Treating agent for second-generation low-dielectric glass fiber cloth and preparation method of treating agent

Abstract

The invention relates to the technical field of electronic glass fiber cloth treating agents, in particular to a treating agent for second-generation low-dielectric glass fiber cloth and a preparation method of the treating agent. Comprising the following raw materials in parts by weight: 1.0 to 1.2 parts of a methacryloyloxy silane coupling agent, 0.2 to 0.3 part of an epoxy silane coupling agent, 0.78 to 0.82 part of an acidity regulator, 0.3 to 0.5 part of polyethylene glycol, 0.1 to 0.2 part of a titanate coupling agent, 0.05 to 0.1 part of an antioxidant and 96 to 97.5 parts of pure water. The treating agent provided by the invention enables the glass fiber cloth to have excellent aging resistance and mechanical stability while keeping the low dielectric property, is suitable for industrial production of second-generation low-dielectric glass fiber cloth, and has a wide application prospect.

Description

Technical Field

[0001] This invention relates to the field of electronic-grade glass fiber cloth treatment agents, and in particular to a treatment agent for second-generation low-dielectric glass fiber cloth and its preparation method. Background Technology

[0002] As the electronics and information industry develops towards high frequency, high speed, and miniaturization, the requirements for the dielectric properties of substrates used in printed circuit boards (PCBs) are becoming increasingly stringent. Second-generation low-dielectric glass fiber cloth, as a core reinforcing material for PCB substrates, needs to have its dielectric constant and dielectric loss controlled at even lower levels, while also possessing good mechanical properties and interfacial compatibility with the resin matrix. The presence of hydroxyl groups on the surface of glass fiber cloth results in weak interfacial bonding with the resin matrix, directly impacting the overall performance of the composite material. Therefore, surface treatment agents are necessary for modification. Commonly used agents are silane coupling agents, but a single silane coupling agent cannot simultaneously meet the requirements for low dielectric properties and improved interfacial bonding. Therefore, developing a second-generation low-dielectric glass fiber cloth treatment agent that balances low dielectric properties and excellent stability is of great significance. Summary of the Invention

[0003] The purpose of this invention is to provide a treatment agent for second-generation low-dielectric glass fiber cloth and its preparation method, thereby solving the technical problems of high dielectric properties and poor stability of second-generation low-dielectric glass fiber cloth after modification.

[0004] The present invention provides a treatment agent for second-generation low-dielectric glass fiber cloth, comprising the following raw materials in parts by weight: 1.0-1.2 parts of methacryloyloxysilane coupling agent, 0.2-0.3 parts of epoxysilane coupling agent, 0.78-0.82 parts of acidity regulator, 0.3-0.5 parts of polyethylene glycol, 0.1-0.2 parts of titanate coupling agent, 0.05-0.1 parts of antioxidant, and 96-97.5 parts of pure water.

[0005] Furthermore, the acidity regulator is acetic acid.

[0006] Furthermore, the methacryloyloxysilane coupling agent is γ-methacryloyloxypropyltrimethoxysilane.

[0007] Furthermore, the epoxy silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

[0008] Furthermore, the average molecular weight of the polyethylene glycol is 200-400.

[0009] Furthermore, the titanate coupling agent is isopropyl tristearate titanate.

[0010] Furthermore, the antioxidant is antioxidant 1010.

[0011] The epoxy-based silane coupling agent added in this invention serves as an auxiliary coupling agent, complementing the functional groups of the main coupling agent. The epoxy groups exhibit higher reactivity with the resin, which helps to improve interfacial compactness and resistance to humid heat aging, and reduces interfacial hydrolysis attenuation under high temperature and high humidity.

[0012] The polyethylene glycol added in this invention acts as a dispersant and stabilizer. It is adsorbed onto the surface of hydrolysis products through hydrogen bonding, forming a steric hindrance effect that prevents agglomeration and extends the shelf life of the treatment agent to 30-45 days. At the same time, it reduces the surface tension of the treatment agent, optimizes the spreadability of glass fiber, and avoids interface defects.

[0013] The titanate coupling agent added in this invention acts as an interface reinforcing agent. The alkoxy group reacts with the hydroxyl group on the glass fiber surface, and the ester group undergoes an ester exchange reaction with the resin, thereby improving the peel strength, enhancing the stress transmission efficiency, and further increasing the bending strength and impact strength by 5% to 8%.

[0014] The antioxidants added in this invention can capture free radicals during the resin polymerization process, inhibit interfacial oxidative degradation, and are suitable for electronic devices operating at high temperatures above 150°C.

[0015] The present invention provides a method for preparing a treatment agent for second-generation low-dielectric glass fiber cloth, comprising the following steps: S1. Mix the methacryloxysilane coupling agent with the epoxysilane coupling agent to obtain a mixed silane coupling agent, and refrigerate it in a refrigerator at 0-5°C for 4-72 hours; S2. Mix a portion of pure water with an acidic conditioner to obtain an acidic solution; S3. Mix polyethylene glycol, titanate coupling agent, antioxidant and the remaining pure water, stir evenly to obtain the additive premix; S4. Pour the premixed auxiliary agent solution into the acidic solution and stir evenly; then add the refrigerated mixed silane coupling agent dropwise, and stir evenly after the addition is complete to obtain the treatment agent.

[0016] Furthermore, the pH value of the acidic solution obtained in step S2 is 2.7-3.0.

[0017] Furthermore, in step S4, the dropping rate of the mixed silane coupling agent is 5-10 mL / min.

[0018] In summary, compared with the prior art, the present invention has the following advantages: The treatment agent provided by this invention utilizes the synergistic effect of methacryloxysilane coupling agent and epoxysilane coupling agent. The peel strength between the treated glass fiber cloth and epoxy resin is increased by more than 20%, and the flexural strength and impact strength of the composite material are significantly improved. The addition of antioxidants effectively delays the aging of glass fiber cloth. After aging for 1000 hours at 120°C and 85% humidity, the mechanical properties of the treated glass fiber cloth retain more than 90%. The cold storage pretreatment and step-by-step mixing process of the coupling agent during preparation ensure that the treatment agent can be stored for 35-40 days and maintains stable dispersibility. Detailed Implementation It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0019] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application. As used herein, the singular form includes the plural form unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this description, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0020] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0021] Example 1 A treatment agent for second-generation low-dielectric glass fiber cloth is composed of the following raw materials: 1 kg of methacryloyloxysilane coupling agent, 0.25 kg of epoxysilane coupling agent, 0.8 kg of acidity regulator, 0.4 kg of polyethylene glycol, 0.1 kg of titanate coupling agent, 0.05 kg of antioxidant, and 97.4 kg of pure water.

[0022] The acid regulator is acetic acid; the methacryloyloxysilane coupling agent is γ-methacryloyloxypropyltrimethoxysilane; the epoxysilane coupling agent is γ-glycidoxypropyltrimethoxysilane; the average molecular weight of polyethylene glycol is 200; the titanate coupling agent is isopropyl tristearate titanate; and the antioxidant is antioxidant 1010.

[0023] The preparation process of the above-mentioned treatment agent is as follows: S1. Mix the methacryloxysilane coupling agent with the epoxysilane coupling agent to obtain a mixed silane coupling agent, seal it and refrigerate it in a 0°C refrigerator for 72 hours; S2. Mix some pure water with acetic acid to obtain an acetic acid solution with a pH of 2.7; S3. Mix polyethylene glycol, titanate coupling agent, antioxidant and the remaining pure water, stir evenly to obtain the additive premix; S4. Pour the premixed auxiliary agent solution into the acetic acid solution and stir for 10 minutes; then add the refrigerated mixed silane coupling agent dropwise at a rate of 5 mL / min. After the addition is complete, stir evenly to obtain the treatment agent.

[0024] The above-mentioned treatment agent is used as follows: Immerse the second-generation low-dielectric glass fiber cloth in the treatment agent for 10 minutes, and then dry it at 120℃ for 30 minutes.

[0025] Example 2 A treatment agent for second-generation low-dielectric glass fiber cloth is composed of the following raw materials: 1.1 kg of methacryloyloxysilane coupling agent, 0.25 kg of epoxysilane coupling agent, 0.8 kg of acidity regulator, 0.4 kg of polyethylene glycol, 0.15 kg of titanate coupling agent, 0.1 kg of antioxidant, and 97.3 kg of pure water.

[0026] The acid regulator is acetic acid; the methacryloyloxysilane coupling agent is γ-methacryloyloxypropyltrimethoxysilane; the epoxysilane coupling agent is γ-glycidoxypropyltrimethoxysilane; the average molecular weight of polyethylene glycol is 300; the titanate coupling agent is isopropyl tristearate titanate; and the antioxidant is antioxidant 1010.

[0027] The preparation process of the above-mentioned treatment agent is as follows: S1. Mix the methacryloxysilane coupling agent with the epoxysilane coupling agent to obtain a mixed silane coupling agent, seal it and refrigerate it in a refrigerator at 3°C ​​for 48 hours; S2. Mix some pure water with acetic acid to obtain an acetic acid solution with a pH of 2.9; S3. Mix polyethylene glycol, titanate coupling agent, antioxidant and the remaining pure water, stir evenly to obtain the additive premix; S4. Pour the premixed auxiliary agent solution into the acetic acid solution and stir for 10 minutes; then add the refrigerated mixed silane coupling agent dropwise at a rate of 8 mL / min. After the addition is complete, stir evenly to obtain the treatment agent.

[0028] The above-mentioned treatment agent is used as follows: Immerse the second-generation low-dielectric glass fiber cloth in the treatment agent for 10 minutes, and then dry it at 120℃ for 30 minutes.

[0029] Example 3 A treatment agent for second-generation low-dielectric glass fiber cloth is composed of the following raw materials: 1.2 kg of methacryloyloxysilane coupling agent, 0.3 kg of epoxysilane coupling agent, 0.82 kg of acidity regulator, 0.5 kg of polyethylene glycol, 0.2 kg of titanate coupling agent, 0.08 kg of antioxidant, and 96.9 kg of pure water.

[0030] The acid regulator is acetic acid; the methacryloyloxysilane coupling agent is γ-methacryloyloxypropyltrimethoxysilane; the epoxysilane coupling agent is γ-glycidoxypropyltrimethoxysilane; the average molecular weight of polyethylene glycol is 400; the titanate coupling agent is isopropyl tristearate titanate; and the antioxidant is antioxidant 1010.

[0031] The preparation process of the above-mentioned treatment agent is as follows: S1. Mix the methacryloxysilane coupling agent with the epoxysilane coupling agent to obtain a mixed silane coupling agent, seal it and refrigerate it in a 0°C refrigerator for 72 hours; S2. Mix some pure water with acetic acid to obtain an acetic acid solution with a pH of 3.0; S3. Mix polyethylene glycol, titanate coupling agent, antioxidant and the remaining pure water, stir evenly to obtain the additive premix; S4. Pour the premixed auxiliary agent solution into the acetic acid solution and stir for 10 minutes; then add the refrigerated mixed silane coupling agent dropwise at a rate of 10 mL / min. After the addition is complete, stir evenly to obtain the treatment agent.

[0032] The above-mentioned treatment agent is used as follows: Immerse the second-generation low-dielectric glass fiber cloth in the treatment agent for 10 minutes, and then dry it at 120℃ for 30 minutes.

[0033] Comparative Example 1 A fiberglass cloth treatment agent is composed of the following raw materials: 1.25 kg of methacryloyloxysilane coupling agent, 0.8 kg of acidity regulator, 0.4 kg of polyethylene glycol, 0.1 kg of titanate coupling agent, 0.05 kg of antioxidant, and 97.4 kg of pure water. The remaining contents are the same as in Example 1.

[0034] Comparative Example 2 A fiberglass cloth treatment agent is composed of the following raw materials: 1 kg of methacryloyloxysilane coupling agent, 0.25 kg of epoxysilane coupling agent, 0.8 kg of acidity regulator, 0.1 kg of titanate coupling agent, 0.05 kg of antioxidant, and 97.8 kg of pure water.

[0035] Comparative Example 3 A fiberglass cloth treatment agent is composed of the following raw materials: 1 kg of methacryloyloxysilane coupling agent, 0.25 kg of epoxysilane coupling agent, 0.8 kg of acidity regulator, 0.4 kg of polyethylene glycol, 0.05 kg of antioxidant, and 97.5 kg of pure water.

[0036] Comparative Example 4 A fiberglass cloth treatment agent is composed of the following raw materials: 1 kg of methacryloyloxysilane coupling agent, 0.25 kg of epoxysilane coupling agent, 0.6 kg of acidity regulator, 0.4 kg of polyethylene glycol, 0.1 kg of titanate coupling agent, 0.05 kg of antioxidant, and 97.6 kg of pure water.

[0037] The preparation method is basically the same as in Example 1, except that the pH value of the acetic acid solution prepared in step S2 is 3.5.

[0038] Comparative Example 5 A glass fiber cloth treatment agent, consistent with Example 1, is prepared in a manner that is basically the same as that of Example 1, except that the cold storage treatment of mixing silane coupling agent in step S1 is omitted.

[0039] The second-generation low-dielectric glass fiber cloth was treated with the treatment agents prepared in Examples 1-3 and Comparative Examples 1-5. After treatment, the various properties of the glass fiber cloth were tested according to the standards in the art. The test results are shown in Table 1 below: Table 1 Performance Test Results

[0040] The storage period of the treatment agent was obtained by storing it at room temperature (25±2℃) under sealed conditions, observing it visually every 2 days, and recording the time when the first layering and turbidity appeared. Three parallel samples were set up for each group, and the average value was taken as the storage period of the treatment agent.

[0041] The performance tests in Table 1 show that: The peel strength (1.9-2.3 N / mm), tensile strength (880-920 MPa), and flexural strength (1250-1350 MPa) of the second-generation low-dielectric glass fiber cloth treated with the treatment agents provided in Examples 1-3 are significantly better than those of the comparative examples.

[0042] The treatment agent prepared in Comparative Example 1 without the addition of epoxy silane coupling agent resulted in a peel strength retention rate of only 77.8% for the treated glass fiber cloth after wet heat aging, which was 13.1 percentage points lower than that in Example 1, demonstrating the key role of the auxiliary coupling agent in the wet heat resistance performance. The treatment agent prepared using Comparative Example 2 without the addition of polyethylene glycol resulted in a 22.7% decrease in the peel strength of the treated glass fiber cloth, verifying the importance of the dispersant stabilizer for the stability and interfacial spreadability of the treatment agent. The treatment agent prepared using Comparative Example 3 without the addition of titanate coupling agent resulted in a 9.2% decrease in flexural strength and a 27.3% decrease in peel strength of the treated glass fiber cloth compared to Example 1, demonstrating the effect of the interface reinforcing agent on improving mechanical strength and adhesive properties.

[0043] The pH of the acetic acid solution in Comparative Example 4 was adjusted to 3.5, which resulted in incomplete hydrolysis of the silane coupling agent and slight turbidity of the treatment agent. The peel strength of the treated glass fiber cloth was only 1.5 N / mm, which was 31.8% lower than that in Example 1, and the wet heat aging retention rate was 80.0%.

[0044] In Comparative Example 5, after omitting the refrigeration step, the treatment agent delaminated after 10 days of storage. The peel strength of the treated glass fiber cloth was only 1.4 N / mm, a decrease of 36.4% compared to Example 1, and the tensile strength decreased by 10.9%. This indicates that refrigeration at 0-5℃ for 4-72 hours can effectively inhibit the pre-hydrolysis and self-polymerization of the coupling agent, ensuring the stability of the treatment agent and the utilization rate of the effective components.

[0045] Compared with Comparative Examples 1-5, the treatment agents provided in Examples 1-3 of the present invention have significant advantages, with the storage period of the treatment agent extended by 2-4 times; the peel strength of the treated glass fiber cloth is increased by 35.7%-64.3%, the mechanical strength is increased by 8.4%-15.9%, and the peel strength retention rate after wet heat aging is >90%, far exceeding the 77.8%-82.4% of the comparative examples, which is suitable for the long-term use requirements of electronic devices.

[0046] Furthermore, the treated glass fiber cloth exhibits stable low dielectric properties, with dielectric constants ≤3.2 (1GHz), showing no significant increase compared to the comparative example. This demonstrates that the added epoxy silane coupling agent, polyethylene glycol, and titanate coupling agent did not introduce impurity ions or high dielectric components, making it fully suitable for the application scenarios of second-generation low dielectric glass fiber cloth.

[0047] The treatment agent prepared in Example 1 has a storage period of 40 days. After treatment, the glass fiber cloth has a peel strength of 2.2 N / mm, a tensile strength of 920 MPa, and a flexural strength of 1300 MPa, balancing strength and stability. The wet heat aging retention rate is 90.9%, and the dielectric constant is 3.1. It achieves the best balance between performance, stability, and cost, providing the optimal choice for industrial applications.

[0048] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A treatment agent for second-generation low-dielectric glass fiber cloth, characterized in that, The raw materials include the following parts by weight: 1.0-1.2 parts of methacryloyloxysilane coupling agent, 0.2-0.3 parts of epoxysilane coupling agent, 0.78-0.82 parts of acidity regulator, 0.3-0.5 parts of polyethylene glycol, 0.1-0.2 parts of titanate coupling agent, 0.05-0.1 parts of antioxidant, and 96-97.5 parts of pure water.

2. The treatment agent according to claim 1, characterized in that, The acid regulator is acetic acid.

3. The treatment agent according to claim 1, characterized in that, The methacryloyloxysilane coupling agent is γ-methacryloyloxypropyltrimethoxysilane.

4. The treatment agent according to claim 1, characterized in that, The epoxy silane coupling agent is γ-glycidoxypropyltrimethoxysilane.

5. The treatment agent according to claim 1, characterized in that, The average molecular weight of the polyethylene glycol is 200-400.

6. The treatment agent according to claim 1, characterized in that, The titanate coupling agent is isopropyl tristearate titanate.

7. The treatment agent according to claim 1, characterized in that, The antioxidant is antioxidant 1010.

8. A method for preparing the treatment agent for second-generation low-dielectric glass fiber cloth according to any one of claims 1-7, characterized in that, Includes the following steps: S1. Mix the methacryloxysilane coupling agent with the epoxysilane coupling agent to obtain a mixed silane coupling agent, and refrigerate it in a refrigerator at 0-5°C for 4-72 hours; S2. Mix some pure water with an acid regulator to obtain an acidic solution; S3. Mix polyethylene glycol, titanate coupling agent, antioxidant and the remaining pure water, stir evenly to obtain the additive premix; S4. Pour the premixed auxiliary agent solution into the acidic solution and stir evenly; then add the refrigerated mixed silane coupling agent dropwise, and stir evenly after the addition is complete to obtain the treatment agent.

9. The preparation method according to claim 8, characterized in that, The acidic solution obtained in step S2 has a pH value of 2.7-3.

0.

10. The preparation method according to claim 8, characterized in that, In step S4, the dropping rate of the mixed silane coupling agent is 5-10 mL / min.

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