Slurry for low-dielectric fiber cloth as well as preparation method and application of slurry

Abstract

The invention belongs to the technical field of electronic cloth, and particularly relates to slurry for low-dielectric fiber cloth as well as a preparation method and application of the slurry. The slurry for the low-dielectric fiber cloth is prepared from the following components in percentage by mass: 3.0 to 4.0 percent of vinyl alcohol polymer, 1.0 to 2.0 percent of ethylene oxide polymer, 0.1 to 0.3 percent of lubricating agent, 0.1 to 0.3 percent of dispersing agent, 0.1 to 0.3 percent of antistatic agent, 0.1 to 0.2 percent of coupling agent and the balance of pure water. According to the sizing agent for the low-dielectric fiber cloth, a low-polarity auxiliary agent system is adopted, the abrasion resistance of a sizing agent film and the stability of a sizing agent system are improved, fiber hairiness is reduced, the prepared electronic cloth is good in fiber dispersity and high in resin binding force after being subjected to high-temperature desizing, the use requirement of a high-speed PCB is met, and the reliability and CAF resistance of the electronic cloth in a severe environment can be improved; the invention also provides a preparation method thereof.

Description

Technical Field

[0001] This invention belongs to the field of electronic fabric technology, specifically relating to a low-dielectric fiber fabric slurry, its preparation method, and its application. Background Technology

[0002] Currently, traditional sizing agents in the electronic fabric industry are mostly based on polyvinyl alcohol and polyethylene glycol as core two-components, which can meet the basic weaving needs of traditional E-glass fiber. However, with the rapid development of fields such as AI, high-frequency communication, and radar, the market demand for low-dielectric fiber fabrics is growing exponentially. Low-dielectric special electronic fibers have emerged as a result, becoming a core material supporting the upgrading of the high-end electronic information industry, and also posing new requirements for the performance of supporting sizing agents.

[0003] Compared to traditional E-fibers, low-dielectric fibers have inherent defects such as low strength and poor flexibility, which directly leads to poor weaving performance and yarn breakage during weaving. This problem is particularly prominent in the warp direction. Therefore, the coating, bundling and abrasion resistance of the sizing agent are required to be much higher than those of traditional sizing agents. At the same time, when traditional two-component sizing agents are adapted to low-dielectric fibers, there is also the problem of high ash content after desizing, which will affect the coating effect of subsequent post-treatment agents and the interfacial bonding force between the fiber and the copper clad laminate resin.

[0004] CN119243477A discloses a sizing agent for electronic-grade glass fiber cloth, its preparation method, products, and applications. The sizing agent is composed of water-soluble polyester, polypropylene glycol, a combustion aid, a lubricant, an antistatic agent, a defoamer, and water. This sizing agent can improve the coverage and bundle properties of glass fibers, reduce weaving defects, and has excellent desizing properties and low ash content. Electronic cloths with fine yarns of 9 microns and below produced using this sizing agent have low air permeability, good impregnation performance, stable warp sizing rate, and high warp tensile strength. It is suitable for copper-clad laminates and printed circuit boards, and can effectively solve the problems of poor wear resistance and difficult desizing of traditional sizing agents. However, its lubricant has the defects of strong hydrophobicity, difficult desizing, and easy residue. The film-forming system composed of water-soluble polyester and polypropylene glycol is prone to delamination.

[0005] CN121021011A discloses a high-temperature starch sizing agent for electronic-grade glass fiber yarn, its preparation method, and its application. The sizing agent is composed of a compound starch emulsifier, a lubricant, a plasticizer, a siloxane functional additive A, an AFCONA-7319 type functional additive B, and water. The compound starch is a mixture of esterified starch, etherified starch, and network-type quaternary ammonium cationic starch. The compound emulsifier is a mixture of polyethylene glycol laurate, imidazoline ethyl sulfate, and fatty amine polyoxyethylene ether. This sizing agent... With low migration, it can significantly reduce the breakage rate, fuzz rate and dust loss of glass fiber yarn, and improve abrasion resistance and breaking strength, making it suitable for the preparation of low-expansion electronic-grade glass fiber yarn; however, the starch system used has problems such as insufficient thermal stability, stiff film formation and poor flexibility. The stiffness of modified starch compound yarn is too high, which makes it prone to pilling, breakage and uneven fabric surface during high-speed weaving and high-tension warping. In addition, the starch film has poor chemical compatibility with PCB substrate resin and low interfacial bonding force, which will reduce the interlayer shear strength, heat resistance and reliability of copper clad laminate. Summary of the Invention

[0006] To overcome the aforementioned problems in the prior art, the low-dielectric fiber cloth slurry provided by the present invention adopts a low-polarity additive system to improve the abrasion resistance of the slurry film and the stability of the slurry system, reduce fiber fuzz, and the resulting electronic cloth has good fiber dispersion and strong bonding force with resin after high-temperature desizing, which is suitable for the use requirements of high-speed PCBs and can improve its reliability and CAF resistance in harsh environments; the present invention also provides its preparation method.

[0007] The low-dielectric fiber fabric slurry of the present invention comprises, by mass percentage, the following components: 3.0-4.0% vinyl alcohol polymer, 1.0-2.0% ethylene oxide polymer, 0.1-0.3% lubricant, 0.1-0.3% dispersant, 0.1-0.3% antistatic agent, 0.1-0.3% coupling agent, and the balance being pure water; wherein the lubricant is a fatty acid ester compound, the dispersant is a polyether dispersant, the antistatic agent is a polyoxyethylene amine compound, and the coupling agent is an organic carboxylic acid polymer.

[0008] The ethylene alcohol polymer is polyvinyl alcohol with a degree of polymerization of 1700-2400 and a degree of hydrolysis of 80-99%, preferably one of PVA 237, PVA 240, and PVA 246 commercially available from Kuraray Co., Ltd.

[0009] The ethylene oxide polymer is polyethylene glycol, with a number average molecular weight of 2000-6000 g / mol.

[0010] The organic carboxylic acid polymer is one or two of maleic anhydride-acrylic acid copolymer, polymaleic anhydride, and polyacrylic acid.

[0011] The fatty acid ester compound is one or both of butyl stearate and isopropyl palmitate.

[0012] The polyether dispersant is one or two of polyethylene glycol ether and polypropylene glycol ether with a number average molecular weight of 1000-3000 g / mol, preferably polyethylene glycol ether and polypropylene glycol ether with a number average molecular weight of 2000 g / mol.

[0013] The polyoxyethylene amine compound is one or both of octadecylamine polyoxyethylene ether and cocoamine polyoxyethylene ether.

[0014] The method for preparing the slurry for low-dielectric fiber fabric includes the following steps: (1) Mix the dispersant and antistatic agent, inject into pure water, and stir evenly to obtain slurry A; (2) Add the vinyl alcohol polymer and ethylene oxide polymer to slurry A and stir evenly to obtain slurry B; (3) Add lubricant to slurry B and stir until there is no floating oil. Then, continue to add coupling agent, stir evenly, add the remaining pure water, and keep stirring to obtain slurry for low dielectric fiber cloth.

[0015] The aforementioned low-dielectric fiber fabric sizing agent is used in the warp sizing process during the production of low-dielectric fiber fabric to improve the yarn's bundle properties, smoothness, and abrasion resistance during weaving, reduce fuzz and yarn breakage, and improve sheath clarity and weaving efficiency.

[0016] Preferably, the method for preparing the low-dielectric fiber fabric slurry includes the following steps: (1) Mix the dispersant and antistatic agent, inject into pure water, and stir evenly at room temperature to obtain slurry A; (2) Add the vinyl alcohol polymer and ethylene oxide polymer to slurry A, heat to 50°C and stir evenly to obtain slurry B; (3) Add lubricant to slurry B and stir until there is no floating oil. Then, continue to add coupling agent, heat to 50°C and stir evenly. Add the remaining pure water and keep stirring for 20 minutes to obtain slurry for low dielectric fiber cloth.

[0017] This invention introduces organic carboxylic acid polymers for synergistic modification. These polymers are rich in carboxyl functional groups, which can form stable hydrogen bonds with hydroxyl groups on the glass fiber surface. This significantly improves the emulsification stability, dispersion uniformity, and storage stability of the slurry, enhances the flexibility and density of the film, and reduces film embrittlement, cracking, and detachment. Consequently, the fiberglass cloth exhibits significantly reduced fuzz, dust, and fiber breakage rates during weaving, heat treatment, and subsequent processing, while exhibiting significantly improved abrasion resistance and formability. Simultaneously, the carboxylic acid functional groups enhance the adsorption capacity of the slurry on the fiber surface, which is beneficial for improving the surface cleanliness, resin wettability, and copper clad laminate compatibility of the fiberglass cloth. This has a significant effect on improving the appearance quality, processing performance, and reliability of electronic-grade fiberglass cloth in downstream applications.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) The low dielectric fiber cloth slurry of the present invention adopts a low polarity auxiliary agent system composed of fatty acid ester lubricant, polyether dispersant, polyoxyethylene amine antistatic agent and organic carboxylic acid polymer coupling agent. It has excellent compatibility with the main agent of the slurry, can form a stable lubricating film on the fiber surface, can reduce the generation of fiber hair, and can be easily removed by thermal desizing, which can prevent dust, lint and other cloth surface contamination, effectively reduce the impact of dielectric properties, greatly improve the interlayer bonding of copper clad laminate, and meet the application requirements of high-speed PCB.

[0019] (2) The low dielectric fiber cloth slurry of the present invention can neutralize the excess alkaline components in the slurry and maintain the slightly acidic nature of the system by virtue of its own salt formation characteristics. At the same time, it ensures the dispersion stability of the slurry, realizes uniform coating of the slurry film, and significantly improves the wear resistance of the slurry film.

[0020] (3) The preparation method of the low dielectric fiber cloth slurry of the present invention is simple. The low dielectric fiber cloth obtained has good dispersion between single yarn fibers after the slurry film on the fiber surface is removed at high temperature. The glass fiber cloth after fiber opening has good flatness and uniformity, which can effectively reduce the resin impregnation time, improve the bonding force between the fiber cloth and the resin, effectively improve the reliability of high-speed PCB in harsh environments such as high temperature and high humidity, and greatly improve the CAF resistance. Detailed Implementation

[0021] The present invention will be further described below with reference to the embodiments and comparative examples. Unless otherwise specified, the raw materials used in the embodiments and comparative examples are all conventional commercial raw materials, and the process methods used are all conventional methods in the art unless otherwise specified. The fractions involved in the raw materials in the embodiments and comparative examples are all mass percentages.

[0022] Example 1 The low-dielectric fiber fabric slurry, by mass percentage, comprises the following components: Polyvinyl alcohol 4.0%, polyethylene glycol (number average molecular weight 6000 g / mol) 1.0%, butyl stearate 0.1%, polyethylene glycol ether 0.3%, octadecylamine polyoxyethylene ether 0.15%, maleic anhydride-acrylic acid copolymer 0.2%, balance is pure water.

[0023] The method for preparing the slurry for low-dielectric fiber fabric includes the following steps: (1) Mix polyethylene glycol ether and octadecylamine polyoxyethylene ether by mass percentage, inject into pure water, stir evenly at room temperature to obtain slurry A; (2) Add polyvinyl alcohol PVA 237 and polyethylene glycol (number average molecular weight 6000 g / mol) to slurry A, heat to 50℃ and stir evenly to obtain slurry B; (3) Add butyl stearate to slurry B and stir until there is no floating oil. Then, continue to add maleic anhydride-acrylic acid copolymer, heat to 50°C and stir until uniform. Add the remaining pure water and keep stirring for 20 minutes to obtain slurry for low dielectric fiber cloth.

[0024] Example 2 The low-dielectric fiber fabric slurry, by mass percentage, comprises the following components: Polyvinyl alcohol 3.0%, polyethylene glycol (number average molecular weight 2000 g / mol) 2.0%, isopropyl palmitate 0.2%, polypropylene glycol ether 0.1%, polyethylene glycol ether 0.1%, cocoamine polyoxyethylene ether 0.1%, polymaleic anhydride 0.15%, balance is pure water.

[0025] The method for preparing the slurry for low-dielectric fiber fabric includes the following steps: (1) Mix polypropylene glycol ether, polyethylene glycol ether and cocoamine polyoxyethylene ether by mass percentage, inject into pure water, stir evenly at room temperature to obtain slurry A; (2) Add polyvinyl alcohol PVA 240 and polyethylene glycol (number average molecular weight 2000 g / mol) to slurry A, heat to 50℃ and stir evenly to obtain slurry B; (3) Add isopropyl palmitate to slurry B and stir until there is no floating oil. Then, continue to add polymaleic anhydride, heat to 50°C and stir until uniform. Add the remaining pure water and keep stirring for 20 minutes to obtain slurry for low dielectric fiber cloth.

[0026] Example 3 The low-dielectric fiber fabric slurry, by mass percentage, comprises the following components: Polyvinyl alcohol 3.5%, polyethylene glycol (number average molecular weight 4000 g / mol) 1.5%, butyl stearate 0.2%, isopropyl palmitate 0.1%, polypropylene glycol ether 0.1%, octadecylamine polyoxyethylene ether 0.2%, cocoamine polyoxyethylene ether 0.1%, polyacrylic acid 0.1%, and the balance is pure water.

[0027] The method for preparing the slurry for low-dielectric fiber fabric includes the following steps: (1) Mix polypropylene glycol ether, octadecylamine polyoxyethylene ether and cocoamine polyoxyethylene ether by mass percentage, inject into pure water, stir evenly at room temperature to obtain slurry A; (2) Add polyvinyl alcohol PVA 246 and polyethylene glycol (number average molecular weight 4000 g / mol) to slurry A, heat to 50℃ and stir evenly to obtain slurry B; (3) Add butyl stearate and isopropyl palmitate to slurry B and stir until there is no floating oil. Then, continue to add polyacrylic acid, heat to 50°C and stir until uniform. Add the remaining pure water and keep stirring for 20 minutes to obtain slurry for low dielectric fiber cloth.

[0028] Comparative Example 1 This comparative example is the same as Example 1, except that the coupling agent maleic anhydride-acrylic acid copolymer is replaced with an equal amount of KH-550 (γ-aminopropyltriethoxysilane), while the other raw materials and preparation process remain unchanged.

[0029] Comparative Example 2 The difference between this comparative example and Example 1 is that a traditional starch system is used to prepare the slurry. The preparation method of the traditional low-dielectric fiber fabric slurry includes the following steps: (1) The starch accounts for 6% by mass percentage. Add the starch to pure water, heat to 50°C and stir evenly to obtain slurry A; (2) By mass percentage, polyethylene glycol accounts for 1.5%. Add polyethylene glycol to slurry A, heat to 90°C, stir until there is no floating oil, add the remaining pure water, keep the temperature at 60°C and stir for 20 minutes to obtain slurry for later use.

[0030] The low-dielectric fiber cloth slurry prepared in the above examples and comparative examples was applied to prepare low-dielectric fiber cloth using conventional processes, and its performance was tested. The number of fuzz and defects per kilometer was measured according to standard GB / T 7689.2-2013; the air permeability was measured according to standard GB / T5453-1997; and the resin content was measured according to standard GB / T2577-2005. Finally, the CAF resistance test was performed according to IPC-TM-6502.3.25D. The test results are shown in Table 1.

[0031] Table 1 Performance Test Results

[0032] Based on Table 1, a comparative analysis of Example 1 and Comparative Example 1 revealed that using organic carboxylic acid polymers instead of conventional silane coupling agents facilitates uniform coating and film formation, significantly improves the abrasion resistance of the film, reduces fuzz and knots by more than 50%, and significantly improves the fabric surface quality.

[0033] Comparative analysis of Example 1 and Comparative Example 2 revealed that the low-dielectric fiber cloth slurry of the present invention has better wear resistance than traditional slurries, greatly improves the interlayer bonding force of copper clad laminate, effectively reduces resin impregnation time, enhances the bonding force between glass cloth and resin, effectively improves the reliability of high-speed PCBs in harsh environments such as high temperature and high humidity, and significantly improves CAF resistance.

Claims

1. A slurry for low-dielectric fiber fabrics, characterized in that, By mass percentage, it comprises the following components: 3.0-4.0% vinyl alcohol polymer, 1.0-2.0% ethylene oxide polymer, 0.1-0.3% lubricant, 0.1-0.3% dispersant, 0.1-0.3% antistatic agent, 0.1-0.3% coupling agent, and the balance being pure water; The lubricant is a fatty acid ester compound, the dispersant is a polyether dispersant, the antistatic agent is a polyoxyethylene amine compound, and the coupling agent is an organic carboxylic acid polymer.

2. The slurry for low-dielectric fiber fabric according to claim 1, characterized in that, The ethylene alcohol polymer is polyvinyl alcohol, with a degree of polymerization of 1700-2400 and a degree of alcoholysis of 80-99%.

3. The slurry for low-dielectric fiber fabric according to claim 1, characterized in that, The ethylene oxide polymer is polyethylene glycol, with a number average molecular weight of 2000-6000 g / mol.

4. The slurry for low-dielectric fiber fabric according to claim 1, characterized in that, The organic carboxylic acid polymer is one or two of maleic anhydride-acrylic acid copolymer, polymaleic anhydride, and polyacrylic acid.

5. The slurry for low-dielectric fiber fabric according to claim 1, characterized in that, The fatty acid ester compounds are one or both of butyl stearate and isopropyl palmitate.

6. The slurry for low-dielectric fiber fabric according to claim 1, characterized in that, The polyether dispersant is one or both of polyethylene glycol ether and polypropylene glycol ether with a number average molecular weight of 1000-3000 g / mol.

7. The slurry for low-dielectric fiber fabric according to claim 1, characterized in that, The polyoxyethylene amine compounds are one or both of octadecylamine polyoxyethylene ether and cocoamine polyoxyethylene ether.

8. A method for preparing a low-dielectric fiber fabric slurry according to any one of claims 1-7, characterized in that, Includes the following steps: (1) Mix the dispersant and antistatic agent, inject into pure water, and stir evenly to obtain slurry A; (2) Add the vinyl alcohol polymer and ethylene oxide polymer to slurry A and stir evenly to obtain slurry B; (3) Add lubricant to slurry B and stir until there is no floating oil. Then, continue to add coupling agent, stir evenly, add the remaining pure water, and keep stirring to obtain slurry for low dielectric fiber cloth.

9. The application of the low-dielectric fiber fabric slurry according to any one of claims 1-7, characterized in that, Used in the warp sizing process during the production of low dielectric fiber cloth.

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