A low dielectric constant high-performance copper clad laminate and its preparation method

Abstract

The present invention relates to the field of copper clad laminates, and discloses a copper clad laminate with low dielectric constant and high performance and a preparation method thereof. The specific steps are as follows: taking epoxy resin, phenolic resin, polyphenylene ether modified resin, modified nano-silica, etc. and mixing them to obtain a resin glue solution; impregnating glass fiber cloth in the resin glue solution to obtain a prepreg; taking the prepregs and laminating them and hot pressing them with copper foil; the polyphenylene ether modified resin includes epoxy resin, diallyl cyanate, and a fluorinated polyphenylene ether resin prepared by reacting polyphenylene ether, bisphenol AF, and benzoyl peroxide; the modified nano-silica is prepared by reacting allyl glycidyl ether and vinyltriethoxysilane with phenyltris(dimethylsilyl)silane, and then grafting it with a phosphorus-containing intermediate to form a modified additive, and grafting the modified additive with nano-silica. The phosphorus-containing intermediate is prepared by reacting phenylphosphoryl dichloride and eugenol. A copper clad laminate with high flame retardancy, high peel strength, and heat-resistant low dielectric constant is prepared.

Description

Technical Field

[0001] The present invention belongs to the technical field of copper clad laminates, and particularly relates to a low dielectric constant high-performance copper clad laminate and a preparation method thereof. Background Art

[0002] Copper clad laminates are mainly used for manufacturing printed circuit boards (PCBs) and are one of the basic raw materials in modern electronic manufacturing industries. In high-frequency and high-speed scenarios, PCBs particularly require small and stable dielectric constants and dielectric loss factors to ensure high signal transmission speeds and transmission efficiencies. As the most important part of PCBs, copper clad laminates are composed of matrix resins, reinforcing materials, and copper foils, and their performance directly determines the heat resistance, mechanical strength, plasticity, dielectric properties, etc. of PCBs, among which the performance of matrix resins often plays a decisive role.

[0003] With the rapid development of electronic products in the 5G high-frequency era, the requirements for electronic device circuit boards are becoming increasingly strict, and electronic devices are developing towards miniaturization, high integration, and fine structure. As one of the representative basic circuit boards in the field of electronic circuit boards, the higher the integration and complexity of copper clad laminates, the higher the requirements for the heat resistance, flame retardancy, and low dielectric constant of substrate materials to meet their stability, safety, and processability. In addition, as a signal transmission material, there should be excellent adhesion performance between its dielectric material and copper foil to prevent interlayer damage during processing.

[0004] Epoxy resins are widely used in copper clad laminates because of their high bonding strength, low curing shrinkage rate, no volatile substances, good chemical resistance, excellent comprehensive performance, and low price. FR-4 type copper clad laminates are currently the copper clad laminates with a large consumption, and the resin matrix used in them is epoxy resin. However, ordinary epoxy resins have disadvantages such as high dielectric constant and dielectric loss, poor heat resistance and dimensional stability, and low flame retardancy, which seriously restrict their development in the field of high-performance electronic applications. Summary of the Invention

[0005] To solve the deficiencies mentioned in the above background art, the purpose of the present invention is to provide a low dielectric constant high-performance copper clad laminate and a preparation method thereof. Using epoxy resin, phenolic resin, and polyphenylene ether modified resin as matrix resin materials, fiberglass cloth as a reinforcing material, and modified nano-silica as a filler, a high-performance copper clad laminate with high flame retardancy, high peel strength, and low heat-resistant dielectric constant is prepared by using impregnation and vacuum hot pressing technologies.

[0006] The purpose of the present invention can be achieved by the following technical solutions:

[0007] A preparation method of a low dielectric constant high-performance copper clad laminate, comprising the following steps:

[0008] S1. Take 40 - 70 parts of epoxy resin, 10 - 20 parts of phenolic resin, 10 - 20 parts of polyphenylene ether modified resin, 5 - 15 parts of modified nano - silica, 2 - 3 parts of curing accelerator and 30 - 50 parts of organic solvent, and mix them to obtain a resin adhesive solution;

[0009] S2. Immerse the fiberglass cloth in the resin adhesive solution, and bake it at 100 - 170 °C for 6 - 10 min to obtain a prepreg;

[0010] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot - press them at a temperature of 220 - 240 °C and a pressure of 2 - 4 MPa for 90 - 120 min to prepare a low - dielectric - constant high - performance copper - clad laminate;

[0011] The polyphenylene ether modified resin comprises the following components in parts by weight: 20 - 30 parts of epoxy resin, 15 - 25 parts of diallyl cyanate, and 50 - 70 parts of fluorinated polyphenylene ether resin; the fluorinated polyphenylene ether resin is prepared by using polyphenylene ether and bisphenol AF as raw materials, benzoyl peroxide as a free - radical initiator, through a redistribution reaction;

[0012] The modified nano - silica is prepared by grafting a modified additive onto the surface of nano - silica. The modified additive is prepared by a hydrosilylation reaction of allyl glycidyl ether and vinyltriethoxysilane with phenyltris(dimethylsilyl)silane, and then further reacting with a phosphorus - containing intermediate by hydrosilylation reaction. The phosphorus - containing intermediate is prepared by a substitution reaction of phenylphosphoryl dichloride and eugenol.

[0013] Preferably, the curing accelerator is 2 - methylimidazole; the organic solvent is toluene.

[0014] Preferably, the preparation method of the modified nano - silica comprises the following steps:

[0015] (1) Take phenylphosphoryl dichloride in a reactor, add toluene solvent, introduce nitrogen and stir at room temperature until completely dissolved, then add eugenol, mix and stir, and slowly dropwise add triethylamine, and stir at 40 - 55 °C for 2 - 4 h. After the reaction is completed, filter, wash, and dry to prepare a phosphorus - containing intermediate;

[0016] (2) Take phenyltris(dimethylsilyl)silane in a reactor, heat it to 105 - 115 °C, introduce nitrogen and keep the temperature for 20 - 30 min, then add chloroplatinic acid catalyst, and at the same time add allyl glycidyl ether and vinyltriethoxysilane, and stir at 105 - 120 °C for 3 - 5 h to prepare a modified silane coupling agent;

[0017] (3) Take the phosphorus-containing intermediate and the modified silane coupling agent in a reactor, add toluene solvent, heat up to 80-95 °C, introduce nitrogen and keep warm for 10-30 min, then add chloroplatinic acid catalyst, and stir the reaction at a constant temperature for 6-8 h. After the reaction is completed, evaporate the unreacted substances by rotary evaporation to prepare the modified additive;

[0018] (4) Take nano-silica and ultrasonically disperse it in xylene, heat up to 120-135 °C in a nitrogen atmosphere, add the modified additive and stir the reaction for 6-8 h. After the reaction is completed, filter, wash, and dry to prepare the modified nano-silica.

[0019] Preferably, in the step (1), the molar ratio of phenylphosphoryl dichloride to eugenol is 1:2-2.6.

[0020] Preferably, in the step (2), the molar ratio of phenyltris(dimethylsiloxy)silane, allyl glycidyl ether, and vinyltriethoxysilane is 1:1-1.2:1-1.2.

[0021] Preferably, in the step (3), the molar ratio of the phosphorus-containing intermediate to the modified silane coupling agent is 1:2-2.3.

[0022] Preferably, in the step (4), the mass ratio of nano-silica to the modified additive is 1:0.5-1.

[0023] Preferably, the preparation method of the polyphenylene ether modified resin includes the following steps:

[0024] A. Take polyphenylene ether and toluene in a reactor, stir and dissolve at 85-95 °C in a nitrogen atmosphere, then add bisphenol AF, continue to stir at a constant temperature for 0.5-1 h, and then add a mixed solution of benzoyl peroxide and toluene, continue to react at a constant temperature for 3-5 h. After the reaction is completed, cool to room temperature, pour the product into methanol to precipitate and filter to prepare the fluorine-containing polyphenylene ether resin;

[0025] B. Take epoxy resin, diallyl cyanate, and fluorine-containing polyphenylene ether resin in parts by weight, mix them, and stir and react at 60-80 °C for 55-70 min. After the reaction is completed, cool to room temperature to prepare the polyphenylene ether modified resin.

[0026] Preferably, in the step A, the mass ratio of polyphenylene ether, bisphenol AF, and benzoyl peroxide is 8-12:4-6:1.

[0027] A low dielectric constant and high performance copper clad laminate is made by the preparation method as described above.

[0028] The beneficial effects of the present invention:

[0029] The present invention utilizes the substitution reaction between the chlorine atom in the structure of phenylphosphoryl dichloride and the hydroxyl group in the structure of eugenol to prepare a phosphorus-containing intermediate. Meanwhile, the present invention utilizes the hydrosilylation reaction between the double bond groups in the structures of allyl glycidyl ether and vinyltriethoxysilane and phenyltris(dimethylsilyloxy)silane to prepare a modified silane coupling agent, thereby introducing epoxy groups and silicon-oxygen bonds into the structure of phenyltris(dimethylsilyloxy)silane, and further carrying out the hydrosilylation reaction between the double bond group in the structure of the phosphorus-containing intermediate and the Si-H bond not grafted in the structure of the modified silane coupling agent to prepare a modified additive. Then, the condensation reaction occurs between the silanol group in the structure of the modified additive and the hydroxyl group on the surface of nano-silica to prepare modified nano-silica, thereby combining nano-silica and the modified additive through strong chemical bonds, which is beneficial to the dispersion of nano-silica, enables the comprehensive performance of nano-silica to be fully exerted, and introduces epoxy groups that can participate in the curing reaction, which is beneficial to the completion of the crosslinking reaction, can improve the peel strength, and at the same time introduces low-polarity silicon-oxygen bonds to prepare a heat-resistant and low-dielectric resin material.

[0030] The present invention uses polyphenylene ether and bisphenol AF as raw materials and benzoyl peroxide as a radical initiator to prepare a low-molecular-weight fluorinated polyphenylene ether resin through a redistribution reaction. The polyphenylene ether resin has low water absorption, low dielectric properties, excellent dimensional stability, and excellent organic solvent resistance. The introduced fluorine-containing groups have low polarity and large free volume, which can further reduce the dielectric constant. Then, it is added to the epoxy resin system to improve the dielectric and thermal stability of the epoxy resin. The present invention uses epoxy resin, phenolic resin, and polyphenylene ether modified resin as matrix resin materials, glass fiber cloth as a reinforcing material, and modified nano-silica as a filler, and uses impregnation and vacuum hot pressing techniques to prepare a high-performance copper clad laminate with high flame retardancy, high peel strength, and heat-resistant low dielectric constant. Detailed implementation manners

[0031] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0032] Example 1 A preparation method of modified nano-silica includes the following steps:

[0033] (1) Take 3.8 g of phenylphosphoryl dichloride in a reactor, add 50 mL of toluene solvent, and stir while introducing nitrogen at room temperature until completely dissolved. Then add 6.6 g of eugenol, mix and stir, and slowly dropwise add 8 mL of triethylamine. Place it at 50 °C and stir for 4 h. After the reaction is completed, filter, wash, and dry to prepare a phosphorus-containing intermediate.

[0034] (2) Take 13.2 g of phenyltris(dimethylsiloxanyl)silane in a reactor, heat up to 110 °C, introduce nitrogen and keep the temperature for 30 min. Then add 100 μL of chloroplatinic acid catalyst, and at the same time add 4.8 g of allyl glycidyl ether and 7.6 g of vinyltriethoxysilane. Place it at 120 °C and stir for 5 h to prepare a modified silane coupling agent.

[0035] (3) Take 4.5 g of the phosphorus-containing intermediate (Mr = 450.38) and 12.7 g of the modified silane coupling agent (Mr = 635.12) in a reactor, add 50 mL of toluene solvent, heat up to 90 °C, introduce nitrogen and keep the temperature for 30 min. Then add 112 μL of chloroplatinic acid catalyst, and stir at a constant temperature for 8 h. After the reaction is completed, rotary evaporate to remove the unreacted substances to prepare a modified additive.

[0036] (4) Take 5 g of nano-silica and ultrasonically disperse it in 120 mL of xylene. Heat it up to 125 °C in a nitrogen atmosphere, add 2.5 g of the modified additive and stir for 7 h. After the reaction is completed, filter, wash, and dry to prepare modified nano-silica.

[0037] Example 2 A polyphenylene ether modified resin comprises the following components in parts by weight: 25 parts of o-cresol novolac epoxy resin, 20 parts of diallyl cyanate, and 65 parts of fluorinated polyphenylene ether resin.

[0038] The preparation method of the above polyphenylene ether modified resin comprises the following steps:

[0039] A. Take 40 g of polyphenylene ether and 160 mL of toluene in a reactor. Under a nitrogen atmosphere, place it at 90 °C and stir to dissolve. Then add 20 g of bisphenol AF, continue to stir at a constant temperature for 0.5 h. Subsequently, add a mixed solution of 4 g of benzoyl peroxide and 80 mL of toluene, and continue to react at a constant temperature for 4 h. After the reaction is completed, cool to room temperature, pour the product into methanol to precipitate and filter to prepare a fluorinated polyphenylene ether resin.

[0040] B. Take the o-cresol novolac epoxy resin, diallyl cyanate, and fluorinated polyphenylene ether resin in parts by weight and mix them. Place it at 80 °C and stir for 60 min. After the reaction is completed, cool to room temperature to prepare a polyphenylene ether modified resin.

[0041] Example 3 A preparation method of a low dielectric constant and high performance copper clad laminate comprises the following steps:

[0042] S1. Take 42 parts of o-cresol novolac epoxy resin, 10 parts of phenolic resin, 11 parts of the polyphenylene ether modified resin prepared in Example 2, 7 parts of the modified nano-silica prepared in Example 1, 2 parts of the curing accelerator 2-methylimidazole, and 38 parts of the organic solvent toluene, and mix them to obtain a resin adhesive solution;

[0043] S2. Immerse the glass fiber cloth in the resin adhesive solution, and bake it at 165 °C for 8 minutes to obtain a prepreg;

[0044] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot press at a temperature of 240 °C and a pressure of 2 MPa for 120 minutes to prepare a low dielectric constant high performance copper clad laminate.

[0045] Example 4 A method for preparing a low dielectric constant high performance copper clad laminate includes the following steps:

[0046] S1. Take 55 parts of o-cresol novolac epoxy resin, 14 parts of phenolic resin, 15 parts of the polyphenylene ether modified resin prepared in Example 2, 10 parts of the modified nano-silica prepared in Example 1, 3 parts of the curing accelerator 2-methylimidazole, and 43 parts of the organic solvent toluene, and mix them to obtain a resin adhesive solution;

[0047] S2. Immerse the glass fiber cloth in the resin adhesive solution, and bake it at 165 °C for 8 minutes to obtain a prepreg;

[0048] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot press at a temperature of 240 °C and a pressure of 2 MPa for 120 minutes to prepare a low dielectric constant high performance copper clad laminate.

[0049] Example 5 A method for preparing a low dielectric constant high performance copper clad laminate includes the following steps:

[0050] S1. Take 67 parts of o-cresol novolac epoxy resin, 18 parts of phenolic resin, 18 parts of the polyphenylene ether modified resin prepared in Example 2, 14 parts of the modified nano-silica prepared in Example 1, 3 parts of the curing accelerator 2-methylimidazole, and 48 parts of the organic solvent toluene, and mix them to obtain a resin adhesive solution;

[0051] S2. Immerse the glass fiber cloth in the resin adhesive solution, and bake it at 165 °C for 8 minutes to obtain a prepreg;

[0052] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot press at a temperature of 240 °C and a pressure of 2 MPa for 120 minutes to prepare a low dielectric constant high performance copper clad laminate.

[0053] Comparative Example 1 A method for preparing modified nano-silica includes the following steps:

[0054] (1) Take 13.2 g of phenyltris(dimethylsiloxy)silane in a reactor, heat it up to 110 °C, introduce nitrogen and keep the temperature for 30 min, then add 100 μL of chloroplatinic acid catalyst, and at the same time add 4.8 g of allyl glycidyl ether and 7.6 g of vinyltriethoxysilane, and stir and react at 120 °C for 5 h to prepare a modified silane coupling agent;

[0055] (2) Take 5 g of nano-silica and ultrasonically disperse it in 120 mL of xylene, heat it up to 125 °C in a nitrogen atmosphere, add 2.5 g of the modified silane coupling agent and stir and react for 7 h. After the reaction is completed, filter, wash, and dry to prepare modified nano-silica.

[0056] Comparative Example 2 A method for preparing modified nano-silica includes the following steps:

[0057] (1) Take 3.8 g of phenylphosphoryl dichloride in a reactor, add 50 mL of toluene solvent, introduce nitrogen and stir at room temperature until completely dissolved, then add 6.6 g of eugenol, mix and stir, and slowly dropwise add 8 mL of triethylamine, and stir and react at 50 °C for 4 h. After the reaction is completed, filter, wash, and dry to prepare a phosphorus-containing intermediate;

[0058] (2) Take 13.2 g of phenyltris(dimethylsiloxy)silane in a reactor, heat it up to 110 °C, introduce nitrogen and keep the temperature for 30 min, then add 100 μL of chloroplatinic acid catalyst, and at the same time add 7.6 g of vinyltriethoxysilane, and stir and react at 120 °C for 5 h to prepare a modified silane coupling agent;

[0059] (3) Take 4.5 g of the phosphorus-containing intermediate (Mr = 450.38) and 10.4 g of the modified silane coupling agent (Mr = 520.98) in a reactor, add 50 mL of toluene solvent, heat it up to 90 °C, introduce nitrogen and keep the temperature for 30 min, then add 112 μL of chloroplatinic acid catalyst, and stir and react at a constant temperature for 8 h. After the reaction is completed, rotary evaporate to remove the unreacted substances to prepare a modified additive;

[0060] (4) Take 5 g of nano-silica and ultrasonically disperse it in 120 mL of xylene, heat it up to 125 °C in a nitrogen atmosphere, add 2.5 g of the modified additive and stir and react for 7 h. After the reaction is completed, filter, wash, and dry to prepare modified nano-silica.

[0061] Comparative Example 3 A polyphenylene ether modified resin includes the following components in parts by weight: 25 parts of o-cresol novolac epoxy resin, 20 parts of diallyl cyanate, and 65 parts of polyphenylene ether resin;

[0062] The preparation method of the above polyphenylene ether modified resin includes the following steps:

[0063] A. Take 40 g of polyphenylene ether and 160 mL of toluene in a reactor. Under a nitrogen atmosphere, place it at 90 °C and stir to dissolve. Then add 20 g of bisphenol A, continue stirring at a constant temperature for 0.5 h. Subsequently, add a mixed solution of 4 g of benzoyl peroxide and 80 mL of toluene, continue the reaction at a constant temperature for 4 h. After the reaction is completed, cool it to room temperature, pour the product into methanol to precipitate and filter it by suction to prepare polyphenylene ether resin;

[0064] B. Take a mixture of weight parts of o-cresol novolac epoxy resin, diallyl cyanate ester, and polyphenylene ether resin, place it at 80 °C and stir to react for 60 min. After the reaction is completed, cool it to room temperature to prepare polyphenylene ether modified resin.

[0065] Comparative Example 4 A method for preparing a low dielectric constant and high performance copper clad laminate, comprising the following steps:

[0066] S1. Take 67 parts of o-cresol novolac epoxy resin, 18 parts of phenolic resin, 18 parts of the polyphenylene ether modified resin prepared in Example 2, 14 parts of the modified nano-silica prepared in Comparative Example 1, 3 parts of the curing accelerator 2-methylimidazole, and 48 parts of the organic solvent toluene and mix them to obtain a resin adhesive solution;

[0067] S2. Immerse the glass fiber cloth in the resin adhesive solution, place it at 165 °C and bake for 8 min to obtain a prepreg;

[0068] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot press at a temperature of 240 °C and a pressure of 2 MPa for 120 min to prepare a low dielectric constant and high performance copper clad laminate.

[0069] Comparative Example 5 A method for preparing a low dielectric constant and high performance copper clad laminate, comprising the following steps:

[0070] S1. Take 67 parts of o-cresol novolac epoxy resin, 18 parts of phenolic resin, 18 parts of the polyphenylene ether modified resin prepared in Example 2, 14 parts of the modified nano-silica prepared in Comparative Example 2, 3 parts of the curing accelerator 2-methylimidazole, and 48 parts of the organic solvent toluene and mix them to obtain a resin adhesive solution;

[0071] S2. Immerse the glass fiber cloth in the resin adhesive solution, place it at 165 °C and bake for 8 min to obtain a prepreg;

[0072] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot press at a temperature of 240 °C and a pressure of 2 MPa for 120 min to prepare a low dielectric constant and high performance copper clad laminate.

[0073] Comparative Example 6 A method for preparing a low dielectric constant and high performance copper clad laminate, comprising the following steps:

[0074] S1. Take 67 parts of o-cresol novolac epoxy resin, 18 parts of phenolic resin, 18 parts of the polyphenylene ether modified resin prepared in Example 2, 14 parts of nano-silica, 3 parts of the curing accelerator 2-methylimidazole, and 48 parts of the organic solvent toluene, and mix them to obtain a resin adhesive;

[0075] S2. Immerse the fiberglass cloth in the resin adhesive, and bake it at 165 °C for 8 minutes to obtain a prepreg;

[0076] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot press them at a temperature of 240 °C and a pressure of 2 MPa for 120 minutes to prepare a low dielectric constant and high performance copper clad laminate.

[0077] Comparative Example 7 A method for preparing a low dielectric constant and high performance copper clad laminate, comprising the following steps:

[0078] S1. Take 67 parts of o-cresol novolac epoxy resin, 18 parts of phenolic resin, 18 parts of the polyphenylene ether modified resin prepared in Comparative Example 3, 14 parts of the modified nano-silica prepared in Example 1, 3 parts of the curing accelerator 2-methylimidazole, and 48 parts of the organic solvent toluene, and mix them to obtain a resin adhesive;

[0079] S2. Immerse the fiberglass cloth in the resin adhesive, and bake it at 165 °C for 8 minutes to obtain a prepreg;

[0080] S3. Take the prepregs and stack them, cover each side with a copper foil, and hot press them at a temperature of 240 °C and a pressure of 2 MPa for 120 minutes to prepare a low dielectric constant and high performance copper clad laminate.

[0081] Performance testing

[0082] Perform performance testing on the copper clad laminates prepared in Examples 3-5 and Comparative Examples 4-7:

[0083] (1) Dielectric constant and dissipation factor test: According to the IPC-TM-650 2.5.5 standard, use a microwave network analyzer to test the dielectric constant and dielectric loss of the sample, and the test frequency is 10 GHz. The data results are shown in Table 1.

[0084] (2) Peel strength test: According to the IPC-TM-650 2.4.8 standard, use a copper foil peel strength tester to test, and the data results are shown in Table 1.

[0085] (3) Heat resistance test: Use a thermogravimetric analyzer to test. The whole test process is carried out under nitrogen protection, the heating rate is 10 °C / min, and the temperature is 30-800 °C. The data results are shown in Table 1.

[0086] (4)Flame retardancy test: The vertical burning performance test was carried out in accordance with the UL94 standard (ASTM D3801), and the data results are shown in Table 1.

[0087]

[0088] It can be seen from the data in Table 1 that the copper clad laminates prepared in Examples 3-5 of the present invention have low dielectric constant and loss, high peel strength, and excellent heat resistance and flame retardancy. Among them, the modified nano-silica component added in Comparative Example 4 did not introduce a phosphorus-containing intermediate, and its measured heat resistance and flame retardancy were lower than those in Examples 3-5. In Comparative Example 5, the modified nano-silica component added did not introduce allyl glycidyl ether, and its measured peel strength was lower than that in Examples 3-5. In Comparative Example 6, the nano-silica was not modified, and its measured peel strength, heat resistance and flame retardancy were significantly lower than those in Examples 3-5, and the dielectric constant was larger than that in Examples 3-5. The reason is that phosphorus element, epoxy group and silicon-oxygen bond were not introduced on the surface of nano-silica. In Comparative Example 7, the polyphenylene ether modified resin component added did not introduce fluorine element, and its measured dielectric constant was larger than that in Examples 3-5, indicating that the grafting of fluorine element can reduce the dielectric constant to a certain extent.

[0089] In the description of this specification, the descriptions referring to the terms "one embodiment", "example", "specific example", etc. mean that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in a suitable manner in any one or more embodiments or examples.

[0090] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art of this industry should understand that the present invention is not limited by the above embodiments. The above embodiments and the descriptions in the specification only illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed.

Claims

1. A preparation method of a low dielectric constant and high performance copper clad laminate, characterized in that, It includes the following steps: S1. Take 40 - 70 parts of epoxy resin, 10 - 20 parts of phenolic resin, 10 - 20 parts of polyphenylene ether modified resin, 5 - 15 parts of modified nano - silica, 2 - 3 parts of curing accelerator and 30 - 50 parts of organic solvent, and mix them to obtain a resin adhesive solution; S2. Immerse the fiberglass cloth in the resin adhesive solution, and bake it at 100 - 170 °C for 6 - 10 min to obtain a prepreg; S3. Take the prepregs and stack them, cover each side with a copper foil, and hot - press them at a temperature of 220 - 240 °C and a pressure of 2 - 4 MPa for 90 - 120 min to prepare a low - dielectric - constant high - performance copper - clad laminate; The polyphenylene ether modified resin includes the following components in parts by weight: 20 - 30 parts of epoxy resin, 15 - 25 parts of diallyl cyanate, and 50 - 70 parts of fluorinated polyphenylene ether resin; the fluorinated polyphenylene ether resin is prepared by using polyphenylene ether and bisphenol AF as raw materials and benzoyl peroxide as a free - radical initiator through a redistribution reaction; The modified nano - silica is prepared by grafting a modified additive onto the surface of nano - silica. The modified additive is prepared by subjecting allyl glycidyl ether and vinyltriethoxysilane to a hydrosilylation reaction with phenyltris(dimethylsilyl)silane, and then further subjecting it to a hydrosilylation reaction with a phosphorus - containing intermediate. The phosphorus - containing intermediate is prepared by subjecting phenylphosphoryl dichloride and eugenol to a substitution reaction; 2. The preparation method of the low dielectric constant and high performance copper clad laminate according to claim 1, characterized in that, The curing accelerator is 2 - methylimidazole; the organic solvent is toluene.

3. The preparation method of the low dielectric constant and high performance copper clad laminate according to claim 1, wherein, The preparation method of the modified nano - silica includes the following steps: (1) Take phenylphosphoryl dichloride in a reactor, add toluene solvent, introduce nitrogen and stir at room temperature until completely dissolved, then add eugenol, mix and stir, and slowly dropwise add triethylamine. Stir and react at 40 - 55 °C for 2 - 4 h. After the reaction is completed, filter, wash, and dry to prepare a phosphorus - containing intermediate; (2) Take phenyltris(dimethylsilyl)silane in a reactor, heat up to 105 - 115 °C, introduce nitrogen and keep warm for 20 - 30 min, then add chloroplatinic acid catalyst, and at the same time add allyl glycidyl ether and vinyltriethoxysilane. Stir and react at 105 - 120 °C for 3 - 5 h to prepare a modified silane coupling agent; (3) Take the phosphorus - containing intermediate and the modified silane coupling agent in a reactor, add toluene solvent, heat up to 80 - 95 °C, introduce nitrogen and keep warm for 10 - 30 min, then add chloroplatinic acid catalyst, and stir and react at a constant temperature for 6 - 8 h. After the reaction is completed, rotary evaporate to remove the unreacted substances to prepare a modified additive; (4) Take nano - silica, ultrasonically disperse it in xylene, heat up to 120 - 135 °C in a nitrogen atmosphere, add the modified additive and stir and react for 6 - 8 h. After the reaction is completed, filter, wash, and dry to prepare the modified nano - silica.

4. The preparation method of the low dielectric constant and high performance copper clad laminate according to claim 3, characterized in that, In step (1), the molar ratio of phenylphosphoryl dichloride to eugenol is 1:2 - 2.

6.

5. The preparation method of the low dielectric constant and high performance copper clad laminate according to claim 3, characterized in that, In step (2), the molar ratio of phenyltris(dimethylsilyl)silane, allyl glycidyl ether and vinyltriethoxysilane is 1:1 - 1.2:1 - 1.

2.

6. The preparation method of the low dielectric constant and high performance copper clad laminate according to claim 3, characterized in that, In the step (3), the molar ratio of the phosphorus-containing intermediate to the modified silane coupling agent is 1:2 to 2.

3.

7. The preparation method of the low dielectric constant high-performance copper clad laminate according to claim 3, characterized in that, In the step (4), the mass ratio of the nano-silica to the modified additive is 1:0.5 to 1.

8. The preparation method of the low dielectric constant high performance copper clad laminate according to claim 1, characterized in that, The preparation method of the polyphenylene ether modified resin comprises the following steps: A. Take polyphenylene ether and toluene in a reactor, stir and dissolve them at 85-95°C in a nitrogen atmosphere, then add bisphenol AF, continue stirring at a constant temperature for 0.5-1 h, then add a mixed solution of benzoyl peroxide and toluene, continue reacting at a constant temperature for 3-5 h, cool to room temperature after the reaction is completed, pour the product into methanol for precipitation and filtration to prepare a fluorine-containing polyphenylene ether resin; B. Take epoxy resin, diallyl cyanate and fluorine-containing polyphenylene ether resin in parts by weight, mix them, stir and react at 60-80°C for 55-70 min, and cool to room temperature after the reaction is completed to prepare a polyphenylene ether modified resin.

9. The preparation method of the low dielectric constant and high performance copper clad laminate according to claim 8, wherein, In the step A, the mass ratio of the polyphenylene ether, bisphenol AF and benzoyl peroxide is 8-12:4-6:

1.

10. A low dielectric constant and high performance copper clad laminate, characterized in that, It is made by the preparation method described in claim 1.

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