Copper clad plate based on polyphenyl ether resin glue solution and preparation process thereof

Abstract

The application discloses a kind of based on polyphenyl ether resin glue liquid's copper-clad plate and its preparation process, specifically belongs to copper-clad plate glue liquid manufacturing field;The copper-clad plate is prepared by laminating copper after being impregnated with glue liquid by reinforcing material;Among them, glue liquid includes the following mass fraction components: 20-40 parts polyphenyl ether resin, 20-35 parts benzo oxazine resin, 2-10 parts curing agent, 0.5-1 part curing accelerator, 50-100 parts diluent, 25-30 parts modified filler;The modified filler provided by the application can effectively improve the insulating property, dielectric property and mechanical property of copper-clad plate glue liquid, polytetrafluoroethylene micro powder with specific particle size range in modified filler is used simultaneously with glass fiber powder and barium sulfate powder in a specific amount ratio range, which has a certain synergistic effect on the performance of copper-clad plate.

Description

Technical Field

[0001] This invention belongs to the field of copper clad laminate manufacturing, specifically relating to a copper clad laminate based on polyphenylene ether resin adhesive and its preparation process. Background Technology

[0002] Copper-clad laminates (CCLs) often employ single fillers or simple mixed fillers (such as silica and talc) to reduce the dielectric constant or enhance mechanical properties. However, this approach has several limitations: First, a single filler cannot simultaneously meet the combined requirements of high insulation, low dielectric loss, and high peel strength. Second, uneven filler particle size distribution can lead to poor dispersibility, affecting the thermal stability and interfacial bonding strength of the CCL. Third, while traditional fillers (such as inorganic oxides) can reduce the dielectric constant, they easily introduce hygroscopicity, reducing resistance to damp heat and humidity, and are insufficient for controlling losses in high-frequency signal transmission. Furthermore, some researchers have attempted to introduce polytetrafluoroethylene (PTFE) to utilize its excellent insulation and chemical inertness; however, its compatibility with the resin matrix is ​​poor, and its use alone makes it difficult to achieve a synergistic improvement in mechanical properties. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to innovatively employ a multi-component synergistic modification strategy. By optimizing the mass ratio and particle size control of polytetrafluoroethylene micro powder, glass fiber powder, and barium sulfate powder, the key challenges of filler dispersibility, interfacial bonding, and functional synergy are solved.

[0004] To achieve the above objectives, the present invention discloses the following solutions:

[0005] In a first aspect, the present invention provides a copper-clad laminate based on polyphenylene ether resin adhesive, wherein the copper-clad laminate is obtained by impregnating a reinforcing material with the adhesive and then laminating copper.

[0006] The adhesive comprises the following components by weight:

[0007]

[0008]

[0009] The method for preparing the modified filler includes the following steps:

[0010] 1-1. Pretreatment: After mixing polytetrafluoroethylene micro powder, glass fiber powder and barium sulfate powder in a mass ratio of (8-10):(3-5):1 evenly, soak them in 10-15 times the amount of sodium hydroxide solution with a concentration of 15wt% for 1.5h-2.5h, take them out and drain them to obtain the pretreated mixed powder.

[0011] 1-2. Reaction system setup: The pretreated mixed powder and 75 v / v% ethanol aqueous solution were mixed at a material-to-liquid ratio of 1:(15-20) g / mL to obtain the reaction system;

[0012] 1-3. Initial stirring reaction: The reaction system is stirred at (200-300) r / min for 1-2 hours under a nitrogen atmosphere at 28℃-30℃.

[0013] 1-4. Secondary stirring reaction: Add a certain amount of silane coupling agent KH-540 to the reaction system, maintain a nitrogen atmosphere and the same stirring rate, and continue the reaction for 50-70 minutes. The amount of silane coupling agent added is 5-7% of the total mass of the reaction system.

[0014] 1-5. Heating reaction: Heat the reaction system to 90-100℃, maintain the stirring rate, and continue the reaction for 2.5-3.5h to obtain the reaction product;

[0015] 1-6. Post-processing: Cool the reaction product to room temperature, centrifuge to obtain the precipitate, and dry the precipitate at 55-65℃ for 2.5-3.5h to obtain the modified filler.

[0016] Preferably, the particle size of the polytetrafluoroethylene micro powder is 2-5 μm;

[0017] The glass fiber powder has a single filament length diameter of 11-17 μm, a single filament cross-sectional diameter of 11-17 μm, and a single filament length-to-diameter ratio of 1:1;

[0018] The barium sulfate has a particle size of 0.7-1 μm.

[0019] Preferably, the benzoxazine resin is a liquid ODA type benzoxazine resin.

[0020] Preferably, the curing agent is at least one of dicyandiamide and phenolic resin.

[0021] Preferably, the curing accelerator is at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

[0022] Preferably, the diluent is at least one of acetone and butanone.

[0023] Secondly, the present invention provides a method for preparing a copper-clad laminate, comprising the following steps:

[0024] 2-1. Preparation of adhesive solution: First, dissolve polyphenylene ether resin in a diluent to obtain a polyphenylene ether resin solution. Then, mix the polyphenylene ether resin solution, benzoxazine resin, curing agent, and curing accelerator, and stir at 2000-3000 r / min for 30-60 min. After adding the modified filler, continue stirring at 4000 r / min for 10-30 min to obtain the adhesive solution.

[0025] 2-2. Impregnation and drying: Impregnate the reinforcing material in the adhesive solution, and after impregnation, dry it at 100-150℃ for 5-15 minutes to obtain a semi-cured sheet;

[0026] 2-3. Lamination molding: The prepreg and copper foil are laminated and hot-pressed at 100-150℃ and 10-20MPa for 20-40 minutes to obtain the copper-clad laminate.

[0027] Preferably, the reinforcing material is at least one of glass fiber cloth and ceramic fiber cloth.

[0028] Preferably, the hot pressing in the lamination process is as follows: first, pre-press at 100-120℃ for 5-10 minutes, and then heat up to 130-150℃ for main pressing for 30-40 minutes.

[0029] The beneficial effects of this invention are:

[0030] The modified filler provided by this invention can effectively improve the insulation, dielectric and mechanical properties of copper clad laminate adhesive. When polytetrafluoroethylene micro powder with a specific particle size range is used simultaneously with glass fiber powder and barium sulfate powder within a specific dosage ratio range, it has a certain synergistic effect on the performance of copper clad laminate. Detailed Implementation

[0031] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0032] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are only used to explain the present invention and are not intended to limit the present invention.

[0033] In this invention:

[0034] Polytetrafluoroethylene micro powder: D90 average particle size is 2-5μm, purchased from Shenyang Tianyuxiang Micro Powder Material Factory; other micro powders of different particle sizes used in the examples were also purchased from the same company.

[0035] Polyphenylene oxide resin: purchased from Nagase (China) Co., Ltd.;

[0036] Benzoxazine resin: ODA type benzoxazine resin, purchased from Jinan Shengquan Group Co., Ltd.;

[0037] Glass fiber powder: the length diameter of the single filament is 11-17μm, the cross-sectional diameter of the single filament is 11-17μm, and the ratio of the length diameter to the diameter of the single filament is 1:1. It was purchased from Weijia Composite Materials Co., Ltd.

[0038] Barium sulfate powder: D90 average particle size is 0.7-1μm, purchased from Hongzhi New Materials Co., Ltd.;

[0039] Silane coupling agent: Model KH-540, purchased from Hangzhou Jessica Chemical Co., Ltd.;

[0040] Phenolic resin: Dicyclopentadiene phenolic resin, purchased from Jinan Shengquan Group Co., Ltd.;

[0041] In the specific embodiments, all other raw materials are commercially available, and the particle size can be customized by the aforementioned raw material suppliers.

[0042] Preparation of modified fillers

[0043] Modified filler ①

[0044] Step 1-1. Pretreatment: Mix polytetrafluoroethylene micro powder, glass fiber powder and barium sulfate powder in a mass ratio of 8:3:1 evenly, then soak them in 10 times the amount of sodium hydroxide solution with a concentration of 15wt% for 2 hours. After soaking, remove and drain to obtain the pretreated mixed powder.

[0045] Step 1-2. Reaction system setup: The pretreated mixed powder and 75 v / v% ethanol aqueous solution were added to a three-necked flask at a material-to-liquid ratio of 1:20 g / mL to obtain the reaction system. The three-necked flask was equipped with a stirrer, a thermometer and a gas delivery tube.

[0046] Steps 1-3. Initial stirring reaction: Nitrogen gas is introduced into the reaction system for protection, and the reaction is continuously stirred at a stirring rate of 200 r / min for 1 h under constant temperature of 28℃.

[0047] Steps 1-4. Secondary stirring reaction: Add a certain amount of silane coupling agent KH-540 to the reaction system, maintain a nitrogen atmosphere and the same stirring rate, and continue the reaction for 50 minutes. The amount of silane coupling agent added is 5% of the total mass of the reaction system.

[0048] Steps 1-5. Heating reaction: Heat the reaction system to 93℃, maintain a stirring rate of 200r / min, and continue the reaction for 3h to obtain the reaction product;

[0049] Steps 1-6. Post-processing: Cool the reaction product to room temperature, centrifuge to obtain the precipitate, place the precipitate in a vacuum drying oven and dry it at 60℃ for 3 hours to finally obtain the modified filler ①.

[0050] Modified filler ②

[0051] Step 1-1. Pretreatment: Mix polytetrafluoroethylene micro powder, glass fiber powder and barium sulfate powder in a mass ratio of 10:5:1 evenly, then soak them in 12 times the amount of sodium hydroxide solution with a concentration of 15wt% for 1.5 hours. After soaking, remove and drain to obtain the pretreated mixed powder.

[0052] Step 1-2. Reaction system setup: The pretreated mixed powder and 75 v / v% ethanol aqueous solution were added to a three-necked flask at a material-to-liquid ratio of 1:15 g / mL to obtain the reaction system. The three-necked flask was equipped with a stirrer, a thermometer and a gas delivery tube.

[0053] Steps 1-3. Initial stirring reaction: Nitrogen gas is introduced into the reaction system for protection, and the reaction is continuously stirred at a stirring rate of 300 r / min for 2 hours under constant temperature of 30℃.

[0054] Steps 1-4. Secondary stirring reaction: Add a certain amount of silane coupling agent KH-540 to the reaction system, maintain a nitrogen atmosphere and the same stirring rate, and continue the reaction for 70 min. The amount of silane coupling agent added is 7% of the total mass of the reaction system.

[0055] Steps 1-5. Heating reaction: Heat the reaction system to 90℃, maintain a stirring rate of 300r / min, and continue the reaction for 2.5h to obtain the reaction product;

[0056] Steps 1-6. Post-processing: Cool the reaction product to room temperature, centrifuge to obtain the precipitate, place the precipitate in a vacuum drying oven and dry at 55℃ for 2.5h to finally obtain the modified filler ②.

[0057] Modified filler ③

[0058] Step 1-1. Pretreatment: Mix polytetrafluoroethylene micro powder, glass fiber powder and barium sulfate powder in a mass ratio of 9:4:1 evenly, and then soak them in 15 times the amount of sodium hydroxide solution with a concentration of 15wt% for 2.5 hours. The mass ratio of powder to sodium hydroxide is 1:15. After soaking, take them out and drain them to obtain the pretreated mixed powder.

[0059] Step 1-2. Reaction system setup: The pretreated mixed powder and 75 v / v% ethanol aqueous solution were added to a three-necked flask at a material-to-liquid ratio of 1:17 g / mL to obtain the reaction system. The three-necked flask was equipped with a stirrer, a thermometer and a gas delivery tube.

[0060] Steps 1-3. Initial stirring reaction: Nitrogen gas is introduced into the reaction system for protection, and the reaction is continuously stirred at a stirring rate of 250 r / min for 1.5 h under constant temperature of 29℃.

[0061] Steps 1-4. Secondary stirring reaction: Add a certain amount of silane coupling agent KH-540 to the reaction system, maintain a nitrogen atmosphere and the same stirring rate, and continue the reaction for 60 minutes. The amount of silane coupling agent added is 6% of the total mass of the reaction system.

[0062] Steps 1-5. Heating reaction: Heat the reaction system to 100℃, maintain a stirring rate of 250r / min, and continue the reaction for 3.5h to obtain the reaction product;

[0063] Steps 1-6. Post-processing: Cool the reaction product to room temperature, centrifuge to obtain the precipitate, place the precipitate in a vacuum drying oven and dry at 65℃ for 3.5h to finally obtain the modified filler ③.

[0064] To verify the influence of each component in the modified filler on the properties of the adhesive, the raw materials were omitted or replaced based on modified filler ①, as follows:

[0065] Modified filler ④

[0066] The modified filler ① was prepared according to the same method, except that the particle size of the polytetrafluoroethylene micro powder was adjusted to D90 with an average particle size of ≤1μm.

[0067] Modified filler ⑤

[0068] The modified filler ① was prepared according to the same method, except that the particle size of the polytetrafluoroethylene micro powder was adjusted to D90 with an average particle size of ≥6μm.

[0069] Modified filler⑥

[0070] The modified filler ① is prepared according to the same method, except that the mass ratio of polytetrafluoroethylene micro powder, glass fiber powder and barium sulfate powder in step 1-1 is adjusted to 3:1:8.

[0071] Modified filler ⑦

[0072] The modified filler ① was prepared according to the same method, except that glass fiber powder was not added in the pretreatment step. After the polytetrafluoroethylene and barium sulfate powder were mixed evenly in a mass ratio of 8:1, the subsequent preparation steps were carried out.

[0073] Preparation of copper clad laminate

[0074] Weigh the raw materials precisely according to the mass fractions in Table 1-2;

[0075] 2-1. Preparation of adhesive solution: First, dissolve polyphenylene ether resin in a diluent to obtain a polyphenylene ether resin solution. Then, mix the polyphenylene ether resin solution, benzoxazine resin, curing agent, and curing accelerator, and stir at 2500 r / min for 45 min. After adding the modified filler, continue stirring at 4000 r / min for 20 min to obtain the adhesive solution.

[0076] 2-2. Impregnation and drying: The reinforcing material is impregnated in the adhesive solution, and after impregnation, it is dried at 130℃ for 5 minutes to obtain a semi-cured sheet, wherein the reinforcing material is ceramic fiber cloth;

[0077] 2-3. Lamination molding: The prepreg and copper foil are laminated, prepressed at 120℃ for 10 minutes, and then heated to 150℃ for main pressing for 30 minutes to obtain the copper-clad laminate.

[0078] Table 1. Raw material mass parts in the examples

[0079]

[0080] Note: "-" in the table indicates no additions.

[0081] Table 2 Comparative Example Raw Material Mass Parts

[0082]

[0083]

[0084] Note: "-" in the table indicates no additions.

[0085] Performance testing

[0086] The copper-clad laminates prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests.

[0087] The test items are as follows:

[0088] CTI value: Tested according to the IEC-112 standard method;

[0089] Peel strength: Tested according to the IPC-TM-650 2018 test standard;

[0090] Glass transition temperature Tg: Tested according to the 2018 test standard of IPC-TM-650;

[0091] Dielectric constant and dielectric loss: tested according to ASTM D150 standard;

[0092] The results are shown in Table 3.

[0093] Table 3 Performance Test Results

[0094] Project / Group Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 CTI value (V) 600 650 600 400 500 350 300 Peel strength (N / mm) 1.632 1.652 1.638 1.283 1.408 1.179 1.113 Tg (°C) 275 278 276 221 229 201 195 Dielectric constant (Dk, 1 GHz) 2.32 2.43 2.34 3.16 3.07 3.24 2.28 Dielectric loss (Df, 1 GHz) 0.0038 0.0040 0.0039 0.0061 0.0056 0.0073 0.0034

[0095] Results analysis:

[0096] The results show that the particle size of polytetrafluoroethylene (PTFE) micropowder has a significant impact on the performance of copper clad laminates. When the particle size of PTFE micropowder is controlled within 2-5 μm, the CTI value of the copper clad laminate reaches above 600V, the peel strength remains above 1.5 N / mm, the glass transition temperature (Tg) is approximately 275-278℃, and the dielectric constant Dk and dielectric loss Df are 2.32-2.43 and 0.0038-0.0040, respectively, exhibiting excellent dielectric properties. When the particle size of PTFE is too small (e.g., PTFE micropowder with an average D90 particle size ≤ 1 μm used in Comparative Example 1), the CTI value of the resulting copper-clad laminate drops to 400 V, while the dielectric constant increases to 3.16. This indicates that in this modified filler system, excessively small particle size leads to uneven filler dispersion, reducing insulation performance and dielectric properties. When the particle size of PTFE is too large (e.g., PTFE micropowder with an average D90 particle size ≥ 6 μm used in Comparative Example 2), the CTI value of the resulting copper-clad laminate is 500 V, which is better than Comparative Example 1, but still significantly lower than the example. This indicates that excessively large particle size reduces the interfacial bonding ability of the filler, affecting the overall material performance. This demonstrates that a PTFE micropowder particle size in the range of 2-5 μm can optimize the compatibility between the filler and the matrix, thereby improving the electrical, mechanical, and thermal stability of the copper-clad laminate.

[0097] The mass ratio of polytetrafluoroethylene (PTFE) powder, glass fiber powder, and barium sulfate powder in the modified filler has a crucial effect on the synergistic effect of copper clad laminate performance. In Examples 1-3, when PTFE powder, glass fiber powder, and barium sulfate powder were used within a specific mass ratio range, all performance indicators were within their optimal range. Example 2 achieved a maximum CTI value of 650V and a maximum glass transition temperature (Tg) of 278℃, with stable dielectric properties. However, in Comparative Example 3, because the mass ratio of PTFE, glass fiber powder, and barium sulfate was not within the specific range, the CTI value of its copper clad laminate plummeted to 350V, the Tg was only 201℃, and the dielectric loss (Df) significantly increased to 0.0073. This indicates that an imbalanced mass ratio can disrupt the synergistic effect of the filler, leading to a comprehensive deterioration in insulation, thermal stability, and dielectric properties. Furthermore, the lack of glass fiber powder in Comparative Example 4 resulted in a CTI value of only 300V, a peel strength reduced to 1.113 N / mm, and a Tg of only 195℃ for its copper clad laminate, indicating that glass fiber powder is indispensable for enhancing mechanical strength and improving heat resistance. Polytetrafluoroethylene (PTFE) micropowder provides excellent insulation and chemical stability, glass fiber powder enhances mechanical properties, and barium sulfate powder improves dispersibility and optimizes electrical insulation and dielectric properties. All three are indispensable and have a certain synergistic effect. Therefore, this invention, by adding PTFE micropowder, glass fiber powder, and barium sulfate powder in a mass ratio of (8-10):(3-5):1, can precisely balance the functions of each component, achieving a comprehensive improvement in the performance of the copper clad laminate.

[0098] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A copper-clad laminate based on polyphenylene ether resin adhesive, characterized in that, The copper-clad laminate is made by impregnating a reinforcing material with an adhesive solution and then laminating it with copper. The adhesive comprises the following components by weight: 20-40 parts of polyphenylene ether resin; 20-35 parts of benzoxazine resin; 2-10 parts of curing agent; Curing accelerator 0.5-1 part; 50-100 parts of diluent; 25-30 parts of modified filler; The method for preparing the modified filler includes the following steps: 1-1. Pretreatment: After mixing polytetrafluoroethylene micro powder, glass fiber powder and barium sulfate powder in a mass ratio of (8-10):(3-5):1 evenly, soak them in 10-15 times the amount of sodium hydroxide solution with a concentration of 15wt% for 1.5h-2.5h, take them out and drain them to obtain the pretreated mixed powder. 1-2. Reaction system setup: The pretreated mixed powder and 75 v / v% ethanol aqueous solution were mixed at a material-to-liquid ratio of 1:(15-20) g / mL to obtain the reaction system; 1-3. Initial stirring reaction: The reaction system is stirred at (200-300) r / min for 1-2 hours under a nitrogen atmosphere at 28℃-30℃; 1-4. Secondary stirring reaction: Add a certain amount of silane coupling agent KH-540 to the reaction system, maintain a nitrogen atmosphere and the same stirring rate, and continue the reaction for 50-70 minutes. The amount of silane coupling agent added is 5-7% of the total mass of the reaction system. 1-5. Heating reaction: Heat the reaction system to 90-100℃, maintain the stirring rate, and continue the reaction for 2.5-3.5h to obtain the reaction product; 1-6. Post-processing: Cool the reaction product to room temperature, centrifuge to obtain the precipitate, and dry the precipitate at 55-65℃ for 2.5-3.5h to obtain the modified filler; The particle size of the polytetrafluoroethylene micro powder is 2-5 μm; The glass fiber powder has a single filament length diameter of 11-17 μm, a single filament cross-sectional diameter of 11-17 μm, and a single filament length-to-diameter ratio of 1:1; The barium sulfate has a particle size of 0.7-1 μm.

2. The copper-clad laminate according to claim 1, characterized in that, The benzoxazine resin is a liquid ODA type benzoxazine resin.

3. The copper-clad laminate according to claim 1, characterized in that, The curing agent is at least one of dicyandiamide and phenolic resin.

4. The copper-clad laminate according to claim 1, characterized in that, The curing accelerator is at least one of 2-methylimidazole and 2-ethyl-4-methylimidazole.

5. The copper-clad laminate according to claim 1, characterized in that, The diluent is at least one of acetone and butanone.

6. A method for preparing the copper-clad laminate according to any one of claims 1-5, characterized in that, Includes the following steps: 2-1. Preparation of adhesive solution: First, dissolve polyphenylene ether resin in a diluent to obtain a polyphenylene ether resin solution. Then, mix the polyphenylene ether resin solution, benzoxazine resin, curing agent, and curing accelerator, and stir at 2000-3000 r / min for 30-60 min. After adding the modified filler, continue stirring at 4000 r / min for 10-30 min to obtain the adhesive solution. 2-2. Impregnation and drying: Impregnate the reinforcing material in the adhesive solution, and after impregnation, dry it at 100-150℃ for 5-15 minutes to obtain a semi-cured sheet; 2-3. Lamination molding: The prepreg and copper foil are laminated and hot-pressed at 100-150℃ and 10-20MPa for 20-40 minutes to obtain the copper-clad laminate.

7. The preparation method according to claim 6, characterized in that, The reinforcing material is at least one of glass fiber cloth and ceramic fiber cloth.

8. The preparation method according to claim 6, characterized in that, The hot pressing in the lamination process is as follows: first, pre-press at 100-120℃ for 5-10 minutes, then raise the temperature to 130-150℃ for main pressing for 30-40 minutes.

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