Preparation method of high-frequency and high-speed copper-clad plate and copper-clad plate
Through the combination of modified cyanate resin and functional filler, the shortcomings of dielectric and mechanical properties of copper clad laminates in high-frequency and high-speed signal transmission are solved, the preparation of copper clad laminates with low dielectric constant, low dielectric loss and good toughness is achieved, and the signal transmission quality and structural stability are improved.
Patent Information
- Application Number
- CN202511094458.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-06
- Publication Date
- 2025-10-17
AI Technical Summary
Existing copper clad laminates are difficult to simultaneously meet the requirements of low dielectric constant, low dielectric loss, good toughness and mechanical properties in high-frequency and high-speed signal transmission. Traditional resin materials have poor dielectric stability during the modification process, and high-performance resins are brittle and have insufficient impact resistance.
A combination of modified cyanate ester resin and functional filler is used. The cyanate ester resin is modified by a modifier to form a covalent organic framework, introduce a porous structure, and use a toughening agent to react with the bismaleimide resin to form a uniformly dispersed microphase structure. The boron nitride is treated with a silane coupling agent to improve the mechanical and dielectric properties.
It achieves ultra-low dielectric constant and dielectric loss, significantly improves the dielectric stability and impact strength of the copper clad laminate, reduces dielectric loss, and improves thermal conductivity and structural stability.
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Figure CN120792299A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of copper-clad plate, in particular to a preparation method of high-frequency high-speed copper-clad plate and the copper-clad plate. BACKGROUND
[0002] With the rapid development of new generation information technologies such as 5G communication, data center and artificial intelligence, signal transmission evolves towards high frequency and high speed, which puts forward strict requirements on the dielectric properties of copper-clad plate. In high-frequency high-speed scenarios, signal transmission loss mainly comes from dielectric loss and conductor loss, among which dielectric loss is directly affected by material dielectric constant (Dk) and dielectric loss factor (Df), and low dielectric constant and low dielectric loss become the core indicators to ensure signal transmission rate and integrity. At the same time, the copper-clad plate also needs to have excellent mechanical properties, heat conduction properties and structural stability to meet the use requirements under complex working conditions.
[0003] In the prior art, traditional copper-clad plates often use epoxy resin, ordinary cyanate ester resin and other matrix materials, but it is difficult to meet the demand of high-frequency signal transmission. In order to reduce the dielectric constant, researchers often modify by introducing porous structure or low dielectric filler, but often face problems such as poor dielectric stability and decreased mechanical properties. In addition, although high-performance resins such as cyanate ester resin and bismaleimide resin have low dielectric potential, they are brittle and lack impact resistance.
[0004] Therefore, it is a key problem to be solved in the industry to develop a high-frequency high-speed copper-clad plate with ultra-low dielectric constant, low dielectric loss and good toughness. SUMMARY
[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide a preparation method of high-frequency high-speed copper-clad plate and the copper-clad plate.
[0006] The present application provides a high-frequency high-speed copper-clad plate, comprising: an upper copper foil layer, a middle prepreg layer and a lower copper foil layer; The prepreg is obtained by impregnating glass fiber cloth in a composite resin glue solution and then curing; The prepreg is stacked and combined, then a copper foil is placed on the upper surface and the lower surface of the stacked and combined prepreg, and finally the copper-clad plate is obtained by pressing in a hot press; The composite resin glue solution comprises 60-70 parts by weight of bismaleimide resin, 100-120 parts by weight of modified cyanate ester resin, 20-30 parts by weight of butanone, 100-120 parts by weight of toluene, 2-3 parts by weight of curing accelerator, 1-2 parts by weight of antioxidant, 20-30 parts by weight of functional filler and 10-15 parts by weight of toughening agent; The modified cyanate ester resin is prepared by modifying a cyanate ester resin prepolymer by a modifier prepared by reacting hexachlorocyclotriphosphazene and 3,3-dimethylbenzidine.
[0007] The application further provides a preparation method of the high-frequency high-speed copper-clad plate. S1: preparation of the modified cyanate ester resin; The modifier is prepared by reacting hexachlorocyclotriphosphazene and 3,3-dimethylbenzidine, and then the cyanate ester resin prepolymer is prepared by mixing dicyanatophenylpropane and epoxy resin, and the cyanate ester resin prepolymer is modified by the modifier to obtain the modified cyanate ester resin. S2: preparation of the functional filler; The functional filler is prepared by modifying boron nitride powder by silane coupling agent KH550 and then modifying by carboxyl-terminated hyperbranched polyester. S3: preparation of the copper-clad plate; The toughening agent is synthesized by toluene diisocyanate trimer and methyl nadic anhydride, and then the composite resin glue solution is prepared by mixing raw materials, and the glass fiber cloth is immersed in the composite resin glue solution to prepare a prepreg, and the copper-clad plate is obtained by laminating and combining the prepreg and copper foil and then being pressed and molded.
[0008] As a preferred aspect, the step S1: preparation of the modified cyanate ester resin, specifically includes the following steps: S1.1: 2-3 parts by weight of hexachlorocyclotriphosphazene and 6-10 parts by weight of 3,3-dimethylbenzidine are added to 50-60 parts by weight of N,N-dimethylformamide, stirred and mixed for 20-30 min to obtain a mixed solution, the mixed solution is placed in a reaction kettle, sealed and transferred to a 90-95℃ air oven for constant temperature heating reaction for 24-28h, after the reaction is completed, the precipitate is filtered and washed with deionized water and acetone alternately for 3-5 times, and the washed precipitate is dried to obtain a modifier; S1.2: 50-60 parts by weight of dicyanatophenylpropane is mixed with 5-6 parts by weight of epoxy resin, and then stirred and mixed at 160-163℃ and 120-150r / min until no crystal residue is left to obtain a cyanate ester resin prepolymer; S1.3: 10-12 parts by weight of the modifier is added to 10-12 parts by weight of acetone, ultrasonic dispersion treatment is performed for 1-2h, and then added to 90-100 parts by weight of the cyanate ester resin prepolymer, stirred and mixed, and then stirred at 120-130℃ until the acetone is completely evaporated, and then degassed at 120-123℃ for 2-3h, and then phase curing is performed to obtain the modified cyanate ester resin.
[0009] As a preferred aspect, the staged curing in step S1.3 specifically comprises: curing at 140-142℃ for 60-70min, curing at 160-162℃ for 60-70min, curing at 180-182℃ for 60-70min, curing at 200-210℃ for 60-70min, and curing at 220-230℃ for 60-70min.
[0010] As a preferred aspect, step S2: preparation of the functional filler, specifically comprises the following steps: S2.1: 8-9 parts by weight of boron nitride powder is added to 100-120 parts by weight of ethanol, ultrasonic stirring and mixing for 20-30min, and ultrasonic dispersion for 20-30min to obtain a suspension, 0.2-0.3 parts by weight of silane coupling agent KH550 is added to 10-12 parts by weight of 90-95wt% ethanol aqueous solution, stirring and mixing for 20-30min, then added to the suspension, ultrasonic stirring and mixing for 2-3h, then filtered, dried and ground to obtain the coupling agent modified boron nitride; S2.2: 10-12 parts by weight of the coupling agent modified boron nitride is added to 100-120 parts by weight of acetone solution, ultrasonic stirring and mixing for 20-30min, then 0.5-0.8 parts by weight of carboxyl-terminated hyperbranched polyester and 0.005-0.008 parts by weight of p-toluene sulfonic acid are added under magnetic stirring, stirring and mixing for 40-50min, then filtered, washed, dried and ground to obtain the functional filler.
[0011] As a preferred aspect, step S3: preparation of the copper-clad plate, specifically comprises the following steps: S3.1: 1-3 parts by weight of toluene diisocyanate trimer and 3-9 parts by weight of methyl nadic anhydride are mixed, then 10-12 parts by weight of N,N-dimethylformamide is added, and condensation reflux reaction is carried out at 150-200rpm, nitrogen is introduced during the reaction, and the reaction is carried out at 90-92℃ for 4-5h, after the reaction is completed, vacuum distillation is carried out at 90-92℃, then the reaction is carried out at 120-125℃ for 4-5h to obtain the toughening agent; S3.2: 60-70 parts by weight of bismaleimide resin, 100-120 parts by weight of modified cyanate ester resin are mixed uniformly, heated to 120-130℃, then 20-30 parts by weight of butanone, 100-120 parts by weight of toluene, 2-3 parts by weight of curing accelerator, 1-2 parts by weight of antioxidant, 20-30 parts by weight of functional filler and 10-15 parts by weight of toughening agent are added, and mixed uniformly at 200-300rpm to obtain the composite resin glue solution; S3.3: The glass fiber cloth is immersed in a composite resin glue solution, and after pre-impregnation, impregnation, exhaust impregnation treatment in an impregnator, it is dried to prepare a prepreg, the prepreg is stacked and combined, then a copper foil is placed on the upper surface and the lower surface of the stacked combination, and finally it is sent into a hot press to be pressed and formed under the conditions of 190-200 DEG C and 4-6 MPa, to obtain a copper-clad plate.
[0012] As a preferred aspect, the curing accelerator in step S3.2 is one of 2-methylimidazole, 2-phenylimidazole and 2-ethyl-4-methylimidazole.
[0013] As a preferred aspect, the antioxidant in step S3.2 is one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
[0014] The present application has the following advantages: 1. The cyanate ester resin is modified by the modifier, the modifier is a covalent organic framework covalently cross-linked to form a phosphazene group, the pore size is larger, more air is introduced, and it is more conducive to improving the low dielectric property, the modifier is introduced into the cyanate ester resin, and the dielectric property and the mechanical property are synergistically enhanced through the dual mechanisms of intermolecular interaction and chain entanglement, the highly ordered porous structure in the modifier and the covalently connected network framework can effectively inhibit the charge accumulation, and the covalent bond network can weaken the polarization effect, and the ordered pore can eliminate the interface defects, and the synergistic effect in many aspects makes the modifier maintain the ultra-low dielectric constant while significantly improving the dielectric stability of the composite material, and the modifier acts as a physical crosslinking agent in the polymer matrix, thereby limiting the movement of the polymer chain, thereby further reducing the dielectric constant and dielectric loss.
[0015] 2. The toughening agent synthesized by introducing toluene diisocyanate trimer and methyl nadic anhydride is introduced, the active groups of the toughening agent can react with the bismaleimide resin and the modified cyanate ester resin, the toughening agent molecules are “anchored” in the resin cross-linked network, a uniform dispersed “micro-phase structure” is formed, the toughening phase is distributed in the rigid resin matrix, and when stressed, the stress is dispersed through deformation, the crack propagation is inhibited, the impact strength of the copper-clad plate is significantly improved, the toughening effect is achieved, and since the toughening agent is rich in functional end groups, it can react with the bismaleimide resin, so that the resin system is more compact, the vibration of the polymer chain segment under high-frequency alternating electric field is effectively inhibited, and the dielectric loss is effectively reduced.
[0016] 3、The application introduces ammonia active groups on the surface of boron nitride by pretreating boron nitride with silane coupling agent KH550, reduces the surface energy, and further modifies the boron nitride with carboxyl-terminated hyperbranched polyester, avoids the agglomeration of boron nitride in the resin matrix, forms a more continuous heat conduction path, and the surface active groups of the modified boron nitride can form hydrogen bond action with glass fiber cloth, helping the resin glue to better penetrate the fiber gap, reducing bubbles and voids during the impregnation process, making the prepreg structure more dense, ultimately improving the performance stability of the copper-clad plate, and the multi-branched structure of the hyperbranched polyester in the functional filler can fill the interface voids, reduce the charge traps, and the strong interface bonding force formed by chemical modification limits the movement of molecular chains at the interface, reduces the dipole orientation polarization, and thus reduces the dielectric loss. BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 The preparation method process flow chart of the high-frequency high-speed copper-clad plate adopted by the embodiment of the application is shown in the figure. Figure 2 The modifier structure characterization diagram of the application is shown in the figure. Figure 3 The toughening agent synthesis reaction formula of the application is shown in the figure. DETAILED DESCRIPTION
[0018] In order to enable personnel in the technical field to better understand the technical solutions in the application, the technical solutions in the embodiments of the application will be clearly and completely described below in combination with the drawings in the embodiments of the application.
[0019] Embodiment 1, a preparation method of a high-frequency high-speed copper-clad plate, refer to Figure 1 , including: S1: preparation of modified cyanate ester resin S1.1: 2 parts by weight of hexachlorocyclotriphosphazene and 6 parts by weight of 3,3-dimethylbenzidine are added to 50 parts by weight of N,N-dimethylformamide, stirred and mixed for 20 min, the mixed solution is placed in a reaction kettle, sealed and transferred to a 90℃ air oven for constant temperature heating reaction for 24h, after the reaction is completed, the precipitate is filtered and washed with deionized water and acetone alternately for 3 times, the washed precipitate is dried to obtain a modifier; S1.2: 50 parts by weight of dicyanatophenyl propane is mixed with 5 parts by weight of epoxy resin, and then stirred and mixed at 160℃ and 120r / min until no crystal residue is left, to obtain a cyanate ester resin prepolymer; S1.3: 10 parts by weight of the modifier is added to 10 parts by weight of acetone, ultrasonic dispersion treatment is carried out for 1h, then it is added to 90 parts by weight of the cyanate ester resin prepolymer, stirred and mixed, and then stirred at 120℃ until the acetone is completely evaporated, then degassed at 120℃ for 2h, and then phase curing is carried out to obtain the modified cyanate ester resin; The staged curing is specifically: curing at 140℃ for 60min, curing at 160℃ for 60min, curing at 180℃ for 60min, curing at 200℃ for 60min, and curing at 220℃ for 60min; S2: Preparation of functional filler S2.1: 8 parts by weight of boron nitride powder was added to 100 parts by weight of ethanol, ultrasonic stirring and mixing for 20min, and ultrasonic dispersion for 20min to obtain a suspension, 0.2 parts by weight of silane coupling agent KH550 was added to 10 parts by weight of 90-95wt% ethanol aqueous solution, stirring and mixing for 20min, then added to the suspension, ultrasonic stirring and mixing for 2h, then filtered, dried and ground to obtain the coupling agent modified boron nitride; S2.2: 10 parts by weight of the coupling agent modified boron nitride was added to 100 parts by weight of acetone solution, ultrasonic stirring and mixing for 20min, then 0.5 parts by weight of carboxyl-terminated hyperbranched polyester and 0.005 parts by weight of p-toluene sulfonic acid were added under magnetic stirring, stirring and mixing for 40min, then filtered, washed, dried and ground to obtain the functional filler; S3: Preparation of copper-clad plate S3.1: 1 part by weight of toluene diisocyanate trimer and 3 parts by weight of methyl nadic anhydride were mixed, then 10 parts by weight of N,N-dimethylformamide was added, and condensation reflux reaction was carried out at 150rpm, nitrogen was introduced during the reaction, and the reaction was carried out at 90℃ for 4h, then vacuum distillation was carried out at 90℃, and then the reaction was carried out at 120℃ for 4h to obtain the toughening agent; S3.2: 60 parts by weight of bismaleimide resin and 100 parts by weight of modified cyanate resin were uniformly mixed, and then heated to 120℃, then 20 parts by weight of butanone, 100 parts by weight of toluene, 2 parts by weight of 2-methyl imidazole, 1 part by weight of antioxidant 1010, 20 parts by weight of functional filler and 10 parts by weight of toughening agent were added, and uniformly mixed at 200rpm to obtain the composite resin glue solution; S3.3: The glass fiber cloth was immersed in the composite resin glue solution, and after pre-impregnation, impregnation, exhaust impregnation treatment in the impregnation machine, it was dried to prepare a prepreg, the prepreg was stacked and combined, then a copper foil was placed on the upper surface and the lower surface of the stacked and combined prepreg, and finally sent into a hot press to be pressed and formed under the conditions of 190℃ and 4MPa to obtain a copper-clad plate.
[0020] Example 2, a method for preparing a high-frequency high-speed copper-clad plate, referring to Figure 1 , comprising: S1: Preparation of modified cyanate resin S1.1: 3 parts by weight of hexachlorocyclotriphosphazene and 10 parts by weight of 3,3-dimethylbenzidine were added to 60 parts by weight of N,N-dimethylformamide, and the mixture was stirred for 20 min to obtain a mixed solution. The mixed solution was placed in a reaction kettle, sealed, and then transferred to a 90°C air oven for constant temperature heating reaction for 24 h. After the reaction was completed, the precipitate was filtered and washed with deionized water and acetone alternately for 3 times. The washed precipitate was dried to obtain a modifier; S1.2: 60 parts by weight of dicyanatophenylpropane was mixed with 6 parts by weight of epoxy resin, and then stirred at 160°C and 120 r / min until no crystal residue was left to obtain a cyanate ester resin prepolymer; S1.3: 2 parts by weight of the modifier was added to 12 parts by weight of acetone, and ultrasonic dispersion treatment was performed for 1 h. Then, it was added to 100 parts by weight of the cyanate ester resin prepolymer, stirred and mixed, and stirred at 120°C until the acetone was completely evaporated. Then, it was degassed at 120°C for 2 h, and then phase curing was performed to obtain a modified cyanate ester resin; The phase curing was specifically as follows: 140°C for 60 min, 160°C for 60 min, 180°C for 60 min, 200°C for 60 min, and 220°C for 60 min; S2: Preparation of functional filler S2.1: 9 parts by weight of boron nitride powder was added to 120 parts by weight of ethanol, and ultrasonic stirring and mixing was performed for 20 min and ultrasonic dispersion was performed for 20 min to obtain a suspension. 0.3 parts by weight of silane coupling agent KH550 was added to 12 parts by weight of 95wt% ethanol aqueous solution, stirred and mixed for 20 min, and then added to the suspension, ultrasonic stirring and mixing was performed for 2 h, and then filtered, dried and ground to obtain a coupling agent modified boron nitride; S2.2: 12 parts by weight of the coupling agent modified boron nitride was added to 120 parts by weight of acetone solution, and ultrasonic stirring and mixing was performed for 20 min. Then, 0.8 parts by weight of carboxyl-terminated hyperbranched polyester and 0.008 parts by weight of p-toluene sulfonic acid were added under magnetic stirring, and stirring and mixing was performed for 40 min. Then, it was filtered, washed, dried and ground to obtain a functional filler; S3: Preparation of copper-clad plate S3.1: 3 parts by weight of toluene diisocyanate trimer and 9 parts by weight of methyl nadic anhydride were mixed, and then 12 parts by weight of N,N-dimethylformamide was added. Condensation reflux reaction was performed at 150 rpm, nitrogen was introduced during the reaction, and reaction was performed at 90°C for 4 h. After the reaction was completed, vacuum distillation was performed at 90°C, and then reaction was performed at 120°C for 4 h to obtain a toughening agent; S3.2: 70 parts by weight of bismaleimide resin, 120 parts by weight of modified cyanate ester resin are mixed uniformly, heated to 120℃, then 30 parts by weight of butanone, 120 parts by weight of toluene, 3 parts by weight of 2-phenylimidazole, 2 parts by weight of antioxidant 168, 30 parts by weight of functional filler and 15 parts by weight of toughening agent are added, mixed uniformly at 200 rpm, to obtain a composite resin glue solution; S3.3: The glass fiber cloth is immersed in the composite resin glue solution, and after pre-impregnation, impregnation, exhaust impregnation treatment in the impregnation machine, it is dried to prepare a prepreg. The prepreg is combined by stacking, then a copper foil is placed on the upper surface and the lower surface of the stacked combination, and finally it is sent into a hot press to be pressed and formed under the conditions of 190℃ and 4MPa, to obtain a copper-clad plate.
[0021] Example 3, a method for preparing a high-frequency high-speed copper-clad plate, referring to Figure 1 , comprising: S1: Preparation of modified cyanate ester resin S1.1: 2 parts by weight of hexachlorocyclotriphosphazene and 6 parts by weight of 3,3-dimethylbenzidine are added to 50 parts by weight of N,N-dimethylformamide, stirred and mixed for 30 min, to obtain a mixed solution. The mixed solution is placed in a reaction kettle, sealed and transferred to a 95℃ air oven for constant temperature heating reaction for 28h. After the reaction is completed, the precipitate is filtered and washed with deionized water and acetone alternately for 5 times. The washed precipitate is dried to obtain a modifier; S1.2: 50 parts by weight of dicyanatophenyl propane is mixed with 5 parts by weight of epoxy resin, and stirred and mixed at 163℃ and 150r / min until no crystal residue is left, to obtain a cyanate ester resin prepolymer; S1.3: 10 parts by weight of the modifier is added to 10 parts by weight of acetone, ultrasonic dispersion treatment is performed for 2h, then it is added to 90 parts by weight of the cyanate ester resin prepolymer, stirred and mixed, and stirred at 130℃ until the acetone is completely evaporated. Then it is degassed at 123℃ for 3h, and then phase curing is performed, to obtain a modified cyanate ester resin; The phase curing is specifically as follows: 142℃ for 70min, 162℃ for 70min, 182℃ for 70min, 210℃ for 70min, and 230℃ for 70min; S2: Preparation of functional filler S2.1: 8 parts by weight of boron nitride powder is added to 100 parts by weight of ethanol, ultrasonic stirring and mixing is performed for 30min, and ultrasonic dispersion is performed for 30min, to obtain a suspension. 0.2 parts by weight of silane coupling agent KH550 is added to 10 parts by weight of 90wt% ethanol aqueous solution, stirred and mixed for 30min, then it is added to the suspension, ultrasonic stirring and mixing is performed for 3h, then it is filtered and dried and ground to obtain a coupling agent modified boron nitride; S2.2: 10 parts by weight of coupling agent modified boron nitride was added into 100 parts by weight of acetone solution, ultrasonic stirring mixed for 30 min, then 0.5 parts by weight of carboxyl-terminated hyperbranched polyester and 0.005 parts by weight of p-toluene sulfonic acid were added under magnetic stirring, stirring mixed for 50 min, then filtered, washed, dried and ground to obtain a functional filler; S3: Preparation of copper-clad plate S3.1: 1 part by weight of toluene diisocyanate trimer and 3 parts by weight of methyl nadic anhydride were mixed, then 10 parts by weight of N,N-dimethylformamide was added, and condensation reflux reaction was carried out at 200 rpm, nitrogen was introduced during the reaction, and the reaction was carried out at 92℃ for 5h, then vacuum distillation was carried out at 92℃, and then the reaction was carried out at 125℃ for 5h to obtain a toughening agent; S3.2: 60 parts by weight of bismaleimide resin and 100 parts by weight of modified cyanate ester resin were mixed uniformly, and then heated to 130℃, then 20 parts by weight of butanone, 100 parts by weight of toluene, 2 parts by weight of 2-ethyl-4-methyl imidazole, 1 part by weight of antioxidant 1076, 20 parts by weight of functional filler and 10 parts by weight of toughening agent were added, and mixed uniformly at 300 rpm to obtain a composite resin glue solution; S3.3: The glass fiber cloth was immersed in the composite resin glue solution, and after pre-impregnation, impregnation, exhaust impregnation treatment in the impregnator, it was dried to prepare a prepreg. The prepreg was stacked and combined, then a copper foil was placed on the upper surface and lower surface of the stacked and combined prepreg, and finally it was sent into a hot press to be pressed and formed under the conditions of 200℃ and 6MPa to obtain a copper-clad plate.
[0022] Comparative Example 1, compared with Example 1, the difference between Comparative Example 1 and Example 1 is that step S1.1 and step S1.3 are removed in Comparative Example 1, and the modified cyanate ester resin in step S3.2 is replaced by cyanate ester resin prepolymer, and the rest of the steps are unchanged to prepare a copper-clad plate, which is denoted as Comparative Example 1.
[0023] Comparative Example 2, compared with Example 1, the difference between Comparative Example 2 and Example 1 is that step S2 is removed in Comparative Example 2, and the functional filler in step S3.2 is replaced by boron nitride powder, and the rest of the steps are unchanged to prepare a copper-clad plate, which is denoted as Comparative Example 2.
[0024] Comparative Example 3, compared with Example 1, the difference between Comparative Example 3 and Example 1 is that the toughening agent in step S3.1 and step S3.2 is removed in Comparative Example 3, and the rest of the steps are unchanged to prepare a copper-clad plate, which is denoted as Comparative Example 3.
[0025] The dielectric constant and dielectric loss of the copper-clad plates prepared in Examples 1-3 and Comparative Example 1 were determined, and the determination results are shown in Table 1.
[0026] Table 1. Performance determination results of Examples 1-3 and Comparative Example 1
[0027] From the data in Table 1, it can be seen that after the cyanate ester resin is modified with the modifier, the dielectric constant and dielectric loss can be reduced.
[0028] The thermal conductivity and dielectric loss of the copper-clad plates prepared in Examples 1-3 and Comparative Example 2 were determined, and the determination results are shown in Table 2.
[0029] Table 2. Performance determination results of Examples 1-3 and Comparative Example 2
[0030] From the data in Table 2, it can be seen that the modified boron nitride as a functional filler can significantly improve the thermal conductivity of the copper-clad plate, and also can reduce the dielectric loss.
[0031] The impact strength and dielectric loss of Examples 1-3 and Comparative Example 3 were determined, and the determination results are shown in Table 3.
[0032] Table 3. Performance determination results of Examples 1-3 and Comparative Example 3
[0033] From the data in Table 3, it can be seen that the introduction of the toughening agent synthesized by toluene diisocyanate trimer and methyl nadic anhydride can significantly increase the impact strength of the copper-clad plate, achieve good toughening effect, and effectively reduce the dielectric loss.
[0034] Figure 2 A is the XRD pattern of the modifier, it can be seen that the modifier has long-range ordered structure of crystal form, B is the XPS high-resolution N1s spectrum, C is the pore size distribution of the modifier, and the above can prove that the successfully synthesized modifier is a covalent organic framework, which has a supermicroporous structure. The introduction of the microporous structure can reduce the dielectric constant and dielectric loss of the material.
[0035] Figure 3 The reaction formula for the synthesis of the toughening agent.
[0036] It should be understood that those skilled in the art can make improvements or changes according to the above description, and all these improvements and changes shall fall within the protection scope of the appended claims of the present application. The parts not described in detail in the specification belong to the prior art known to those skilled in the art.
Claims
1. A high-frequency and high-speed copper-clad laminate, characterized in that: include: An upper copper foil layer, a middle prepreg layer and a lower copper foil layer; The prepreg is made by impregnating glass fiber cloth in composite resin glue and curing it; The prepregs are stacked together, and then a copper foil is placed on the upper and lower surfaces of the stacked combination, and finally sent to a hot press for pressing to obtain a copper clad laminate; The composite resin glue comprises: 60-70 parts by weight of bismaleimide resin, 100-120 parts by weight of modified cyanate ester resin, 20-30 parts by weight of butanone, 100-120 parts by weight of toluene, 2-3 parts by weight of curing accelerator, 1-2 parts by weight of antioxidant, 20-30 parts by weight of functional filler and 10-15 parts by weight of toughening agent; The modified cyanate resin is prepared by modifying a cyanate resin prepolymer with a modifier prepared by reacting hexachlorocyclotriphosphazene with 3,3-dimethylbenzidine.
2. A method for preparing a high-frequency and high-speed copper-clad laminate according to claim 1, characterized in that: The steps include: S1: Preparation of modified cyanate resin; Hexachlorocyclotriphosphazene and 3,3-dimethylbenzidine are reacted as raw materials to prepare a modifier, and then dicyanatophenylpropane is mixed with epoxy resin to prepare a cyanate resin prepolymer, and the cyanate resin prepolymer is modified by the modifier to prepare a modified cyanate resin; S2: Preparation of functional fillers; Boron nitride powder was first modified with silane coupling agent KH550, and then modified with carboxyl-terminated hyperbranched polyester to prepare a functional filler. S3: Preparation of copper clad laminate; A toughening agent is synthesized by toluene diisocyanate trimer and methyl nadic anhydride, and then the raw materials are mixed to prepare a composite resin adhesive. Glass fiber cloth is immersed in the composite resin adhesive to prepare a semi-cured sheet. The semi-cured sheet and copper foil are stacked and combined, and pressed into shape to obtain a copper clad laminate.
3. The method for preparing a high-frequency and high-speed copper-clad laminate according to claim 2, wherein: Step S1: Preparation of modified cyanate ester resin, specifically comprising the following steps: S1.1: Add 2-3 parts by weight of hexachlorocyclotriphosphazene and 6-10 parts by weight of 3,3-dimethylbenzidine to 50-60 parts by weight of N,N-dimethylformamide, and stir for 20-30 minutes to obtain a mixed solution. Place the mixed solution in a reaction kettle, seal it, and transfer it to a forced air oven at 90-95°C for constant temperature heating to react for 24-28 hours. After the reaction is completed, filter, and wash the precipitate alternately with deionized water and acetone 3-5 times. Dry the washed precipitate to obtain a modifier. S1.2: Mix 50-60 parts by weight of dicyanatophenylpropane and 5-6 parts by weight of epoxy resin, stirring at 160-163°C and 120-150 rpm until no crystals remain, to obtain a cyanate resin prepolymer; S1.3: Add 10-12 parts by weight of the modifier to 10-12 parts by weight of acetone, ultrasonically disperse for 1-2 hours, then add to 90-100 parts by weight of the cyanate ester resin prepolymer, stir and mix, and stir at 120-130°C until the acetone is completely evaporated. Then degas at 120-123°C for 2-3 hours, and then perform staged curing to obtain a modified cyanate ester resin.
4. The method for preparing a high-frequency and high-speed copper-clad laminate according to claim 3, wherein: The staged curing in step S1.3 is specifically as follows: curing at 140-142°C for 60-70 min, curing at 160-162°C for 60-70 min, curing at 180-182°C for 60-70 min, curing at 200-210°C for 60-70 min, and curing at 220-230°C for 60-70 min.
5. The method for preparing a high-frequency and high-speed copper-clad laminate according to claim 3, wherein: Step S2: Preparation of functional filler, specifically comprising the following steps: S2.1: Add 8-9 parts by weight of boron nitride powder to 100-120 parts by weight of ethanol, mix with ultrasonic stirring for 20-30 minutes, and disperse with ultrasonic stirring for 20-30 minutes to obtain a suspension. Add 0.2-0.3 parts by weight of silane coupling agent KH550 to 10-12 parts by weight of 90-95wt% ethanol aqueous solution, mix with stirring for 20-30 minutes, then add to the suspension, mix with ultrasonic stirring for 2-3 hours, filter, dry and grind to obtain coupling agent-modified boron nitride; S2.2: Add 10-12 parts by weight of coupling agent-modified boron nitride to 100-120 parts by weight of acetone solution, mix with ultrasonic stirring for 20-30 minutes, then add 0.5-0.8 parts by weight of end-carboxyl hyperbranched polyester and 0.005-0.008 parts by weight of p-toluenesulfonic acid under magnetic stirring, stir and mix for 40-50 minutes, then filter, wash, dry and grind to obtain a functional filler.
6. The method for preparing a high-frequency and high-speed copper-clad laminate according to claim 5, wherein: Step S3: Preparation of copper clad laminate, specifically comprising the following steps: S3.1: 1-3 parts by weight of toluene diisocyanate trimer and 3-9 parts by weight of methyl nadic anhydride are mixed, followed by the addition of 10-12 parts by weight of N,N-dimethylformamide. The mixture is reacted at 150-200 rpm under condensation reflux, with nitrogen introduced during the reaction. The reaction is carried out at 90-92°C for 4-5 hours. After the reaction is completed, the mixture is subjected to reduced pressure distillation at 90-92°C, followed by the reaction at 120-125°C for 4-5 hours to obtain a toughening agent. S3.2: 60-70 parts by weight of bismaleimide resin and 100-120 parts by weight of modified cyanate ester resin are mixed uniformly, and the temperature is raised to 120-130°C. Then, 20-30 parts by weight of butanone, 100-120 parts by weight of toluene, 2-3 parts by weight of curing accelerator, 1-2 parts by weight of antioxidant, 20-30 parts by weight of functional filler, and 10-15 parts by weight of toughening agent are added, and the mixture is mixed uniformly at 200-300 rpm to obtain a composite resin adhesive; S3.3: Immerse the glass fiber cloth in the composite resin glue, and after pre-impregnation, impregnation, and degassing impregnation treatment in an impregnation machine, dry it to prepare a semi-cured sheet. The semi-cured sheets are stacked and combined, and then a copper foil is placed on the upper and lower surfaces of the stacked combination. Finally, it is sent to a hot press and pressed into shape at 190-200℃ and 4-6MPa to obtain a copper clad laminate.
7. The method for preparing a high-frequency and high-speed copper-clad laminate according to claim 6, wherein: In step S3.2, the curing accelerator is one of 2-methylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole.
8. The method for preparing a high-frequency and high-speed copper-clad laminate according to claim 6, wherein: In step S3.2, the antioxidant is one of antioxidant 1010, antioxidant 168, and antioxidant 1076.