wash with 75vol% ethanol aqueous solution, dry at 50℃ for 8h, pulverize and pass through a 100-mesh sieve to obtain maleic anhydride esterified starch. Step (3): Mix 5g of KH550, 5g of KH570, 10mL of water and 90mL of ethanol to obtain a silane coupling agent solution. By mass, 20 parts PVA, 15 parts maleic anhydride esterified starch, 8 parts hyperbranched polyether, and 100 parts water are stirred and mixed evenly. Then, 15 parts silane coupling agent solution and 3 parts photoinitiator are added and stirred and mixed evenly to obtain textile sizing agent.

[0024] Example 2 This embodiment discloses a method for preparing textile sizing agents, including the following steps: Step (1): Mix and dissolve 0.1 mol of 3,5-dihydroxybenzoic acid, 0.1 mol of allyl glycidyl ether, 0.005 mol of tetrabutylammonium bromide and 40 mL of N,N-dimethylformamide. React at 90°C for 5 h under a nitrogen atmosphere. After the reaction is complete, add trimethylolpropane triglycidyl ether solution and continue to react at 90°C under a nitrogen atmosphere for 4 h. After the reaction is complete, concentrate by rotary evaporation, dissolve in tetrahydrofuran, and wash with 80°C hot water and 0°C diethyl ether to precipitate. Take the precipitate and dry it at 40°C to obtain hyperbranched polyether. The trimethylolpropane triglycidyl ether solution was prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.015 mol of tetrabutylammonium bromide, and 100 mL of N,N-dimethylformamide. Step (2): Mix and dissolve 180g of acid-hydrolyzed starch and 450g of 5wt% sodium sulfate aqueous solution to obtain a suspension. Add 6wt% sodium carbonate aqueous solution to adjust the pH to 8. Add 20g of acetone solution containing 40wt% maleic anhydride dropwise at 30℃ for 1.5h, and maintain the pH of the system at 8 during the dropwise addition. After the dropwise addition is completed, react at 30℃ for 1h. After the reaction is completed, add 2mol / L hydrogen chloride aqueous solution to neutralize to pH 7. Filter, wash with 75vol% ethanol aqueous solution, dry at 50℃ for 8h, pulverize and pass through a 100-mesh sieve to obtain maleic anhydride esterified starch. Step (3): Mix 5g of KH550, 5g of KH570, 10mL of water and 90mL of ethanol to obtain a silane coupling agent solution. By mass, 19 parts PVA, 16 parts maleic anhydride esterified starch, 9 parts hyperbranched polyether, and 100 parts water are stirred and mixed evenly. Then, 16 parts silane coupling agent solution and 3 parts photoinitiator are added and stirred and mixed evenly to obtain textile sizing agent.

[0025] Example 3 This embodiment discloses a method for preparing textile sizing agents, including the following steps: Step (1): Mix and dissolve 0.1 mol of 3,5-dihydroxybenzoic acid, 0.1 mol of allyl glycidyl ether, 0.005 mol of tetrabutylammonium bromide and 40 mL of N,N-dimethylformamide. React at 90°C for 5 h under a nitrogen atmosphere. After the reaction is complete, add trimethylolpropane triglycidyl ether solution and continue to react at 90°C under a nitrogen atmosphere for 4 h. After the reaction is complete, concentrate by rotary evaporation, dissolve in tetrahydrofuran, and wash with 80°C hot water and 0°C diethyl ether to precipitate. Take the precipitate and dry it at 40°C to obtain hyperbranched polyether. The trimethylolpropane triglycidyl ether solution was prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.015 mol of tetrabutylammonium bromide, and 100 mL of N,N-dimethylformamide. Step (2): Mix and dissolve 180g of acid-hydrolyzed starch and 450g of 5wt% sodium sulfate aqueous solution to obtain a suspension. Add 6wt% sodium carbonate aqueous solution to adjust the pH to 8. Add 20g of acetone solution containing 40wt% maleic anhydride dropwise at 30℃ for 1.5h, and maintain the pH of the system at 8 during the dropwise addition. After the dropwise addition is completed, react at 30℃ for 1h. After the reaction is completed, add 2mol / L hydrogen chloride aqueous solution to neutralize to pH 7. Filter, wash with 75vol% ethanol aqueous solution, dry at 50℃ for 8h, pulverize and pass through a 100-mesh sieve to obtain maleic anhydride esterified starch. Step (3): Mix 5g of KH550, 5g of KH570, 10mL of water and 90mL of ethanol to obtain a silane coupling agent solution. By mass, 18 parts PVA, 17 parts maleic anhydride esterified starch, 10 parts hyperbranched polyether, and 100 parts water are stirred and mixed evenly. Then, 18 parts silane coupling agent solution and 3 parts photoinitiator are added and stirred and mixed evenly to obtain textile sizing agent.

[0026] Example 4 This embodiment discloses a method for preparing textile sizing agents, including the following steps: Step (1): Mix and dissolve 0.1 mol of 3,5-dihydroxybenzoic acid, 0.1 mol of allyl glycidyl ether, 0.005 mol of tetrabutylammonium bromide and 40 mL of N,N-dimethylformamide. React at 90°C for 5 h under a nitrogen atmosphere. After the reaction is complete, add trimethylolpropane triglycidyl ether solution and continue to react at 90°C under a nitrogen atmosphere for 4 h. After the reaction is complete, concentrate by rotary evaporation, dissolve in tetrahydrofuran, and wash with 80°C hot water and 0°C diethyl ether to precipitate. Take the precipitate and dry it at 40°C to obtain hyperbranched polyether. The trimethylolpropane triglycidyl ether solution was prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.015 mol of tetrabutylammonium bromide, and 100 mL of N,N-dimethylformamide. Step (2): Mix and dissolve 180g of acid-hydrolyzed starch and 450g of 5wt% sodium sulfate aqueous solution to obtain a suspension. Add 6wt% sodium carbonate aqueous solution to adjust the pH to 8. Add 20g of acetone solution containing 40wt% maleic anhydride dropwise at 30℃ for 1.5h, and maintain the pH of the system at 8 during the dropwise addition. After the dropwise addition is completed, react at 30℃ for 1h. After the reaction is completed, add 2mol / L hydrogen chloride aqueous solution to neutralize to pH 7. Filter, wash with 75vol% ethanol aqueous solution, dry at 50℃ for 8h, pulverize and pass through a 100-mesh sieve to obtain maleic anhydride esterified starch. Step (3): Mix 5g of KH550, 5g of KH570, 10mL of water and 90mL of ethanol to obtain a silane coupling agent solution. By mass, 16 parts PVA, 19 parts maleic anhydride esterified starch, 11 parts hyperbranched polyether, and 100 parts water are stirred and mixed evenly. Then, 19 parts silane coupling agent solution and 3 parts photoinitiator are added and stirred and mixed evenly to obtain textile sizing agent.

[0027] Example 5 This embodiment discloses a method for preparing textile sizing agents, including the following steps: Step (1): Mix and dissolve 0.1 mol of 3,5-dihydroxybenzoic acid, 0.1 mol of allyl glycidyl ether, 0.005 mol of tetrabutylammonium bromide and 40 mL of N,N-dimethylformamide. React at 90°C for 5 h under a nitrogen atmosphere. After the reaction is complete, add trimethylolpropane triglycidyl ether solution and continue to react at 90°C under a nitrogen atmosphere for 4 h. After the reaction is complete, concentrate by rotary evaporation, dissolve in tetrahydrofuran, and wash with 80°C hot water and 0°C diethyl ether to precipitate. Take the precipitate and dry it at 40°C to obtain hyperbranched polyether. The trimethylolpropane triglycidyl ether solution was prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.015 mol of tetrabutylammonium bromide, and 100 mL of N,N-dimethylformamide. Step (2): Mix and dissolve 180g of acid-hydrolyzed starch and 450g of 5wt% sodium sulfate aqueous solution to obtain a suspension. Add 6wt% sodium carbonate aqueous solution to adjust the pH to 8. Add 20g of acetone solution containing 40wt% maleic anhydride dropwise at 30℃ for 1.5h, and maintain the pH of the system at 8 during the dropwise addition. After the dropwise addition is completed, react at 30℃ for 1h. After the reaction is completed, add 2mol / L hydrogen chloride aqueous solution to neutralize to pH 7. Filter, wash with 75vol% ethanol aqueous solution, dry at 50℃ for 8h, pulverize and pass through a 100-mesh sieve to obtain maleic anhydride esterified starch. Step (3): Mix 5g of KH550, 5g of KH570, 10mL of water and 90mL of ethanol to obtain a silane coupling agent solution. By mass, 15 parts PVA, 20 parts maleic anhydride esterified starch, 12 parts hyperbranched polyether, and 100 parts water are stirred and mixed evenly. Then, 20 parts silane coupling agent solution and 3 parts photoinitiator are added and stirred and mixed evenly to obtain textile sizing agent.

[0028] Example 6 This embodiment discloses the application of a textile sizing agent on electronic-grade glass fiber cloth. The application method includes the following steps: The temperature of the sizing tank of the single yarn sizing machine was set to 60℃, and the drying temperature was set to 80℃. The textile sizing agents prepared in Examples 1-5 were placed in the sizing tank to sizing the electronic-grade glass fiber yarn. The sizing speed was 50m / min, the yarn tension was 0.5kN, and after sizing, the yarn was taken out and photocured using a photochemical reactor with a power of 1kW, a distance of 5cm, and a curing time of 30s. After photocuring, samples 1-5 of the sized electronic-grade glass fiber yarn were obtained. The electronic-grade glass fiber yarn was then woven to obtain electronic-grade glass fiber cloth.

[0029] Comparative Example 1 This comparative example discloses a method for preparing a textile sizing agent, comprising the following steps: Step (1): Mix and dissolve 180g of acid-hydrolyzed starch and 450g of 5wt% sodium sulfate aqueous solution to obtain a suspension. Add 6wt% sodium carbonate aqueous solution to adjust the pH to 8. Add 20g of acetone solution containing 40wt% maleic anhydride dropwise at 30℃ for 1.5h, and maintain the pH of the system at 8 during the dropwise addition. After the dropwise addition is completed, react at 30℃ for 1h. After the reaction is completed, add 2mol / L hydrogen chloride aqueous solution to neutralize to pH 7. Filter, wash with 75vol% ethanol aqueous solution, dry at 50℃ for 8h, pulverize and pass through a 100-mesh sieve to obtain maleic anhydride esterified starch. Step (2): Mix 5g of KH550, 5g of KH570, 10mL of water and 90mL of ethanol to obtain a silane coupling agent solution. By mass, 20 parts PVA, 15 parts maleic anhydride esterified starch, and 100 parts water are stirred and mixed evenly. Then, 15 parts silane coupling agent solution and 3 parts photoinitiator are added and stirred and mixed evenly to obtain textile sizing agent.

[0030] Comparative Example 2 This embodiment discloses a method for preparing textile sizing agents, including the following steps: Step (1): Mix and dissolve 0.1 mol of 3,5-dihydroxybenzoic acid, 0.1 mol of octyl glycidyl ether, 0.005 mol of tetrabutylammonium bromide and 40 mL of N,N-dimethylformamide. React at 90°C for 5 h under a nitrogen atmosphere. After the reaction is complete, add trimethylolpropane triglycidyl ether solution and continue to react at 90°C under a nitrogen atmosphere for 4 h. After the reaction is complete, concentrate by rotary evaporation, dissolve in tetrahydrofuran, and wash with 80°C hot water and 0°C diethyl ether to precipitate. Take the precipitate and dry it at 40°C to obtain hyperbranched polyether. The trimethylolpropane triglycidyl ether solution was prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.015 mol of tetrabutylammonium bromide, and 100 mL of N,N-dimethylformamide. Step (2): Mix and dissolve 180g of acid-hydrolyzed starch and 450g of 5wt% sodium sulfate aqueous solution to obtain a suspension. Add 6wt% sodium carbonate aqueous solution to adjust the pH to 8. Add 20g of acetone solution containing 40wt% succinic anhydride dropwise at 30℃ for 1.5h, and maintain the pH of the system at 8 during the dropwise addition. After the dropwise addition is completed, react at 30℃ for 1h. After the reaction is completed, add 2mol / L hydrogen chloride aqueous solution to neutralize to pH 7. Filter, wash with 75vol% ethanol aqueous solution, dry at 50℃ for 8h, and pulverize through a 100-mesh sieve to obtain succinic anhydride esterified starch. Step (3): Mix 10g of KH550, 10mL of water and 90mL of ethanol to obtain a silane coupling agent solution; By mass, 20 parts PVA, 15 parts succinic anhydride esterified starch, 8 parts hyperbranched polyether, and 100 parts water are stirred and mixed evenly. Then, 15 parts silane coupling agent solution are added and stirred and mixed evenly to obtain textile sizing agent.

[0031] Comparative Example 3 This comparative example discloses the application of a textile sizing agent on electronic-grade glass fiber cloth. The application method includes the following steps: The temperature of the sizing tank of the single yarn sizing machine was set to 60℃, and the drying temperature was set to 80℃. The textile sizing agent prepared in Comparative Example 1 was placed in the sizing tank and sizing was performed on the electronic-grade glass fiber yarn. The sizing speed was 50m / min, the yarn tension was 0.5kN, and after sizing, the yarn was taken out and photocured using a photochemical reactor with a power of 1kW, a distance of 5cm, and a curing time of 30s. After photocuring, sample 6 of the sized electronic-grade glass fiber yarn was obtained. The electronic-grade glass fiber yarn was then woven to obtain electronic-grade glass fiber cloth.

[0032] Comparative Example 4 This comparative example discloses the application of a textile sizing agent on electronic-grade glass fiber cloth. The application method includes the following steps: The temperature of the sizing tank of the single yarn sizing machine was set to 60℃ and the drying temperature was set to 80℃. The textile sizing agent prepared in Comparative Example 2 was placed in the sizing tank and sized on the electronic-grade glass fiber yarn. The sizing speed was 50m / min and the yarn tension was 0.5kN. After sizing, the yarn was taken out and sample 7 of the sized electronic-grade glass fiber yarn was obtained. The electronic-grade glass fiber yarn was woven to obtain electronic-grade glass fiber cloth.

[0033] In the above embodiments and comparative examples: the electronic-grade glass fiber yarn is a low-dielectric glass electronic yarn with a specification of 11.2 tex; the polyvinyl alcohol is PVA-1788; KH550 is γ-aminopropyltriethoxysilane; KH570 is γ-methacryloyloxypropyltrimethoxysilane; and the photoinitiator is photoinitiator 1173. Acid-hydrolyzed starch is prepared from corn starch through refining and acid hydrolysis. The apparent viscosity of the corn starch is 53 mPa·s. The specific preparation method includes the following steps: Step (1): Pass corn starch through a 100-mesh sieve and disperse it in a methanol / water solution (v / v = 85 / 15) to obtain a starch suspension with a starch concentration of 40wt%. Stir the starch suspension with a concentration of 40wt% at 40℃ for 1 hour, filter the filter cake, wash it 3-4 times with a methanol / water solution (v / v = 85 / 15), filter the filter cake again, disperse it in water and wash it 1-2 times, filter the filter cake, dry it at 50℃ for 12 hours, grind it through a 100-mesh sieve to obtain refined starch. Step (2): Disperse refined starch in water to prepare a starch suspension of 1500g with a refined starch concentration of 40wt%. Add 27mL of 2mol / L hydrogen chloride aqueous solution at 50℃ and stir for 4.5h. After the reaction is completed, add 1mol / L sodium carbonate aqueous solution to neutralize to neutral. Filter, wash with water, dry at 50℃ for 6h, grind through a 100-mesh sieve to obtain acid hydrolyzed starch.

[0034] Test case Performance tests were performed on samples 1-7 prepared in Example 6 and Comparative Examples 3-4; the specific test results are shown in Table 1: Table 1 Raw yarn 0 82 5.20 Sample 1 3.02 206 10.77 Sample 2 3.04 207 10.89 Sample 3 3.05 210 11.04 Sample 4 3.09 212 11.19 Sample 5 3.11 215 11.32 Sample 6 2.97 165 8.76 Sample 7 3.01 131 6.85 The testing methods for each indicator in Table 1 are as follows: The sizing rate is tested by drying a certain mass of sized yarn in a 105℃ forced-air drying oven for 2 hours, weighing the yarn, then placing it in a muffle furnace and simmering it at 625℃ for 2 hours, weighing the yarn again, and calculating the sizing rate by calculating the mass fraction of combustible matter on the yarn surface; the number of friction breaks is tested according to FZ / T01058-1999 "Test Method for Abrasion Resistance of Yarn - Reciprocating Roller Method"; the breaking strength is tested according to GB / T 7690.3-2013 "Test Methods for Reinforcing Materials Yarn - Part 3: Determination of Breaking Strength and Elongation at Break of Glass Fiber".

[0035] As can be seen from the test results in Table 1, the textile sizing agent prepared by this invention can effectively improve the performance of glass fibers.

[0036] The textile sizing agent prepared in Comparative Example 1 did not contain hyperbranched polyether; the sizing system consisted only of PVA, maleic anhydride esterified starch, silane coupling agent, and photoinitiator. Due to the lack of compatibilizing and crosslinking effects of hyperbranched polyether, the compatibility between PVA and maleic anhydride esterified starch was poor, and the dispersion uniformity of the sizing components was insufficient, thus affecting the cohesive strength and interfacial adhesion of the sizing film. Therefore, the sizing rate, abrasion resistance, and tensile strength of Sample 6 were all lower than those of the example samples.

[0037] In the textile sizing agent prepared in Comparative Example 2, octyl glycidyl ether was used to replace allyl glycidyl ether to synthesize hyperbranched polyether, and succinic anhydride was used to replace maleic anhydride to synthesize succinic anhydride esterified starch. Only KH550 was used as the silane coupling agent. In this sizing system, neither the hyperbranched polyether, the esterified starch, nor the organic end of the coupling agent contained carbon-carbon double bond active functional groups capable of free radical polymerization under ultraviolet light irradiation. The entire system could not form a cross-linked network structure through photocuring, and the sizing film relied solely on physical drying. Therefore, its density and mechanical strength were lower than those of the sizing film from the example after photocrosslinking and curing. Furthermore, using only KH550, an amino-type silane coupling agent, could not establish covalent bonds between the sizing cross-linked network and the glass fiber surface. Interfacial bonding mainly relied on hydrogen bonding and physical adsorption, resulting in a limited increase in the number of frictional fractures and the tensile strength of Sample 7.

[0038] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A method for preparing a textile sizing agent, characterized in that, Includes the following steps: Step (1): Mix and dissolve 3,5-dihydroxybenzoic acid, allyl glycidyl ether, tetrabutylammonium bromide and N,N-dimethylformamide, and react. After the reaction is completed, add trimethylolpropane triglycidyl ether solution and continue the reaction. After the reaction is completed, concentrate by rotary evaporation, add tetrahydrofuran to dissolve, and wash with water and ether in sequence. Dry to obtain hyperbranched polyether. Step (2): Mix and dissolve the acid-hydrolyzed starch and sodium sulfate aqueous solution to obtain a suspension. Adjust the pH value and add maleic anhydride acetone solution dropwise. After the addition is complete, react. After the reaction is complete, neutralize, filter, wash, dry, pulverize and sieve to obtain maleic anhydride esterified starch. Step (3): Mix polyvinyl alcohol, maleic anhydride esterified starch, hyperbranched polyether, and water evenly, then add silane coupling agent solution and photoinitiator, and continue to mix evenly to obtain textile sizing agent.

2. The method for preparing a textile sizing agent according to claim 1, characterized in that, In step (1), the ratio of 3,5-dihydroxybenzoic acid, allyl glycidyl ether, tetrabutylammonium bromide, N,N-dimethylformamide, and trimethylolpropane triglycidyl ether solution is 0.1mol:0.1mol:0.001-0.005mol:40-50mL:100-110mL.

3. The method for preparing a textile sizing agent according to claim 1, characterized in that, In step (1), the trimethylolpropane triglycidyl ether solution is prepared by mixing and dissolving 0.3 mol of trimethylolpropane triglycidyl ether, 0.01-0.02 mol of tetrabutylammonium bromide, and 100-110 mL of N,N-dimethylformamide.

4. The method for preparing a textile sizing agent according to claim 1, characterized in that, In step (1), the reaction and continued reaction conditions are: reaction in a nitrogen atmosphere at a temperature of 80-95℃ for 3-6 hours.

5. The method for preparing a textile sizing agent according to claim 1, characterized in that, In step (2): the concentration of sodium sulfate aqueous solution is 5-10 wt%; the content of maleic anhydride in acetone solution is 30-50 wt%; the ratio of acid hydrolyzed starch, 5-10 wt% sodium sulfate aqueous solution, and 30-50 wt% maleic anhydride acetone solution is 150-200 g: 400-500 g: 15-25 g.

6. The method for preparing a textile sizing agent according to claim 1, characterized in that, In step (2), the conditions for adding the acetone solution of maleic anhydride are as follows: add the acetone solution of maleic anhydride at 30°C for 1-2 hours, and maintain the pH value of the system at 8-9 during the addition.

7. The method for preparing a textile sizing agent according to claim 1, characterized in that, In step (2), the reaction conditions are: reacting at 25-35℃ for 0.5-2h.

8. The method for preparing a textile sizing agent according to claim 1, characterized in that, In step (3), the mass ratio of polyvinyl alcohol, maleic anhydride esterified starch, hyperbranched polyether, water, silane coupling agent solution, and photoinitiator is 15-20:15-20:8-12:100:15-20:1-5; the silane coupling agent solution is prepared by mixing 1-9g of KH550, 1-9g of KH570, 10-20mL of water, and 80-90mL of ethanol.

9. A textile sizing agent prepared by the method described in claims 1-8.

10. The application of the textile sizing agent as described in claim 9 on electronic-grade glass fiber cloth, the application method comprising the following steps: Set the temperature of the sizing tank of the single yarn sizing machine to 60-70℃ and the drying temperature to 80-100℃. Place the textile sizing agent prepared above into the sizing tank and sizing the electronic-grade glass fiber yarn. The sizing speed is 30-50m / min, the yarn tension is 0.3-0.6kN, and after sizing, remove the yarn and perform photocuring using a photochemical reactor with a power of 0.8-1.5kW, a distance of 3-10cm, and a curing time of 20-40s. After photocuring, the sized electronic-grade glass fiber yarn is obtained. The electronic-grade glass fiber yarn is then woven to obtain electronic-grade glass fiber cloth.

Images