High-efficiency desizing device and method for ultra-low dielectric-loss electronic-grade quartz glass fiber cloth

Abstract

The present invention relates to the technical field of quartz glass fiber cloth desizing. Disclosed are a high-efficiency desizing device and method for an ultra-low dielectric-loss electronic-grade quartz glass fiber cloth. In the present invention, by means of combining CO2 with a desizing solution, the organic matter on the surface of the quartz glass fiber cloth is pre-degraded; and the organic matter is then rinsed by means of ultrasonic water washing, hydroentanglement, spraying and other methods in sequence, thereby achieving fiber opening, such that the desizing time and desizing temperature can be reduced, thereby reducing the energy consumption and improving the desizing effect. Moreover, for a quartz glass fiber cloth product, the strength loss of a cloth surface can be reduced. Compared with the existing process involving the problem of fibers being hardened by smoldering not being conducive to fiber-opening in the subsequent FN process, the fiber opening is achieved during the desizing process in the present invention, thereby solving the problem.

Description

High-efficiency desizing device and method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth Technical Field

[0001] This invention relates to the field of desizing technology for quartz glass fiber cloth, specifically to a high-efficiency desizing device and method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth. Background Technology

[0002] Quartz fiber possesses extremely low dielectric constant and dielectric loss, representing the pinnacle of glass fiber materials. Its application in printed circuit boards can improve signal transmission speed, enhance signal transmission quality, and reduce signal loss. With the rapid development of electronic information equipment such as AI servers, Starlink, and autonomous driving chips, the market demand for electronic-grade quartz glass fiber is experiencing explosive growth.

[0003] Due to the hardness and brittleness of quartz glass fiber, a starch-based sizing agent and sizing agent need to be coated on the yarn surface to improve its abrasion resistance. Since the organic matter coated on the glass fiber can hinder the adhesion between the fiber and the reinforced substrate, thus affecting the electrical performance of downstream PCB boards, it is generally necessary to remove the sizing agent from the glass fiber surface through hot cleaning and post-treatment processes, followed by coupling agent coating and fiber opening treatment in the FN process before use. Currently, the main desizing methods for electronic-grade quartz glass fiber cloth are KH continuous heat treatment desizing and BH secondary desizing. For special electronic-grade quartz glass fiber cloth, these desizing methods have disadvantages such as large loss of fabric strength, incomplete desizing, and poor fiber opening effect. Chinese invention patent CN113957701B discloses a water-soluble one-step desizing solution and its preparation method for ultra-thin electronic-grade glass fiber cloth. The desizing solution includes 6-8 parts of stabilizer, 15-20 parts of alkali, 1-3 parts of hydrogen peroxide, 2-5 parts of additives, and water. The desizing solution in this patent can reduce the loss of fabric strength and achieve clean desizing, but the high alkali content in the desizing solution results in poor fabric fuzziness, which requires further improvement. Therefore, there is an urgent need to develop an efficient desizing method for electronic-grade quartz glass fiber cloth to solve the problems existing in the aforementioned desizing methods. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide an efficient desizing device and method for ultra-low dielectric loss electronic grade quartz glass fiber cloth. The method uses a combination of CO2 and desizing liquid to pre-desizing the organic matter on the surface of the quartz glass fiber cloth, and then washes the organic matter by ultrasonic water washing, hydroentangling, spraying and other methods in sequence, and realizes fiber opening. This can reduce desizing time and desizing temperature, thereby reducing energy consumption and improving desizing effect.

[0005] The technical solution of this invention is as follows:

[0006] On one hand, this invention provides a high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth, including a CO2 desizing reactor, an ultrasonic washing tank, a hydroentangling mechanism, a spraying mechanism, a drying mechanism, and a winding shaft. A conveyor roller is arranged between the ultrasonic washing tank, the hydroentangling mechanism, the spraying mechanism, the drying mechanism, and the winding shaft, and the quartz glass fiber cloth is conveyed through the conveyor roller. The CO2 desizing reactor includes a shell, with an air inlet and an air outlet at both ends of the shell, and a desizing liquid nozzle installed at the top. A winding shaft is arranged inside the shell, and the quartz glass fiber cloth is wound on the winding shaft. The ultrasonic washing tank includes water... The system includes a tank containing a roller driven by a motor, with water outlets on the roller. Quartz glass fiber cloth is attached to the surface of the roller and is conveyed as the roller rolls. An ultrasonic rod is located at the center of the roller. The hydroentangling mechanism includes a water spray pipe with several rows of water spray holes at its bottom to spray water onto the quartz glass fiber cloth below, rinsing off residual organic matter and breaking down the fibers. The spraying mechanism includes a water spray pipe with two water spray holes at its bottom to spray water onto the quartz glass fiber cloth below, rinsing off residual organic matter and breaking down the fibers.

[0007] Preferably, a filter membrane is provided at the air inlet of the CO2 deslurry reactor, and a flow guide horn is provided inside the shell at the air inlet.

[0008] Preferably, the drum has several impellers arranged along its length, and the impellers are driven to rotate by a motor; the water outlet holes on the drum have a diameter of 2-5mm and a spacing of 5-10mm. If the holes are too large or too sparse, the water pressure will be insufficient; if they are too small, the quartz glass fiber cloth will be sprayed out with wrinkles; if the holes are too dense, the drum will not have sufficient support. The ultrasonic washing tank has two tension rollers arranged at the feed end and the discharge end, respectively, and the quartz glass fiber cloth passes between the two tension rollers. The ultrasonic washing tank has a cloth pressing roller arranged at the feed end and the discharge end, respectively, so that the quartz glass fiber cloth adheres to the surface of the drum.

[0009] Preferably, the drying mechanism includes a drying oven, and a plurality of conveying rollers are provided inside the drying oven, through which the quartz glass fiber cloth is conveyed and dried.

[0010] Preferably, the bottom of the first water spray pipe is provided with six rows of first water spray holes, with a hole diameter of 0.05-0.1mm and a hole spacing of 0.1-0.2mm. The distance between the first water spray hole and the quartz glass fiber cloth is 7-9cm. The bottom of the second water spray pipe is provided with one row of second water spray holes, with a hole diameter of 0.4-0.5mm and a hole spacing of 5-8cm. The distance between the second water spray hole and the quartz glass fiber cloth is 9-11cm. If the distance between the first and second water spray holes and the quartz glass fiber cloth is too close, the hydroentangling effect on the ultra-thin cloth will be too strong, damaging the cloth surface; if the distance is too far, the hydroentangling effect will be too weak, failing to achieve the cleaning and fiber opening effects.

[0011] On the other hand, the present invention provides an efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth, which is carried out using the aforementioned efficient desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth, and includes the following steps:

[0012] S1 Pre-desizing: The quartz glass fiber cloth wound on the spool is placed into the CO2 desizing reactor. Desizing liquid is sprayed onto the quartz glass fiber cloth through the desizing liquid nozzle, while CO2 is introduced into the CO2 desizing reactor through the air inlet and flows out through the air outlet. During this process, the sizing material on the surface of the quartz glass fiber cloth reacts with the desizing liquid and is carried away by the CO2 airflow, achieving pre-desizing of the sizing material on the surface of the quartz glass fiber cloth. In this process, the desizing liquid spray covers the entire CO2 desizing reactor, ensuring sufficient and effective contact with CO2 and forming a microemulsion. This promotes the reaction between the desizing liquid and the sizing material and organic matter of the wetting agent on the surface of the quartz glass fiber cloth, accelerating the desizing of the quartz glass fiber cloth. Furthermore, according to the principle of like dissolves like, the slurry on the surface of the quartz glass fiber cloth dissolves in CO2 and flows away from the surface of the quartz glass fiber cloth with the flow of CO2. The slurry inside the quartz glass fiber cloth diffuses to the surface under the action of concentration difference. The newly introduced CO2 molecules quickly approach the surface of the quartz glass fiber cloth, causing the slurry that has diffused to the surface to continue to dissolve in CO2 and be carried away, thereby completing the pre-desizing of the slurry.

[0013] S2 Ultrasonic Washing: The roll of pre-desized quartz glass fiber cloth is removed from the CO2 desizing reactor. Under the action of the winding shaft, the quartz glass fiber cloth is conveyed by a conveyor roller into the ultrasonic washing tank and adheres to the roller surface. The quartz glass fiber cloth is conveyed as the roller rolls, while simultaneously, the ultrasonic waves emitted by the ultrasonic rod further clean the surface of the quartz glass fiber cloth and the slurry trapped within the quartz glass fiber filaments, improving the desizing effect. The ultrasonic waves emitted by the ultrasonic rod have washing, dispersing, and cavitation effects, causing the large organic molecules on the quartz glass fiber cloth to separate, promoting the loosening of the adhesion between the slurry, wetting agent, and fibers, while reducing the surface tension of stains and emulsifying dirt and oil. The emulsification effect caused by the ultrasonic waves transforms the removed slurry from a gel state to a sol state, improving the desizing effect on organic matter. The thermal effect of the ultrasound maintains a certain temperature in the aqueous solution, providing energy for the reaction. Ultimately, it not only cleans the surface organic matter of the quartz glass fiber cloth but also removes the slurry trapped within the quartz glass fiber filaments, improving the desizing effect.

[0014] S3 Hydroentangling: After ultrasonic washing, the quartz glass fiber cloth is conveyed to the hydroentangling mechanism via a conveyor roller. Water is sprayed onto the quartz glass fiber cloth through a water spray pipe to wash away any residual organic matter and open the fibers.

[0015] S4 Spraying: The hydroentangled quartz glass fiber cloth is conveyed to the spraying mechanism via a conveyor roller. Water is sprayed onto the quartz glass fiber cloth through two spray pipes to further wash away any residual organic matter and open the fibers.

[0016] S5 Drying: The sprayed quartz glass fiber cloth is conveyed to the drying mechanism by the conveyor roller for drying.

[0017] S6 winding: The dried quartz glass fiber cloth is wound onto the winding shaft.

[0018] Preferably, in step S1, each 1000L of desizing solution comprises the following components by mass percentage: sodium percarbonate 6.25-10.5%, tetraacetylethylenediamine 2.5-3.5%, PVA degrading enzyme 0.35-0.5%, PEG degrading enzyme 0.35-0.5%, amylase 0.35-0.75%, pH buffer 3.61-4.41%, penetrant 0.5-1.5%, antistaining agent 14.25-21%, and the balance being purified water; wherein the pH buffer is disodium hydrogen phosphate 2.66-3.36% and citric acid 0.95-1.05%, and the antistaining agent is 5.7-6% FMEE and 8.55-15% FMES.

[0019] In the desizing solution used in this invention, sodium percarbonate can slowly decompose into sodium carbonate and hydrogen peroxide in aqueous solution. Sodium carbonate can act as an enzyme activator and provide a weakly alkaline pH. Under alkaline conditions, tetraacetylethylenediamine not only reacts with hydrogen peroxide to form peracetic acid, which has a practical bleaching effect, but also accelerates the decomposition of sodium percarbonate. Each 1000L of desizing solution contains 6.25-10.5% sodium percarbonate. Insufficient addition results in less ·OH formation, a lower pH, and a reduced desizing rate; excessive addition promotes the oxidation of acetic anhydride, lowering the pH of the desizing solution and reducing the efficiency of oxidative desizing.

[0020] The peracetic acid generated above lowers the pH of the desizing solution, but this lower pH is detrimental to further activation, the decomposition of hydrogen peroxide, and the activity of biological enzymes. In contrast, the sodium carbonate produced from the decomposition of sodium percarbonate can appropriately raise the pH of the desizing solution, making it weakly alkaline initially.

[0021] Both hydrogen peroxide and peracetic acid are oxidizing agents that can oxidize and desizing polyester fabrics under alkaline conditions. The ·OH released from the decomposition of hydrogen peroxide has extremely strong oxidizing power. For carbohydrates, under the action of ·OH, starch molecules undergo a dehydrogenation reaction, causing the C-C bonds to break and ultimately be completely oxidized to CO2. ·OH also adds to the carbon-carbon double bonds of water-soluble polymers, causing the double bonds to break and resulting in complete oxidation to CO2.

[0022] Preferably, the mass ratio of sodium percarbonate to tetraacetylatedrethylenediamine is (2.5-3):1. If the ratio is too small, insufficient hydrogen peroxide is generated, resulting in inadequate ·OH and a rapid decrease in desizing rate. If the ratio is too large, insufficient catalyst and insufficient ·OH also lead to a rapid decrease in desizing rate. In the pH buffer, the mass ratio of disodium hydrogen phosphate to citric acid is (2.8-3.2):1. If the pH is too low, hydrogen peroxide remains stable, resulting in insufficient decomposition. If the pH is too high, hydrogen peroxide decomposes too quickly, leading to ineffective decomposition. The enzyme activity is highest at the pH when the mass ratio of disodium hydrogen phosphate to citric acid meets the above-mentioned value. Citric acid can act as a chelating agent, chelating metal ions in the sizing agent to prevent yellowing of the fabric. The sizing coating on the surface of quartz fiberglass cloth mainly consists of starch, polyvinyl alcohol (PVA), and polyethylene glycol (PEG). The mass ratio of PVA-degrading enzyme, PEG-degrading enzyme, and amylase is 1:1:(1-1.5). The amylase is a bacterial α-amylase, such as Bacillus subtilis, Bacillus amyloliquefaciens, and Bacillus licheniformis, which hydrolyzes starch into dextrin and oligosaccharides, which are easily removed during washing. Smaller molecules often surround larger molecules; that is, PVA and PEG encapsulate starch. Amylase can enter through the gaps in PVA and PEG to interact with starch. When the starch is hydrolyzed, the outer layers of PVA and PEG break down and detach from the fabric. PVA-degrading enzymes are hydrolytic enzymes, such as Alcaligenes faecalis and Stenotrophomonas maltophilia, which degrade PVA. PEG-degrading enzymes are redox enzymes, such as Achromobacterium and Bacillus, which degrade PEG. In the antistain agent, the mass ratio of FMEE to FMES is 1:(1.5-2.5). FMEE is an environmentally friendly nonionic surfactant, such as octadecanoic acid fatty acid polyoxybutylene-7 ester and hexadecanoic acid fatty acid polyoxybutylene-7 ester. It has strong penetrability, allowing it to penetrate into the interior of the glass fiber filaments of the fabric, accelerating the removal of sizing agents and providing strong cleaning power. FMES is its sulfonate, such as sodium octadecanoic acid fatty acid polyoxybutylene-7 ester sulfonate and sodium hexadecanoic acid fatty acid polyoxybutylene-7 ester sulfonate. It is anionic surfactant, electrostatically attracting cationic sizing agents and combining with the removed organic matter to form micelles, resulting in strong dispersing effects. When using FMEE alone, as the amount of sizing agent removed increases, the sizing agent in the solution will re-adhere to the glass fiber surface, reducing cleaning power. When using FMES alone, it can only slowly disperse organic matter on the fabric surface and cannot penetrate into the interior of the glass fiber filaments, resulting in low efficiency. Therefore, a combination of the two is necessary. FMEE removes the sizing agent from inside the glass fiber filaments while FMES disperses the removed sizing agent into the solution, preventing the re-adhesion of removed organic matter and improving the desizing efficiency of the glass fiber organic matter. The penetrant is a non-ionic penetrant, such as fatty alcohol polyoxyethylene ether-7 and pentylphenol polyoxyethylene ether-8, which accelerates liquid penetration, promotes the rapid penetration of desizing liquid into the fiber micropores, and assists in the dispersion of sizing material.

[0023] When preparing the desizing solution, add sodium percarbonate for 20 ± 3 minutes, followed by tetraacetylethylenediamine. This initial weakly alkaline condition is conducive to the decomposition of hydrogen peroxide. The addition of tetraacetylethylenediamine lowers the pH, which is beneficial for bleaching with peracetic acid and for bio-enzymatic treatment under neutral conditions. Adding it too late will affect the bleaching effect.

[0024] Preferably, in step S1, the CO2 pressure is 20-25 MPa, the desizing liquid temperature is 52-58℃ (low temperature results in low enzyme activity, while excessively high temperature leads to enzyme inactivation and ineffective decomposition of hydrogen peroxide; however, if the temperature is too low, the organic matter only swells and the degradation is minimal), and the treatment time of the quartz glass fiber cloth in the CO2 desizing reactor is 24-26 min.

[0025] Preferably, in step S2, the water temperature in the water tank is 54-60℃, and the conveying speed of the quartz glass fiber cloth is 28-32m / min. If the speed is too fast, the cloth will have uneven tension, resulting in wrinkles on the cloth surface. In addition, the ultrasonic water washing, hydroentangling cleaning, and spray cleaning times of the cloth are too short, and the cleaning and fiber opening effects cannot be achieved. The impeller rotation speed is 95-100m / min. In step S3, the water pressure of the first spray nozzle is 2.5-4.5kg, and the water temperature is 10-30℃. In step S4, the water pressure of the second spray nozzle is 3.5-5.5kg, and the water temperature is 10-30℃. In step S4, the drying temperature is 59-61℃. If the drying temperature is too high, the strength of the cloth surface will be greatly reduced.

[0026] Compared with the prior art, the present invention has the following advantages:

[0027] 1. The desizing method of this invention replaces the traditional KH continuous heat treatment desizing and BH smoldering secondary desizing high-temperature heat treatment methods. It employs a gentler approach, combining CO2 with the desizing solution. First, the quartz glass fiber cloth is placed in a CO2 fluid for pre-reaction. CO2's permeability and high dispersibility allow for the pre-degradation of organic matter on the surface of the quartz glass fiber cloth, while minimizing directional impact on the fibers. It can penetrate into the yarn gaps, loosening and dispersing the yarn bundles, ensuring yarn integrity and preparing for subsequent hydroentangling and fiber opening. Then, the organic matter is washed away sequentially through ultrasonic washing, hydroentangling, and spraying. Washing removes the decomposed organic matter, while hydroentangling and spraying continue to clean away residual organic matter and achieve fiber opening. Finally, the fabric is dried for the next FN post-treatment. This desizing method reduces the concentration of the desizing solution, shortens the desizing time, and lowers the desizing temperature, thereby reducing energy consumption and improving the desizing effect. Furthermore, for quartz glass fiber cloth products, it reduces fabric strength loss. Compared to the existing process where burning causes fiber hardening and hinders fiber opening in the subsequent FN process, this invention solves the problem by opening the fiber during the desizing process.

[0028] 2. Traditional desizing solutions use strong alkalis and surfactants, which only cause swelling without chemical reaction, damaging the fibers and making the fabric surface rough. The sizing agent coating the surface of quartz glass fiber cloth mainly consists of starch, polyvinyl alcohol (PVA), and polyethylene glycol (PEG). The aqueous solution in the bath has high viscosity, and PVA easily forms gels, which can easily back-adhere to the fabric, forming sizing spots. For ultra-thin specialty fabrics, this can easily clog the fabric's gaps and pores. Traditional desizing solutions use highly specific enzymes and KMnO4, which has strong oxidizing properties, resulting in reduced fabric strength and easy wrinkling and pilling. The acids used can also damage the fibers. This invention utilizes a combination of complex enzymes and H2O2 oxidation to make desizing gentler. Furthermore, by adding auxiliaries, back-adhesion to the fabric is prevented. The desizing solution used in this invention combines chelating agents, penetrants, and surfactants, forming a highly efficient desizing system through the synergistic effect of "chelating impurities → penetrating fibers → emulsifying and dispersing."

[0029] 3. The desizing solution of the present invention contains a pH buffer, so that the pH value is controlled at around 7, and no acid-base neutralization is required after desizing, and it can be discharged directly. Attached Figure Description

[0030] Figure 1 is a schematic diagram of the structure of the high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth of the present invention.

[0031] Figure 2 is a schematic diagram of the CO2 deslurry reactor of the present invention.

[0032] Figure 3 is a schematic diagram of the ultrasonic water washing tank of the present invention.

[0033] Figure 4 is a schematic diagram of the structure of the roller of the present invention.

[0034] Figure 5 is a schematic diagram of the hydroentangling mechanism of the present invention.

[0035] Figure 6 is a schematic diagram of the spraying mechanism of the present invention.

[0036] In the diagram, 101 is the housing; 102 is the air inlet; 103 is the air outlet; 104 is the desizing agent nozzle; 105 is the reel; 106 is the filter membrane; 107 is the flow guide horn; 2 is the ultrasonic water washing tank; 201 is the water tank; 202 is the drum; 203 is the water outlet; 204 is the ultrasonic rod; 205 is the impeller; 3 is the hydroentangling mechanism; 301 is the first water spray pipe; 302 is the first water spray hole; 4 is the spraying mechanism; 401 is the second water spray pipe; 402 is the second water spray hole; 5 is the take-up shaft; 6 is the conveyor roller; 7 is the tension roller; 8 is the pressing roller; 9 is the quartz glass fiber cloth; and 10 is the drying oven. Embodiments of the present invention

[0037] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions of this invention will be clearly and completely described below in conjunction with the embodiments of this invention.

[0038] The high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth used in the following embodiments, as shown in Figure 1, includes a CO2 desizing reactor, an ultrasonic water washing tank 2, a hydroentangling mechanism 3, a spraying mechanism 4, a drying mechanism, and a winding shaft 5. A conveyor roller 6 is arranged between the ultrasonic water washing tank 2, the hydroentangling mechanism 3, the spraying mechanism 4, the drying mechanism, and the winding shaft 5, and the quartz glass fiber cloth 9 is conveyed through the conveyor roller 6.

[0039] As shown in Figure 2, the CO2 deslurry reactor includes a shell 101. An air inlet 102 and an air outlet 103 are respectively provided at both ends of the shell 101. A filter membrane 106 is provided at the air inlet 102, and a flow guide horn 107 is provided inside the shell 101 at the air inlet 102 to make the CO2 fluid fill the entire CO2 deslurry reactor. A deslurry nozzle 104 is installed at the top, and a roller 105 is provided inside the shell 101, on which quartz glass fiber cloth 9 is wound.

[0040] As shown in Figures 1 and 3, two ultrasonic washing tanks 2 are provided. Each ultrasonic washing tank 2 includes a water tank 201. Two tension rollers 7 are respectively installed at the feed end and the discharge end of the water tank 201. The quartz glass fiber cloth 9 passes between the two tension rollers 7. A roller 202 is installed inside the water tank 201. The roller 202 is driven to rotate by a motor. As shown in Figures 3 and 4, the roller 202 is provided with water outlet holes 203 with a diameter of 5 mm and a spacing of 10 mm. As shown in Figure 3, the feed end and the discharge end of the water tank 201 are respectively provided with cloth pressing rollers 8, so that the quartz glass fiber cloth 9 is attached to the surface of the roller 202. The quartz glass fiber cloth 9 is conveyed as the roller 202 rolls. An ultrasonic rod 204 is provided at the center inside the roller 202. As shown in Figure 3, several impellers 205 are arranged along the length of the roller 202 inside the roller 202. The impellers 205 are driven to rotate by a motor.

[0041] As shown in Figure 5, the hydroentangling mechanism 3 includes a water spray pipe 301. The bottom of the water spray pipe 301 has six rows of staggered water spray holes 302, each with a diameter of 0.1 mm and a spacing of 0.2 mm. The distance between the water spray holes 302 and the quartz fiber cloth 9 is 8 cm. Water is sprayed onto the quartz fiber cloth 9 below through the water spray holes 302 to wash away residual organic matter and break up the fibers. As shown in Figure 6, the spraying mechanism 4 includes a second water spray pipe 401. The bottom of the second water spray pipe 401 has a row of second water spray holes 402, each with a diameter of 0.5 mm and a spacing of 5 cm. The distance between the second water spray holes 402 and the quartz fiber cloth 9 is 10 cm. Water is sprayed onto the quartz fiber cloth 9 below through the second water spray holes 402 to wash away residual organic matter and break up the fibers.

[0042] As shown in Figure 1, the drying mechanism includes a drying oven 10, which is equipped with four conveying rollers 6. The quartz glass fiber cloth 9 is conveyed and dried in the drying oven 10 through the conveying rollers 6.

[0043] Example 1

[0044] The efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth in this embodiment includes the following steps:

[0045] S1 Pre-desizing

[0046] Quartz glass fiber cloth 9 is wound onto a roll 105 and placed into a CO2 desizing reactor. Desizing liquid is sprayed onto the quartz glass fiber cloth 9 through desizing liquid nozzle 104. Simultaneously, CO2 is introduced into the CO2 desizing reactor through the air inlet 102 and flows out through the air outlet 103. The CO2 pressure is 20 MPa, the desizing liquid temperature is 55℃, and the treatment time of quartz glass fiber cloth 9 in the CO2 desizing reactor is 25 minutes.

[0047] The desizing solution per 1000L contains the following components by weight percentage: sodium percarbonate 10.5%, tetraacetylated ethylenediamine 3.5%, PVA-degrading enzyme *Alcaligenes faecalis* 0.35%, PEG-degrading enzyme *Bacillus subtilis* 0.35%, amylase *Bacillus subtilis* 0.35%, pH buffer 4%, penetrant 1%, antistaining agent 14.25%, and the balance being purified water. Specifically, the pH buffer consists of disodium hydrogen phosphate 3% and citric acid 1%; the antistaining agent consists of octadecanoic acid polyoxybutylene-7 ester 5.7% and octadecanoic acid polyoxybutylene-7 ester sulfonate 8.55%; and the penetrant is fatty alcohol polyoxyethylene ether-7.

[0048] S2 Ultrasonic Water Washing

[0049] The roll 105 containing the pre-desized quartz glass fiber cloth 9 is removed from the CO2 desizing reactor. Under the action of the take-up roller 5, the quartz glass fiber cloth 9 is conveyed by the conveyor roller 6 to the ultrasonic water washing tank 2 at a conveying speed of 32 m / min. The water temperature in the water tank 201 is 57℃, and the cloth is adhered to the surface of the roller 202 by the action of two pressing rollers 8. The quartz glass fiber cloth 9 is conveyed as the roller 202 rolls. At the same time, the ultrasonic waves emitted by the ultrasonic rod 204 further clean the surface of the quartz glass fiber cloth 9 and the slurry mixed in the quartz glass fiber filaments, improving the desizing effect. Meanwhile, the impeller 205 pushes the water in the roller 202 to the water outlet 203 of the roller 202 and sprays it out. The impeller 205 rotates at a speed of 95 m / min, which can wash away the organic residue of the quartz glass fiber cloth 9 wrapped on the surface of the roller 202.

[0050] S3 spunlace

[0051] After ultrasonic washing, the quartz glass fiber cloth 9 is conveyed to the hydroentangling mechanism 3 via the conveyor roller 6. Water is sprayed onto the quartz glass fiber cloth 9 through the water spray pipe 301 at a pressure of 3.5 kg and a temperature of 20 °C. This washes away residual organic matter and opens the fibers, while also widening the warp yarns to reduce the air permeability of the cloth, thus preparing it for further post-processing.

[0052] S4 spray

[0053] After hydroentangling, the quartz glass fiber cloth 9 is conveyed to the spraying mechanism 4 via the conveyor roller 6. Water is sprayed onto the quartz glass fiber cloth 9 through the water spray pipe 401 at a pressure of 4.5 kg and a temperature of 20 °C. This further washes away the residual organic matter on the quartz glass fiber cloth 9 and opens the fibers. It also opens up the width of the weft yarn, reducing the air permeability of the cloth and preparing it for further post-processing.

[0054] S5 Drying: The sprayed quartz glass fiber cloth 9 is conveyed to the drying mechanism via the conveyor roller 6 and dried at 60°C.

[0055] S6 winding: The dried quartz glass fiber cloth 9 is wound onto the winding shaft 5.

[0056] Example 2

[0057] The efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth in this embodiment includes the following steps:

[0058] S1 Pre-desizing

[0059] Quartz glass fiber cloth 9 is wound onto a winding shaft and placed into a CO2 desizing reactor. Desizing liquid is sprayed onto the quartz glass fiber cloth 9 through desizing liquid nozzle 104. Simultaneously, CO2 is introduced into the CO2 desizing reactor through air inlet 102 and flows out through air outlet 103. The CO2 pressure is 25 MPa, the desizing liquid temperature is 52℃, and the treatment time of quartz glass fiber cloth 9 in the CO2 desizing reactor is 24 min.

[0060] The desizing solution per 1000L contains the following components by weight percentage: sodium percarbonate 6.25%, tetraacetylated ethylenediamine 2.5%, PVA-degrading enzyme Stenotrophomonas maltophilia 0.5%, PEG-degrading enzyme Achromobacterium tumefaciens 0.5%, amylase Bacillus licheniformis 0.5%, pH buffer 4.41%, penetrant 0.5%, antistaining agent 21%, and the balance being purified water. Specifically, the pH buffer consists of disodium hydrogen phosphate 3.36% and citric acid 1.05%; the antistaining agent consists of hexadecanoic acid polyoxybutylene-7 ester 6% and hexadecanoic acid polyoxybutylene-7 ester sulfonate 15%; and the penetrant is pentylphenol polyoxyethylene ether-8.

[0061] S2 Ultrasonic Water Washing

[0062] Same as Example 1, except that: the water temperature of the ultrasonic water washing tank 2 is 54℃, and the conveying speed of the quartz glass fiber cloth 9 is 30m / min.

[0063] S3 spunlace

[0064] After ultrasonic washing, the quartz glass fiber cloth 9 is conveyed to the hydroentangling mechanism 3 via the conveyor roller 6. Water is sprayed onto the quartz glass fiber cloth 9 through the water spray pipe 301 at a pressure of 2.5 kg and a temperature of 10 °C. This washes away residual organic matter and opens the fibers, while also widening the warp yarns to reduce the air permeability of the cloth, thus preparing it for further post-processing.

[0065] S4 spray

[0066] After hydroentangling, the quartz glass fiber cloth 9 is conveyed to the spraying mechanism 4 via the conveyor roller 6. Water is sprayed onto the quartz glass fiber cloth 9 through the water spray pipe 401 at a water pressure of 3.5 kg and a water temperature of 10 °C. This further washes away the residual organic matter on the quartz glass fiber cloth 9 and opens the fibers. It can also open up the width of the weft yarn, reduce the air permeability of the cloth, and prepare for further post-processing.

[0067] S5 Drying: The sprayed quartz glass fiber cloth 9 is conveyed to the drying mechanism via the conveyor roller 6 and dried at 59°C.

[0068] S6 winding: The dried quartz glass fiber cloth 9 is wound onto the winding shaft 5.

[0069] Example 3

[0070] The efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth in this embodiment includes the following steps:

[0071] S1 Pre-desizing

[0072] Quartz glass fiber cloth 9 is wound onto a winding shaft and placed into a CO2 desizing reactor. Desizing liquid is sprayed onto the quartz glass fiber cloth 9 through desizing liquid nozzle 104. Simultaneously, CO2 is introduced into the CO2 desizing reactor through air inlet 102 and flows out through air outlet 103. The CO2 pressure is 24 MPa, the temperature is 58℃, and the treatment time of quartz glass fiber cloth 9 in the CO2 desizing reactor is 26 minutes.

[0073] Each 1000L desizing solution comprises the following components by weight percentage: sodium percarbonate 7.5%, tetraacetylated ethylenediamine 3%, PVA-degrading enzyme *Alcaligenes faecalis* 0.5%, PEG-degrading enzyme *Bacillus* 0.5%, amylase-hydrolyzed *Bacillus amyloliquefaciens* 0.75%, pH buffer 3.61%, penetrant 1.5%, antistaining agent 18%, and the balance being purified water. Specifically, the pH buffer consists of disodium hydrogen phosphate 2.66% and citric acid 0.95%; the antistaining agent consists of hexadecanoic acid polyoxybutylene-7 ester 6% and hexadecanoic acid polyoxybutylene-7 ester sulfonate 12%; and the penetrant is pentylphenol polyoxyethylene ether-8.

[0074] S2 Ultrasonic Water Washing

[0075] Same as Example 1, except that: the water temperature of the ultrasonic water washing tank 2 is 60°C, and the conveying speed of the quartz glass fiber cloth 9 is 28m / min.

[0076] S3 spunlace

[0077] After ultrasonic washing, the quartz glass fiber cloth 9 is conveyed to the hydroentangling mechanism 3 via the conveyor roller 6. Water is sprayed onto the quartz glass fiber cloth 9 through the water spray pipe 301 at a pressure of 4.5 kg and a temperature of 30 °C. This washes away residual organic matter on the quartz glass fiber cloth 9 and opens the fibers. It also opens up the width of the warp yarns, reducing the air permeability of the cloth and preparing it for further post-processing.

[0078] S4 spray

[0079] After hydroentangling, the quartz glass fiber cloth 9 is conveyed to the spraying mechanism 4 via the conveyor roller 6. Water is sprayed onto the quartz glass fiber cloth 9 through the water spray pipe 401 at a pressure of 5.5 kg and a temperature of 30 °C. This further washes away the residual organic matter on the quartz glass fiber cloth 9 and opens the fibers. It also opens up the width of the weft yarn, reducing the air permeability of the cloth and preparing it for further post-processing.

[0080] S5 Drying: The sprayed quartz glass fiber cloth 9 is conveyed to the drying mechanism via the conveyor roller 6 and dried at 61°C.

[0081] S6 winding: The dried quartz glass fiber cloth 9 is wound onto the winding shaft 5.

[0082] Comparative Example 1

[0083] Comparative Example 1 uses the existing KH+BH process to desizing quartz glass fiber cloth 9. KH: Quartz glass fiber cloth 9 is desized at a speed of 60 m / min and passes through a furnace zone of 310℃, with the cloth roll in the furnace zone for 10 seconds. BH: The entire roll of quartz glass fiber cloth 9 is fired in the furnace in two stages: fired at 280℃ for 5 hours, and then heated to 400℃ for 35 hours, with a heating rate of 15℃ / h.

[0084] Comparative Example 2

[0085] The difference from Example 1 is that Comparative Example 2 uses water instead of the desizing solution in Example 1.

[0086] Comparative Example 3

[0087] The difference from Example 1 is that, in the anti-staining agent of the desizing liquid, an equal amount of octadecanoic acid fatty acid polyoxybutene-7 ester is used instead of sodium octadecanoic acid fatty acid polyoxybutene-7 ester sulfonate.

[0088] Comparative Example 4

[0089] The difference from Example 1 is that, in the anti-staining agent of the desizing liquid, sodium octadecanoic acid fatty acid polyoxybutene-7 ester sulfonate is used in an equal amount to replace octadecanoic acid fatty acid polyoxybutene-7 ester.

[0090] Comparative Example 5

[0091] The difference from Example 1 is that in step S1, CO2 is not introduced into the CO2 deslurry reactor.

[0092] Comparative Example 6

[0093] The difference from Example 1 is that in step S1, the temperature of the desizing liquid sprayed in the CO2 desizing reactor is 80°C.

[0094] Comparative Example 7

[0095] The difference from Example 1 is that in step S2, the ultrasonic rod 204 in the ultrasonic water washing tank 2 is turned off.

[0096] The performance of the quartz glass fiber cloth 9 treated in Examples 1-3 and Comparative Examples 1-7 was tested. The test method for the combustible content is as follows:

[0097] Take 95-10g of desizing quartz glass fiber cloth, place it in a drying oven and dry it at 125℃ for 60min to constant weight; then heat it at 625℃ for 40min to constant weight. Combustible content (%) = amount of sample reduction after heating to constant weight / sample weight after heating to constant weight.

[0098] The tensile breaking strength test method is as follows: The tensile breaking strength of glass fiber single yarn coated with sizing agent is tested using a tensile testing machine.

[0099] The width of the warp and weft yarns is measured using a microscope.

[0100] The test results are shown in Table 1:

[0101] Table 1 Performance test results of quartz glass fiber cloth 9 after treatment in Examples 1-3 and Comparative Examples 1-7

[0102]

[0103] Comparative Example 1 uses high-temperature heat desizing, which damages the surface structure of the quartz glass fiber cloth 9, resulting in a decrease in tensile breaking strength; when the whole roll of cloth is burned, the temperature is not uniformly heated and the contact with air is poor, resulting in a high content of combustibles; the yarn hardens after burning, which is not conducive to the subsequent FN fiber opening process, resulting in narrowing of the warp and weft yarn widths.

[0104] Comparative Example 2 uses water as the desizing agent, which cannot degrade the organic matter in the quartz glass fiber cloth 9, resulting in a high content of combustibles. The high content of combustibles will lead to less coupling agent in the subsequent FN coating process, less recovery of the cloth surface strength, and ultimately a decrease in tensile breaking strength.

[0105] In Comparative Example 3, sodium octadecanoic acid fatty acid polyoxybutylene-7 ester sulfonate was not used in the desizing solution, which caused the detached organic matter to become contaminated and could not be effectively degraded. The content of combustibles on the fabric surface was too high, which in turn led to less coupling agent in the subsequent FN coating process, less fabric strength recovery, and reduced tensile breaking strength.

[0106] In Comparative Example 4, the desizing solution did not use octadecanoic acid fatty acid polyoxybutylene-7 ester, which prevented the desizing solution from fully penetrating into the glass fiber. As a result, the organic matter could not be effectively degraded in a short time, and the content of combustibles on the fabric surface was too high. Consequently, there was less coupling agent in the subsequent FN coating process, less fabric strength recovery, and reduced tensile breaking strength.

[0107] Comparative Example 5, due to the absence of CO2 in the CO2 desizing reactor, could not allow the desizing liquid to fully react with the organic matter on the surface of the fiberglass cloth in a short time, resulting in a high content of combustibles on the cloth surface. Consequently, the subsequent FN coating coupling agent was insufficient, the cloth surface strength recovery was minimal, and the tensile breaking strength was reduced.

[0108] The desizing solution used in Comparative Example 6 was at too high a temperature. High temperature can cause hydrogen peroxide to decompose ineffectively and reduce enzyme activity, making it impossible to effectively degrade organic matter. This results in a high content of combustibles on the fabric surface, which in turn leads to less FN coating coupling agent in the subsequent process, less fabric strength recovery, and reduced tensile breaking strength.

[0109] Comparative Example 7 did not undergo ultrasonic treatment during washing, which prevented the effective separation of organic matter on the fabric surface. As a result, the content of combustibles on the fabric surface was too high, which in turn led to less FN coupling agent in the subsequent process, less fabric strength recovery, and reduced tensile breaking strength.

Claims

1. A high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth, characterized in that, It includes a CO2 desizing reactor, an ultrasonic water washing tank (2), a hydroentangling mechanism (3), a spraying mechanism (4), a drying mechanism and a winding shaft (5). A conveyor roller (6) is provided between the ultrasonic water washing tank (2), the hydroentangling mechanism (3), the spraying mechanism (4), the drying mechanism and the winding shaft (5), and the quartz glass fiber cloth (9) is conveyed through the conveyor roller (6). The CO2 deslurry reactor includes a shell (101), with an air inlet (102) and an air outlet (103) at both ends of the shell (101), and a deslurry nozzle (104) installed at the top. A roller (105) is installed inside the shell (101), and quartz glass fiber cloth (9) is wound on the roller (105). The ultrasonic water washing tank (2) includes a water tank (201), a roller (202) is provided inside the water tank (201), the roller (202) is driven to rotate by a motor, a water outlet (203) is provided on the roller (202), a quartz glass fiber cloth (9) is attached to the surface of the roller (202), the quartz glass fiber cloth (9) is conveyed as the roller (202) rolls, and an ultrasonic rod (204) is provided at the center inside the roller (202). The hydroentangling mechanism (3) includes a water spray pipe (301), and several rows of water spray holes (302) are provided at the bottom of the water spray pipe (301) to spray water onto the quartz glass fiber cloth (9) below, to wash away the residual organic matter on the quartz glass fiber cloth (9) and open the fibers. The spraying mechanism (4) includes a second water spray pipe (401), and a second water spray hole (402) is provided at the bottom of the second water spray pipe (401) to spray water onto the quartz glass fiber cloth (9) below, to wash away the residual organic matter on the quartz glass fiber cloth (9) and open the fibers.

2. The high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth (9) as described in claim 1, characterized in that, A filter membrane (106) is provided at the air inlet (102) of the CO2 deslurry reactor, and a flow guide horn (107) is provided at the air inlet (102) inside the shell (101).

3. The high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in claim 1, characterized in that, Several impellers (205) are arranged inside the drum (202) along the length of the drum (202), and the impellers (205) are driven to rotate by a motor; the water outlet holes (203) on the drum (202) have a diameter of 2-5mm and a hole spacing of 5-10mm; the feed end and the discharge end of the ultrasonic water washing tank (2) are respectively provided with two tension rollers (7), and the quartz glass fiber cloth (9) passes between the two tension rollers (7); the feed end and the discharge end of the ultrasonic water washing tank (2) are respectively provided with a cloth pressing roller (8), so that the quartz glass fiber cloth (9) adheres to the surface of the drum (202).

4. The high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in claim 1, characterized in that, The drying mechanism includes a drying oven (10), which is equipped with several conveying rollers (6). The quartz glass fiber cloth (9) is conveyed and dried in the drying oven (10) through the conveying rollers (6).

5. The high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in claim 1, characterized in that, The bottom of the first water spray pipe (301) is provided with six rows of first water spray holes (302), with a hole diameter of 0.05-0.1mm and a hole spacing of 0.1-0.2mm. The distance between the first water spray hole (302) and the quartz glass fiber cloth (9) is 7-9cm. The bottom of the second water spray pipe (401) is provided with one row of second water spray holes (402), with a hole diameter of 0.4-0.5mm and a hole spacing of 5-8cm. The distance between the second water spray hole (402) and the quartz glass fiber cloth (9) is 9-11cm.

6. A highly efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth, characterized in that, The desizing is performed using the high-efficiency desizing device for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in any one of claims 1-5, and includes the following steps: S1 Pre-desizing: The quartz glass fiber cloth (9) wound on the roll (105) is placed into the CO2 desizing reactor. At the same time, desizing liquid is sprayed onto the quartz glass fiber cloth (9) through the desizing liquid nozzle (104), and CO2 is introduced into the CO2 desizing reactor through the air inlet (102) and flows out through the air outlet (103). During this process, the slurry on the surface of the quartz glass fiber cloth (9) reacts with the desizing liquid and is carried away by the CO2 airflow, thereby achieving pre-desizing of the slurry on the surface of the quartz glass fiber cloth (9). S2 Ultrasonic Water Washing: The roll (105) with the pre-desized quartz glass fiber cloth (9) is taken out from the CO2 desizing reactor. Under the action of the take-up roll (5), the quartz glass fiber cloth (9) is conveyed to the ultrasonic water washing tank (2) by the conveyor roller (6) and adhered to the surface of the roller (202). The quartz glass fiber cloth (9) is conveyed as the roller (202) rolls. At the same time, the ultrasonic waves emitted by the ultrasonic rod (204) further clean the surface of the quartz glass fiber cloth (9) and the slurry mixed in the quartz glass fiber filaments, thereby improving the desizing effect. S3 Hydroentangling: The ultrasonically washed quartz glass fiber cloth (9) is conveyed to the hydroentangling mechanism (3) via the conveyor roller (6). Water is sprayed onto the quartz glass fiber cloth (9) through the water spray pipe (301) to wash away the residual organic matter on the quartz glass fiber cloth (9) and open the fibers. S4 spraying: The hydroentangled quartz glass fiber cloth (9) is conveyed to the spraying mechanism (4) via the conveyor roller (6), and water is sprayed onto the quartz glass fiber cloth (9) through the second water spray pipe (401) to further wash away the residual organic matter on the quartz glass fiber cloth (9) and open the fibers. S5 Drying: The sprayed quartz glass fiber cloth (9) is conveyed to the drying mechanism via the conveyor roller (6) for drying; S6 winding: The dried quartz glass fiber cloth (9) is wound onto the winding shaft (5).

7. The efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in claim 6, characterized in that, In step S1, each 1000L of desizing solution contains the following components by mass percentage: sodium percarbonate 6.25-10.5%, tetraacetylethylenediamine 2.5-3.5%, PVA degrading enzyme 0.35-0.5%, PEG degrading enzyme 0.35-0.5%, amylase 0.35-0.75%, pH buffer 3.61-4.41%, penetrant 0.5-1.5%, antistaining agent 14.25-21%, and the balance being purified water; wherein, the pH buffer is disodium hydrogen phosphate 2.66-3.36% and citric acid 0.95-1.05%, and the antistaining agent is 5.7-6% FMEE and 8.55-15% FMES.

8. The efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in claim 7, characterized in that, The mass ratio of sodium percarbonate to tetraacetylated ethylenediamine is (2.5-3):1; in the pH buffer, the mass ratio of disodium hydrogen phosphate to citric acid is (2.8-3.2):1; the mass ratio of PVA degrading enzyme, PEG degrading enzyme to amylase is 1:1:(1-1.5); in the anti-fouling agent, the mass ratio of FMEE to FMES is 1:(1.5-2.5); the penetrant is a non-ionic penetrant.

9. The efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in claim 6, characterized in that, In step S1, the CO2 pressure is 20-25 MPa, the desizing liquid temperature is 52-58℃, and the processing time of the quartz glass fiber cloth (9) in the CO2 desizing reactor is 24-26 min.

10. The efficient desizing method for ultra-low dielectric loss electronic-grade quartz glass fiber cloth as described in claim 6, characterized in that, In step S2, the water temperature in the water tank (201) is 54-60℃, the conveying speed of the quartz glass fiber cloth (9) is 28-32m / min, and the rotation speed of the impeller (205) is 95-100m / min; in step S3, the water spraying pressure of the first spray hole (302) is 2.5-4.5kg, and the water temperature is 10-30℃; in step S4, the water spraying pressure of the second spray hole (402) is 3.5-5.5kg, and the water temperature is 10-30℃; in step S4, the drying temperature is 59-61℃.

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