Preparation method of high-performance low-dielectric high-frequency copper-clad plate resin composition

Abstract

The present application relates to the technical field of resin composition, in particular to a preparation method of high-performance low-dielectric high-frequency copper-clad plate resin composition. The method uses 4,4'-diamino diphenyl methane and 4,4'-diamino diphenyl sulfone to react with maleic anhydride respectively to synthesize a composite bismaleimide, then reacts with acetic anhydride and triethylamine respectively, purifies, and finally mixes with styrene modified polyphenyl ether, hydrocarbon resin, triblock copolymer, olefin crosslinking agent, vinyl silane modified spherical silica, flame retardant and the like according to a specific proportion, and stirs in batches to obtain a target composition. The system synergistically regulates the molecular structure through rigidity-flexibility, combines with surface modified inorganic fillers, significantly improves the high-frequency dielectric properties, heat resistance and copper foil peeling strength, has the advantages of low dielectric loss, high dimensional stability, heat resistance, high interface peeling strength and the like, and is suitable for large-scale application of high-frequency high-reliability PCB substrates.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of resin composition, in particular to a preparation method of high-performance low-dielectric high-frequency copper-clad plate resin composition. BACKGROUND

[0002] High-frequency high-speed printed circuit boards require that the copper-clad plate substrate meet the requirements of low dielectric constant, low dielectric loss and high dimensional stability at the same time, and the copper foil-substrate interface needs to remain stable under the conditions of thermal-mechanical cycle and chemical treatment. Traditional hydrocarbon or olefin resins have the advantage of low loss due to low polarity and small dipole moment, but the chain segment is flexible and the crosslinking density is limited, which makes it difficult to effectively inhibit the thermal expansion in the Z direction, and the through-hole failure and interlayer strain accumulation are easily generated under temperature cycle. In addition, the non-polar matrix is insufficient in wetting and chemical anchoring of the copper foil and glass fiber surface, and it is difficult to balance the peel strength and long-term reliability. The introduction of high-rigidity and low-thermal-expansion aromatic or imide resins can reduce thermal expansion and improve heat resistance, but strong polarity or excessive rigidity often leads to increased dielectric loss, system brittleness and increased interface stress concentration, which is not conducive to laminated reliability and copper foil peeling.

[0003] The addition of inorganic fillers is a common means to reduce thermal expansion, but the unmodified particles have a large interfacial tension with the organic matrix, which easily generates interface defects and micro voids, increases the interface polarization and introduces dielectric loss. At the same time, the mismatch of morphology and surface chemistry will weaken the stress transfer, leading to the initiation and expansion of microcracks under thermal cycle. In order to improve the interface adhesion, surface coupling and participation in the curing reaction are needed to achieve chemical bonding, and the particle morphology is also optimized to reduce stress concentration and processing viscosity.

[0004] In order to improve the interface toughness, the introduction of toughening agent can provide energy dissipation channels and chain entanglement, but if the compatibility or crosslinking synergy is insufficient, it will cause the size of phase separation to be out of control, which affects the dielectric stability and weakens the copper foil interface strength. The selection and reaction path of the crosslinking agent have a decisive influence on the network continuity and the number of phase interfaces. If the curing is only in a single phase, the "island-sea" structure is easily formed, the residual stress is difficult to release, and the dimensional stability and peel strength are difficult to improve simultaneously.

[0005] In addition, during the impregnation-drying process, the volatilization rate and solubility parameters of the solvent system directly determine the wetting of the sizing solution to the glass fiber bundle, the dispersion of the filler and the interface activation degree. The imbalance of volatilization gradient will induce pores, resin content fluctuations and interface defects, which will amplify the dielectric loss at high frequency and weaken the interface adhesion. If the flame-retardant system is not properly selected, it will also introduce additional polarity sources and hygroscopic points, which will amplify the high-frequency dielectric loss and damage the long-term reliability.

[0006] In summary, the existing solutions generally face three constraints: the contradiction between low loss and low thermal expansion in material science, the compatibility between toughening and high-frequency dielectric stability, and the process contradiction between interface strength and process controllability. How to construct a system with low polarization loss, high modulus and low expansion, and with chemical anchoring and continuous stress transfer network through the synergy of molecular design, interface chemistry and process rheology is still a core problem in the field. SUMMARY

[0007] Therefore, the purpose of the present application is to provide a preparation method of a high-performance low-dielectric high-frequency copper-clad plate resin composition to solve the contradiction problems of low dielectric loss and low thermal expansion, interface strength and size stability of high-frequency copper-clad plate.

[0008] Based on the above purpose, the present application provides a preparation method of a high-performance low-dielectric high-frequency copper-clad plate resin composition, comprising the following steps:

[0009] (1) Dissolve 4,4'-diaminodiphenyl methane and maleic anhydride in acetone, respectively, add the maleic anhydride solution to the 4,4'-diaminodiphenyl methane solution at 0℃, stir for 60min at 0℃ after the addition is completed, continue to stir for 60min at room temperature, concentrate, wash, and vacuum dry to obtain 4,4'-diaminodiphenyl methane bismaleimide acid;

[0010] (2) Dissolve 4,4'-diaminodiphenyl sulfone and maleic anhydride in acetone, respectively, add the maleic anhydride solution to the 4,4'-diaminodiphenyl sulfone solution at 0℃, stir for 60min at 0℃ after the addition is completed, continue to stir for 80min at room temperature, concentrate, wash, and vacuum dry to obtain 4,4'-diaminodiphenyl sulfone bismaleimide acid;

[0011] (3) Under nitrogen protection, mix 4,4'-diaminodiphenyl methane bismaleimide acid with acetic anhydride and triethylamine, stir at 110℃ for 120min, then cool, pour into ice water to precipitate solid, recrystallize, and vacuum dry to obtain 4,4'-diaminodiphenyl methane bismaleimide;

[0012] (4) Under nitrogen protection, mix 4,4'-diaminodiphenyl sulfone bismaleimide acid with acetic anhydride and triethylamine, stir at 110℃ for 120min, then cool, pour into ice water to precipitate solid, recrystallize, and vacuum dry to obtain 4,4'-diaminodiphenyl sulfone bismaleimide;

[0013] (5) stirring solvent, 4,4'-diaminodiphenyl methane bismaleimide, 4,4'-diaminodiphenyl sulfone bismaleimide and styrene modified polyphenyl ether at 55℃ for 90min, stirring after adding hydrocarbon resin and styrene-ethylene-butylene triblock copolymer for 60min, stirring after adding 1,2-bis(4-vinylphenyl)ethane and dicumyl peroxide for 120min, stirring after adding phosphorus-containing flame retardant for 60min, stirring after adding vinyl silane modified spherical silica for 120min.

[0014] Preferably, the mass ratio of 4,4'-diaminodiphenyl methane and maleic anhydride in step (1) is 1:1.

[0015] Preferably, the mass ratio of 4,4'-diaminodiphenyl sulfone and maleic anhydride in step (2) is 5:4.

[0016] Preferably, the weight ratio of 4,4'-diaminodiphenyl methane bismaleimide acid, acetic anhydride and triethylamine in step (3) is 24:40:3.

[0017] Preferably, the weight ratio of 4,4'-diaminodiphenyl sulfone bismaleimide acid, acetic anhydride and triethylamine in step (4) is 22:40:4.

[0018] Preferably, the weight ratio of solvent, 4,4'-diaminodiphenyl methane bismaleimide, 4,4'-diaminodiphenyl sulfone bismaleimide, styrene modified polyphenyl ether, hydrocarbon resin, styrene-ethylene-butylene triblock copolymer, 1,2-bis(4-vinylphenyl)ethane, dicumyl peroxide, phosphorus-containing flame retardant and vinyl silane modified spherical silica in step (5) is 250-300:13-18:15-20:30-40:50-60:50:30:0.05-0.1:30:90-110.

[0019] Preferably, the solvent in step (5) is a mixture of N-methyl pyrrolidone, methyl ethyl ketone and toluene in a mass ratio of 50-60:75-90:125-150.

[0020] Preferably, the type of styrene modified polyphenyl ether in step (5) is NORYL SA9000.

[0021] Preferably, the type of hydrocarbon resin in step (5) is ARKON P-125.

[0022] Preferably, the type of styrene-ethylene-butylene triblock copolymer in step (5) is Kraton G1726V.

[0023] Preferably, the structure features of the vinyl silane modified spherical silica in step (5) are 0.97 of sphericity, 5 mu m of D50, and 0.8 wt% of surface vinyl silane content.

[0024] Advantages of the present application:

[0025] The present application is based on the synergistic design of methane / sulfone composite bismaleimide, the strong electron-withdrawing sulfone group and the aromatic skeleton improve the rigidity and density of the crosslinked network, and the methane bridge provides the necessary chain segment flexibility, both of which achieve the balance of polarization degree and chain segment motion at the molecular scale. The structure-property coupling directly brings the consideration of low loss and Z-direction size stability at high frequency, avoiding the bias of single rigidity or single flexibility system.

[0026] The present application introduces styrene modified polyphenyl ether as a low polarity electrical performance skeleton phase, which suppresses the generation of orientation polarization and interface polarization by means of its non-polar aromatic backbone and lower dipole moment; at the same time, it forms an interpenetrating network with the composite bismaleimide to improve the interface modulus of thermal deformation temperature, realizing the consistency of low dielectric and high heat resistance.

[0027] The present application uses vinyl silane modified high-sphericity silica, which reduces stress concentration due to its spherical morphology, and the surface vinyl group can participate in olefin crosslinking to build a chemical anchoring organic-inorganic interface. This dual mechanism of chemical bonding and geometric density reduces thermal expansion and thermal cycle strain on the one hand, and weakens interface polarization and high-frequency loss induced by pores on the other hand, significantly improving interface reliability and signal integrity.

[0028] The present application uses 1,2-bis(4-vinylphenyl)ethane as the main olefin crosslinking system, which cooperates with the surface vinyl group of the olefin matrix and filler to form a continuous stress transfer network. This continuous network reduces the number of phase interfaces and the modulus jump between soft and hard phases, reduces the initiation of microcracks in thermal-mechanical cycles, improves the load transfer efficiency of copper foil-substrate, and brings stable peel strength and durability; SEBS builds a microphase separation toughening structure, which provides an energy dissipation channel in the high modulus aromatic / imide network; its co-crosslinking with BVPE inhibits excessive phase separation, and both dielectric stability and interface adhesion are considered, thereby significantly improving the interface failure resistance under lamination and bending conditions while maintaining low loss.

[0029] The present application uses N-methyl pyrrolidone / methyl ethyl ketone / toluene ternary solvent to control the impregnation rheology and volatilization gradient according to a specific ratio, which is beneficial to the full wetting and filling of resin between glass fiber bundles, and promotes the uniform dispersion and interface activation of fillers, reduces pores and interface defects, and ensures the repeatability of dielectric, size stability and peel strength from the process level. BRIEF DESCRIPTION OF DRAWINGS

[0030] In order to more clearly illustrate the technical solutions of the present application or the prior art, the drawings needed to be used in the following embodiments or prior art description will be briefly introduced.

[0031] Figure 1 Infrared spectra of 4,4'-diaminodiphenyl methane bismaleimide and 4,4'-diaminodiphenyl sulfone bismaleimide in Example 2 of the present application;

[0032] Figure 2 Differential scanning calorimetry spectra of the resin compositions in Examples 1-4 of the present application;

[0033] Figure 3 Differential scanning calorimetry spectra of the resin compositions in Example 2 and Comparative Examples 1-5 of the present application. DETAILED DESCRIPTION

[0034] In order to make the objects, technical solutions and advantages of the present application more clearly understood, the present application will be further described in detail below with specific examples.

[0035] Example 1:

[0036] (1) 12 g of 4,4'-diaminodiphenyl methane was stirred with 200 g of acetone at room temperature until completely dissolved, 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, which was slowly added dropwise to the above-mentioned 4,4'-diaminodiphenyl methane solution at 0°C, after the addition was completed, the solution was incubated at 0°C for 60 min, and then the temperature was increased to room temperature for continuous stirring for 60 min, followed by concentration, washing with deionized water twice, and washing with acetone once, and the obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl methane bismaleimide acid;

[0037] (2) 15 g of 4,4'-diaminodiphenyl sulfone was stirred with 200 g of acetone at room temperature until completely dissolved, 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, which was slowly added dropwise to the above-mentioned 4,4'-diaminodiphenyl sulfone solution at 0°C, after the addition was completed, the solution was incubated at 0°C for 60 min, and then the temperature was increased to room temperature for continuous stirring for 80 min, followed by concentration, washing with deionized water twice, and washing with acetone once, and the obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide acid;

[0038] (3) 24 g of 4,4'-diaminodiphenyl methane bismaleimide acid was mixed with 40 g of acetic anhydride and 3 g of triethylamine, and stirred at 110°C under nitrogen protection for 120 min, after the reaction was completed, the reaction solution was cooled to room temperature, and the solid was precipitated by pouring into ice water, the solid was collected by filtration, and then purified by recrystallization with acetone, and the recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl methane bismaleimide.

[0039] (4) 22 g of 4,4'-diaminodiphenyl sulfone bismaleimide acid was mixed with 40 g of acetic anhydride and 4 g of triethylamine, and stirred at 110°C for 120 min under nitrogen protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the solid was precipitated by pouring into ice water. The solid was collected by filtration, and then purified by recrystallization with acetone. The recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide;

[0040] (5) 13 g of 4,4'-diaminodiphenyl methane bismaleimide, 15 g of 4,4'-diaminodiphenyl sulfone bismaleimide, 30 g of styrene-modified polyphenyl ether NORYL SA9000, 50 g of N-methylpyrrolidone, 75 g of methyl ethyl ketone, and 125 g of toluene were stirred at 55°C for 90 min to form a uniform transparent solution. Then, 50 g of hydrocarbon resin ARKON P-125 and 50 g of styrene-ethylene-butylene triblock copolymer Kraton G1726V were added and stirred for 60 min. Then, 30 g of crosslinking agent 1,2-bis(4-vinylphenyl)ethane and 0.05 g of dicumyl peroxide were added and stirred for 120 min until all components were uniformly dispersed without agglomeration. Then, 30 g of phosphorus-containing flame retardant Exolit OP1230 was added and stirred for 60 min until completely dispersed. Then, 90 g of vinyl silane-modified spherical silica (sphericity 0.97, D50 5 μm, vinyl silane content 0.8 wt%) was added and stirred for 120 min to obtain a high-performance low-dielectric high-frequency copper-clad plate resin composition.

[0041] Example 2:

[0042] (1) 12 g of 4,4'-diaminodiphenyl methane was stirred in 200 g of acetone at room temperature until completely dissolved. 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, which was slowly added to the above 4,4'-diaminodiphenyl methane solution at 0°C. After the addition was completed, the solution was stirred at 0°C for 60 min, and then the temperature was increased to room temperature and the solution was stirred for another 60 min. The solution was concentrated, washed with deionized water twice, and then washed with acetone once. The obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl methane bismaleimide acid;

[0043] (2) 15 g of 4,4'-diaminodiphenyl sulfone was stirred with 200 g of acetone at room temperature until completely dissolved, 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, and the solution was slowly added dropwise to the above 4,4'-diaminodiphenyl sulfone solution at 0°C. After the dropwise addition was completed, the solution was stirred at 0°C for 60 min, and then the temperature was increased to room temperature and the solution was stirred for another 80 min. The solution was concentrated, washed with deionized water twice, and then washed with acetone once. The obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide acid;

[0044] (3) 24 g of 4,4'-diaminodiphenyl methane bismaleimide acid was uniformly mixed with 40 g of acetic anhydride and 3 g of triethylamine, and stirred at 110°C under nitrogen protection for 120 min. After the reaction was completed, the reaction solution was cooled to room temperature, and the solid was precipitated by pouring the reaction solution into ice water. The solid was collected by filtration, and then recrystallized with acetone. The recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl methane bismaleimide.

[0045] (4) 22 g of 4,4'-diaminodiphenyl sulfone bismaleimide acid was uniformly mixed with 40 g of acetic anhydride and 4 g of triethylamine, and stirred at 110°C under nitrogen protection for 120 min. After the reaction was completed, the reaction solution was cooled to room temperature, and the solid was precipitated by pouring the reaction solution into ice water. The solid was collected by filtration, and then recrystallized with acetone. The recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide.

[0046] (5) 15 g of 4,4'-diaminodiphenyl methane bismaleimide, 17 g of 4,4'-diaminodiphenyl sulfone bismaleimide, 30 g of styrene modified polyphenyl ether NORYL SA9000, 60 g of N-methyl pyrrolidone, 90 g of methyl ethyl ketone, and 150 g of toluene were stirred at 55°C for 90 min to form a uniform transparent solution. 60 g of carbon hydrogen resin ARKON P-125, 50 g of styrene ethylene butylene triblock copolymer Kraton G1726V were added in sequence, and stirred for 60 min after addition. Then 30 g of crosslinking agent 1,2-bis(4-vinylphenyl)ethane and 0.07 g of dicumyl peroxide were added in sequence, and stirred for 120 min after addition until all components were uniformly dispersed without agglomeration. Then 30 g of phosphorus-containing flame retardant Exolit OP1230 was added, and stirred for 60 min until completely dispersed. Then 100 g of vinyl silane modified spherical silica (sphericity of 0.97, D50 of 5 μm, and vinyl silane content of 0.8 wt%) was added, and stirred for 120 min to obtain a high-performance low-dielectric high-frequency copper-clad plate resin composition.

[0047] Example 3:

[0048] (1) 12 g of 4,4'-diaminodiphenylmethane was stirred in 200 g of acetone at room temperature until completely dissolved, 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, which was slowly added dropwise to the above-mentioned 4,4'-diaminodiphenylmethane solution at 0°C, and after the addition was completed, it was incubated at 0°C for 60 min, and then it was continuously stirred at room temperature for 60 min. After concentration, it was washed with deionized water twice and then with acetone once. The obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenylmethane bismaleimide acid;

[0049] (2) 15 g of 4,4'-diaminodiphenyl sulfone was stirred in 200 g of acetone at room temperature until completely dissolved, 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, which was slowly added dropwise to the above-mentioned 4,4'-diaminodiphenyl sulfone solution at 0°C, and after the addition was completed, it was incubated at 0°C for 60 min, and then it was continuously stirred at room temperature for 80 min. After concentration, it was washed with deionized water twice and then with acetone once. The obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide acid;

[0050] (3) 24 g of 4,4'-diaminodiphenylmethane bismaleimide acid was mixed with 40 g of acetic anhydride and 3 g of triethylamine, and stirred at 110°C under nitrogen protection for 120 min. After the reaction was completed, it was cooled to room temperature, and the reaction liquid was poured into ice water to precipitate the solid. After the solid was collected by filtration, it was recrystallized and purified with acetone. The recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenylmethane bismaleimide;

[0051] (4) 22 g of 4,4'-diaminodiphenyl sulfone bismaleimide acid was mixed with 40 g of acetic anhydride and 4 g of triethylamine, and stirred at 110°C under nitrogen protection for 120 min. After the reaction was completed, it was cooled to room temperature, and the reaction liquid was poured into ice water to precipitate the solid. After the solid was collected by filtration, it was recrystallized and purified with acetone. The recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide;

[0052] (5) 16 g of 4,4'-diaminodiphenylmethane bismaleimide, 18 g of 4,4'-diaminodiphenyl sulfone bismaleimide, 30 g of styrene-modified polyphenylene ether NORYL SA9000, and 58 g of N-methylpyrrolidone, 87 g of methyl ethyl ketone, 145 g of toluene were stirred at 55°C for 90 min to form a uniform transparent solution, 60 g of hydrocarbon resin ARKON P-125, 50 g of styrene-ethylene-butylene triblock copolymer Kraton G1726V were sequentially added, and stirred for 60 min after the addition, 30 g of crosslinking agent 1,2-bis(4-vinylphenyl)ethane and 0.08 g of dicumyl peroxide were sequentially added, and stirred for 120 min after the addition until all components were uniformly dispersed without agglomeration, 30 g of phosphorus-containing flame retardant Exolit OP1230 was sequentially added, and stirred for 60 min until completely dispersed, and 105 g of vinyl silane-modified spherical silica (sphericity 0.97, D50 5 μm, vinyl silane content 0.8 wt%) was added, and stirred for 120 min to obtain a high-performance low-dielectric high-frequency copper-clad plate resin composition.

[0053] Example 4:

[0054] (1) 12 g of 4,4'-diaminodiphenylmethane was stirred with 200 g of acetone at room temperature until completely dissolved, 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, and the solution was slowly added dropwise to the above 4,4'-diaminodiphenylmethane solution at 0°C, and stirred for 60 min at 0°C after the addition was completed, and then the temperature was increased to room temperature and stirred for 60 min, concentrated, washed with deionized water twice, and then washed with acetone once, and the obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenylmethane bismaleimide acid;

[0055] (2) 15 g of 4,4'-diaminodiphenyl sulfone was stirred with 200 g of acetone at room temperature until completely dissolved, 12 g of maleic anhydride was dissolved in 50 g of acetone to form a solution, and the solution was slowly added dropwise to the above 4,4'-diaminodiphenyl sulfone solution at 0°C, and stirred for 60 min at 0°C after the addition was completed, and then the temperature was increased to room temperature and stirred for 80 min, concentrated, washed with deionized water twice, and then washed with acetone once, and the obtained solid was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide acid;

[0056] (3) 24 g of 4,4'-diaminodiphenylmethane bismaleimide acid was mixed with 40 g of acetic anhydride and 3 g of triethylamine, and stirred at 110°C for 120 min under nitrogen protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the solid was precipitated by pouring into ice water. The solid was collected by filtration, and then purified by recrystallization with acetone. The recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenylmethane bismaleimide;

[0057] (4) 22 g of 4,4'-diaminodiphenyl sulfone bismaleimide acid was mixed with 40 g of acetic anhydride and 4 g of triethylamine, and stirred at 110°C for 120 min under nitrogen protection. After the reaction was completed, the reaction solution was cooled to room temperature, and the solid was precipitated by pouring into ice water. The solid was collected by filtration, and then purified by recrystallization with acetone. The recrystallized product was dried at 60°C under vacuum for 12 h to obtain 4,4'-diaminodiphenyl sulfone bismaleimide.

[0058] (5) 18 g of 4,4'-diaminodiphenylmethane bismaleimide, 20 g of 4,4'-diaminodiphenyl sulfone bismaleimide, 40 g of styrene-modified polyphenyl ether NORYL SA9000, 60 g of N-methylpyrrolidone, 90 g of methyl ethyl ketone, and 150 g of toluene were stirred at 55°C for 90 min to form a uniform transparent solution. Then, 60 g of hydrocarbon resin ARKON P-125, 50 g of styrene-ethylene-butylene triblock copolymer Kraton G1726V were added and stirred for 60 min. Then, 30 g of crosslinking agent 1,2-bis(4-vinylphenyl)ethane and 0.1 g of dicumyl peroxide were added and stirred for 120 min until all components were uniformly dispersed without agglomeration. Then, 30 g of phosphorus-containing flame retardant Exolit OP1230 was added and stirred for 60 min until completely dispersed. Then, 110 g of vinyl silane-modified spherical silica (sphericity 0.97, D50 5 μm, vinyl silane content 0.8 wt%) was added and stirred for 120 min to obtain a high-performance low-dielectric high-frequency copper-clad plate resin composition.

[0059] Comparative Example 1

[0060] The difference between Comparative Example 1 and Example 2 is that 4,4'-diaminodiphenyl sulfone bismaleimide is not used, and only 4,4'-diaminodiphenylmethane bismaleimide 32 g is used, and the rest of the conditions are the same as Example 2.

[0061] Comparative Example 2

[0062] The difference between Comparative Example 2 and Example 2 is that 4,4'-diaminodiphenylmethane bismaleimide is not used, and only 4,4'-diaminodiphenyl sulfone bismaleimide 32 g is used, and the rest of the conditions are the same as Example 2.

[0063] Comparative Example 3:

[0064] Comparative Example 3 differs from Example 2 in that styrene modified polyphenylene ether NORYL SA9000 is not used, and the rest of the conditions are consistent with Example 2.

[0065] Comparative Example 4:

[0066] Comparative Example 4 differs from Example 2 in that styrene ethylene butylene triblock copolymer Kraton G1726 V is not used, and the rest of the conditions are consistent with Example 2.

[0067] Comparative Example 5:

[0068] Comparative Example 5 differs from Example 2 in that unmodified spherical silica is used instead of vinyl silane modified spherical silica 100g, and the rest of the conditions are consistent with Example 2.

[0069] Test sample preparation:

[0070] Copper-clad plate preparation: 30cm x 30cm E-glass cloth of LowDk-2116 type is immersed in the resin composition, and after the glass cloth is completely infiltrated, a prepreg is prepared by baking at 145°C (the resin content is controlled at 60±2%, which exceeds the standard, and after a certain amount of solvent volatilization, the infiltration step is repeated), the prepared prepreg is cut to 28cm x 28cm and weighed to calculate the resin content, 4 prepregs are prepared according to this process, and the 4 prepregs are cross-laminated, 12μm low-profile electrolytic copper foil is covered on the upper and lower surfaces of the laminated layer, the copper foil is attached to the surface of the prepreg, and the laminated layer is placed in a vacuum press for pressing and curing under a pressure of 2MPa:

[0071] From room temperature to 120°C: 1.5-2.0°C / min, hold for 20min;

[0072] From 120 to 180°C: 2.0-2.5°C / min, hold for 30min;

[0073] From 180 to 200°C: 2.0-2.5°C / min, hold for 60min;

[0074] From 200 to 235°C: 1.5-2.0°C / min, hold for 80min;

[0075] After the pressing procedure is completed, cool to below 100°C and remove to obtain a copper-clad plate.

[0076] Performance test:

[0077] Infrared test: tested by Fourier transform infrared spectrometer, the results are shown in Table 1. Figure 1 Table 1

[0078] Dielectric property test: The dielectric constant and dielectric loss factor of copper clad laminate were tested by using network analyzer with 10GHz split post resonator according to GB / T 4722-1992, the results were shown in Table 1.

[0079] Thermal expansion coefficient test: The thermal expansion coefficient in Z direction was tested by using TMA thermal expansion instrument according to IPC-TM-650 2.4.24, the test procedure was set as heating rate 10℃ / min, nitrogen protective atmosphere, test temperature range 25-260℃, the linear thermal expansion coefficient of three temperature intervals of 60-100℃ (Z-CTE1), 200-250℃ (Z-CTE2) and 50-260℃ (Z-CTE3) were calculated respectively, the results were shown in Table 1.

[0080] Glass transition temperature test: The glass transition temperature was determined by using differential scanning calorimetry (DSC), the test conditions were nitrogen atmosphere, heating rate 10℃ / min, temperature range 50-280℃, the Tg point was determined by half-height method, each sample was tested in parallel for 3 times to take the average value, the results were shown in Table 1, the DSC spectrum was shown in Figure 2 and Figure 3 .

[0081] Copper foil peel strength test: The 90 degree peel test was carried out by using universal testing machine according to the peel strength test method specified in IPC-TM-650 2.4.8, the copper strip with width of 3.5-4.0mm was drawn on the surface of copper foil by using precision knife, the peel length was not less than 25mm, the test speed was set as 50mm / min, the test environment was standard condition (23±2℃, 50±5%RH), each sample was tested for 10 copper strips, the average value was taken after removing the highest and lowest value, the unit was Ib / in, the results were shown in Table 1.

[0082]

[0083] Data analysis:

[0084] As can be seen from the data of Examples 1-4 in Table 1, the high-performance low-dielectric high-frequency copper-clad plate resin composition prepared by the present application exhibits excellent comprehensive performance characteristics, in which the dielectric constant gradually increases from 3.12 to 3.18, and the dielectric loss factor overall shows a downward trend from 0.00178 to 0.00161. This change pattern shows that the increase of the content of the composite bismaleimide system to a certain extent improves the polarization degree of the resin molecules, but at the same time the increase of the rigidity of the molecular chain segment and the increase of the crosslinking density effectively inhibit the dielectric loss caused by the molecular motion, especially in Example 4, reaching the minimum value of 0.00161, showing good high-frequency signal transmission performance. The thermal expansion performance data shows that Z-CTE1 fluctuates from 44 ppm / °C to 31 ppm / °C, Z-CTE2 gradually decreases from 145 ppm / °C to 115 ppm / °C, and Z-CTE3 maintains an excellent level of 1.6-1.7%. This change trend shows that the optimized ratio of the content of bismaleimide can effectively build a three-dimensional crosslinking network structure, limit the thermal motion of the molecular chain segment, and thus significantly reduce the thermal expansion coefficient, among which Example 2 balances the dielectric performance while maintaining the best thermal expansion control effect. The glass transition temperature changes in the range of 205-214 °C, indicating that the resin system has excellent heat resistance, and the copper foil peeling strength increases from 5.1 Ib / in to 5.8 Ib / in, indicating that the increase of the content of the vinyl silane modified silica filler improves the inorganic-organic interface bonding strength and enhances the adhesion performance of the resin and the copper foil.

[0085] From the data of Example 2 and Comparative Example 1 in Table 1, the key difference in composition is that Example 2 employs a composite system of 15 g 4,4'-diaminodiphenylmethane bismaleimide and 17 g 4,4'-diaminodiphenyl sulfone bismaleimide, while Comparative Example 1 uses only 32 g of a single 4,4'-diaminodiphenylmethane bismaleimide. The dielectric constant of Example 2 is 3.14, which is slightly increased compared to 3.08 of Comparative Example 1, which can be attributed to the introduction of sulfone groups that enhance the polarization ability of the molecule, but its dielectric loss factor is significantly reduced to 0.00173, which is 15.2% lower than 0.00204 of Comparative Example 1, indicating that the composite bismaleimide system effectively suppresses the generation of dielectric loss through the synergistic effect of the molecular structure. In terms of thermal expansion performance, the Z-CTE1 of Example 2 is 39 ppm / °C, which is significantly lower than 50 ppm / °C of Comparative Example 1, the Z-CTE2 is 126 ppm / °C, which is much lower than 170 ppm / °C of Comparative Example 1, and the Z-CTE3 is 1.6%, which is significantly better than 2.0% of Comparative Example 1. This significant improvement indicates that the strong electron absorption effect of the sulfone group in 4,4'-diaminodiphenyl sulfone bismaleimide and the flexible segment of methane bismaleimide form a complement, constructing a more uniform and dense cross-linked network structure, effectively limiting thermal expansion deformation. The glass transition temperature of Example 2 reaches 210 °C, which is higher than 204 °C of Comparative Example 1, indicating that the composite system improves the heat resistance, while the copper foil peel strength of Example 2 is 5.3 Ib / in, which is significantly higher than 4.6 Ib / in of Comparative Example 1, with an increase of 15.2%, which indicates that the composite bismaleimide system improves the mechanical properties and interfacial bonding characteristics of the resin matrix, enhancing the bonding strength with the copper foil.

[0086] As can be seen from the data of Example 2 and Comparative Example 2 in Table 1, Example 2 uses a composite system of 15 g of methane type and 17 g of sulfone type bismaleimide, while Comparative Example 2 only uses 32 g of a single sulfone type bismaleimide. The dielectric constant of Example 2 is 3.14, which is significantly lower than 3.26 of Comparative Example 2, with a decrease of 3.7%, which indicates that the introduction of methane type bismaleimide effectively reduces the polarization degree of the overall molecule, and the dielectric loss factor of Example 2 is 0.00173, which is significantly lower than 0.00228 of Comparative Example 2 by 24.1%, which shows that the composite system significantly suppresses the dielectric loss caused by the molecular dipole orientation polarization through the balance of the flexibility and rigidity of the molecular chain segments. In terms of thermal expansion performance, Z-CTE1 of Example 2 is 39 ppm / °C, which is slightly higher than 34 ppm / °C of Comparative Example 2, but Z-CTE2 is 126 ppm / °C, which is significantly lower than 160 ppm / °C of Comparative Example 2, and Z-CTE3 is 1.6%, which is significantly better than 1.9% of Comparative Example 2, which shows that although a single sulfone type bismaleimide exhibits good dimensional stability in the low temperature range, the thermal motion of its rigid molecular chain segments is intensified in the high temperature range, resulting in an increase in thermal expansion, while the composite system realizes the control of thermal expansion in the whole temperature range through the flexibility adjustment of the methane type component. In terms of glass transition temperature, Example 2 is 210°C, which is slightly lower than 213°C of Comparative Example 2, which may be due to the moderate adjustment of the flexible chain segments of methane type bismaleimide to the rigidity of the overall crosslinked network, while the copper foil peel strength of Example 2 reaches 5.3 Ib / in, which is significantly higher than 4.3 Ib / in of Comparative Example 2, with an increase of 23.3%, which shows that the composite system effectively enhances the adhesion strength with the copper foil by improving the toughness and interfacial compatibility of the resin matrix.

[0087] As can be seen from the data of Example 2 and Comparative Example 3 in Table 1, Example 2 contains 30 g of styrene modified polyphenyl ether NORYL SA9000, while Comparative Example 3 does not use this component at all. The dielectric constant of Example 2 is 3.14, which is reduced by 4.8% compared with 3.30 of Comparative Example 3, and the dielectric loss factor is 0.00173, which is reduced by 25.4% compared with 0.00232 of Comparative Example 3, which shows that the styrene modified polyphenyl ether effectively improves the dielectric properties through its non-polar benzene ring structure and low loss characteristics. The thermal expansion performance shows that Z-CTE1, Z-CTE2 and Z-CTE3 of Example 2 are 39 ppm / °C, 126 ppm / °C and 1.6% respectively, which are significantly better than 54 ppm / °C, 185 ppm / °C and 2.2% of Comparative Example 3, which shows that this component effectively limits the thermal expansion deformation through the rigid aromatic backbone structure. The glass transition temperature of Example 2 reaches 210°C, which is higher than 195°C of Comparative Example 3, and the copper foil peel strength is 5.3 Ib / in, which is increased by 20.5% compared with 4.4 Ib / in of Comparative Example 3.

[0088] As can be seen from the data in Table 1 for Example 2 and Comparative Example 4, Example 2 contains 50g of the styrene-ethylene-butene triblock copolymer Kraton G1726 V, while Comparative Example 4 lacks this toughening component. Both have similar dielectric constants of 3.14, but the dielectric loss factor of Example 2 is 0.00173, which is 8.9% lower than that of Comparative Example 4 (0.00190). This indicates that the toughening agent effectively reduces dielectric loss through its phase separation structure. Regarding thermal expansion properties, the Z-CTE2 of Example 2 is 126 ppm / ℃, which is better than that of Comparative Example 4 (132 ppm / ℃), and the Z-CTE3 is 1.6%, which is better than that of Comparative Example 4 (1.7%). This demonstrates that the toughening agent alleviates high-temperature thermal expansion stress through flexible adjustment. The most significant difference was in the copper foil peel strength, which reached 5.3 Ib / in in Example 2, a significant increase of 26.2% compared to 4.2 Ib / in in Comparative Example 4. This indicates that the styrene-ethylene-butene triblock copolymer significantly enhanced the adhesion strength between the resin matrix and the copper foil through excellent toughening effect and interface modification ability, via molecular chain entanglement and stress transfer mechanism.

[0089] As can be seen from the data in Table 1 for Example 2 and Comparative Example 5, Example 2 used vinylsilane-modified spherical silica, while Comparative Example 5 used unmodified filler. The dielectric constant of Example 2 was 3.14, a decrease of 3.1% compared to 3.24 in Comparative Example 5, and the dielectric loss factor was 0.00173, a decrease of 19.9% ​​compared to 0.00216 in Comparative Example 5. This indicates that silane modification eliminated polar groups on the filler surface, reducing dielectric loss caused by interfacial polarization and defects. Thermal expansion performance showed that Z-CTE1, Z-CTE2, and Z-CTE3 of Example 2 were 39 ppm / ℃, 126 ppm / ℃, and 1.6%, respectively, all significantly better than the 48 ppm / ℃, 175 ppm / ℃, and 2.1% of Comparative Example 5. This demonstrates that vinylsilane establishes strong interfacial bonding through chemical bonding, forming a continuous stress transfer network that effectively limits thermal expansion. The copper foil peel strength of Example 2 was 5.3 Ib / in, which is 23.3% higher than that of Comparative Example 5 (4.3 Ib / in), indicating that the modified filler enhances the interfacial bonding strength through chemical crosslinking of the surface vinyl group with the matrix.

[0090] from Figure 1 It can be seen that the 4,4'-diaminodiphenylmethane bismaleimide and the 4,4'-diaminodiphenylsulfone bismaleimide synthesized in Example 2 of this invention both exhibit typical imide C=O stretching absorption peaks in their infrared spectra, and the sulfone-type bismaleimide shows a peak at 1324 cm⁻¹. -1 With 1156cm -1 The presence of a distinct SO2 characteristic absorption peak, in contrast to methane-type bismaleimide, verifies the successful synthesis of the two monomer structures and the existence of their characteristic functional groups.

[0091] fromFigures 2-3 It can be seen that the resin compositions of Examples 1-4 all exhibit clear glass transition temperatures on the DSC curves, and with the optimization of the amount of composite bismaleimide and modified silica, the Tg is kept at a high level of 205-214℃, which reflects the excellent heat resistance of the system; at the same time, Example 2, while maintaining a high Tg, its residual exothermic peak is significantly weaker than Comparative Examples 1-5, indicating that the system is fully cured and the crosslinking network is uniform and dense. In comparison, the comparative sample has a strong residual exothermic peak in the range of 220-235℃, indicating that it is not fully cured or the crosslinking structure is not uniform, thus further demonstrating the advantages of the composite system of the present application in terms of thermal stability and structural integrity.

[0092] It should be understood by those of ordinary skill in the art that the above discussion of any of the embodiments is merely exemplary and is not intended to suggest that the scope of the present application is limited to these examples; under the idea of the present application, the technical features of the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other changes of different aspects of the present application as described above. In order to be brief, they are not provided in detail.

Claims

1. A method for preparing a high-performance, low-dielectric, high-frequency copper-clad laminate resin composition, characterized in that, Comprise the following steps: (1) 4,4'-diaminodiphenyl methane and maleic anhydride are dissolved in acetone respectively, the maleic anhydride solution is added dropwise to the 4,4'-diaminodiphenyl methane solution at 0℃, after the dropwise addition is completed, stirring at 0℃ for 60min, continue to stir at room temperature for 60min, concentrate, wash, vacuum drying, 4,4'-diaminodiphenyl methane bismaleamic acid is obtained; (2) 4,4'-diaminodiphenyl sulfone and maleic anhydride are dissolved in acetone respectively, the maleic anhydride solution is added dropwise to the 4,4'-diaminodiphenyl sulfone solution at 0℃, after the dropwise addition is completed, stirring at 0℃ for 60min, continue to stir at room temperature for 80min, concentrate, wash, vacuum drying, 4,4'-diaminodiphenyl sulfone bismaleamic acid is obtained; (3) 4,4'-diaminodiphenyl methane bismaleamic acid is mixed with acetic anhydride and triethylamine under nitrogen protection, after stirring at 110℃ for 120min, cooling, pouring into ice water to precipitate solid, recrystallization, vacuum drying, 4,4'-diaminodiphenyl methane bismaleimide is obtained; (4) 4,4'-diaminodiphenyl sulfone bismaleamic acid is mixed with acetic anhydride and triethylamine under nitrogen protection, after stirring at 110℃ for 120min, cooling, pouring into ice water to precipitate solid, recrystallization, vacuum drying, 4,4'-diaminodiphenyl sulfone bismaleimide is obtained; (5) solvent, 4,4'-diaminodiphenyl methane bismaleimide, 4,4'-diaminodiphenyl sulfone bismaleimide and modified polyphenyl ether NORYL SA9000 are stirred at 55℃ for 90min, after adding hydrocarbon resin and triblock copolymer Kraton G1726 V, stirring for 60min, adding 1,2-bis(4-vinylphenyl)ethane and dicumyl peroxide, stirring for 120min, adding phosphorus-containing flame retardant, stirring for 60min, adding vinyl silane modified spherical silica, stirring for 120min; The weight ratio of solvent, 4,4'-diaminodiphenyl methane bismaleimide, 4,4'-diaminodiphenyl sulfone bismaleimide, modified polyphenyl ether NORYL SA9000, hydrocarbon resin, triblock copolymer Kraton G1726 V, 1,2-bis(4-vinylphenyl)ethane, dicumyl peroxide, phosphorus-containing flame retardant and vinyl silane modified spherical silica in step (5) is 250-300:13-18:15-20:30-40:50-60:50:30:0.05-0.1:30:90-110.

2. The method for preparing a high-performance low-dielectric high-frequency copper-clad plate resin composition according to claim 1, characterized by, The mass ratio of 4,4'-diaminodiphenyl methane and maleic anhydride in step (1) is 1:

1.

3. The method of claim 1, wherein the resin composition is prepared by mixing the components in the following order: (1) the epoxy resin, (2) the curing agent, (3) the filler, (4) the solvent, (5) the coupling agent, and (6) the curing catalyst. The mass ratio of 4,4'-diaminodiphenyl sulfone and maleic anhydride in step (2) is 5:

4.

4. The method for preparing a high-performance low-dielectric high-frequency copper-clad plate resin composition according to claim 1, characterized by, The weight ratio of 4,4'-diaminodiphenyl methane bismaleamic acid, acetic anhydride and triethylamine in step (3) is 24:40:

3.

5. The method of claim 1, wherein the resin composition is prepared by mixing the components in the following order: (1) the epoxy resin, (2) the curing agent, (3) the filler, (4) the solvent, (5) the coupling agent, and (6) the curing catalyst. The weight ratio of 4,4'-diaminodiphenyl sulfone bismaleamic acid, acetic anhydride and triethylamine in the step (4) is 22:40:

4.

6. The method of claim 1, wherein the resin composition is prepared by mixing the components in the following order: (1) the epoxy resin, (2) the curing agent, (3) the filler, (4) the solvent, (5) the coupling agent, and (6) the curing catalyst. The solvent in the step (5) is a mixture of N-methyl pyrrolidone, methyl ethyl ketone and toluene in a mass ratio of 50-60:75-90:125-150.

7. The method of claim 1, wherein the resin composition is prepared by mixing the components in the following order: (1) the epoxy resin, (2) the curing agent, (3) the filler, (4) the solvent, (5) the coupling agent, and (6) the curing catalyst. The model of the hydrocarbon resin is ARKON P-125.

8. The method of claim 1, wherein the resin composition is prepared by mixing the components in the following order: (1) the epoxy resin, (2) the curing agent, (3) the filler, (4) the solvent, (5) the coupling agent, and (6) the curing catalyst. The structural features of the vinyl silane modified spherical silica in the step (5) are as follows: sphericity is 0.97, D50 is 5 μm, and surface vinyl silane content is 0.8 wt%.

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