A method for manufacturing a high-performance cyanate ester resin glass cloth adhesive sheet and a copper-clad plate

Abstract

The application discloses a kind of high-performance cyanate ester resin glass cloth bonding sheet and the manufacturing method of copper-clad plate, comprising the following steps: a, using dicyclopentadiene cyanate ester resin and the middle molecular weight polyphenyl ether resin containing nitrile group at both ends of molecule as main material to prepare resin solution;B, the qualified prepreg is formed by coating and drying the resin solution prepared in step a on glass cloth and waiting for use;C, when making copper-clad plate, the qualified prepreg obtained in step b is stacked according to the required quantity, and electrolytic copper foil is covered on the upper and lower surfaces, and stainless steel plates are used to fix and put into the press at the set temperature and pressure for curing. The problems of existing cyanate ester copper-clad plate composite, such as high rigidity, poor toughness, large white edge during circuit board processing and cutting, and high water absorption, are solved.

Description

Technical Field

[0001] This invention relates to the field of copper clad laminate manufacturing, and in particular to a high-performance cyanate ester resin glass cloth bonding sheet and a method for manufacturing copper clad laminate. Background Technology

[0002] Copper clad laminate is an electronic composite material. It is made by coating a thermosetting polymer mixed resin onto a reinforcing material (usually glass fiber or carbon fiber), baking it to form a prepreg. The prepreg is then mixed in different quantities and molded under high temperature and pressure to form a composite material. The composite material can be flat or made into different three-dimensional shapes like fiberglass.

[0003] Currently, cyanate ester resin copper clad laminates and prepregs refer to products with cyanate ester resin as the main resin, including bisphenol A, E, F, and dicyclopentadiene cyanate ester resins. Thermoplastic polymers or rubbers are used as toughening materials, such as polyether ketone resin, polyether ether ketone resin, SBS rubber, and other high-temperature resistant thermoplastic resins, to improve the rigidity of the resin and reduce the white edge delamination phenomenon of the composite material during shearing. Organometallic compounds are used as catalysts, and hydroxyl-containing compounds are used as co-catalysts. After the resin is mixed, it is coated on the surface of glass fiber or carbon fiber to form a semi-cured composite material, which is then subjected to high temperature and high pressure to form a thermosetting composite material.

[0004] This type of prepreg, formed by coating a mixed resin onto fiberglass cloth and drying it, can be used in high-speed signal transmission engineering structures, such as radomes and missile structural components. Composite materials belong to the fields of circuit board processing and fiberglass structure processing, while copper-clad laminates produced using this type of prepreg are used in circuit boards for high-speed signal transmission.

[0005] Existing technological shortcomings:

[0006] ① Currently, composite materials based on cyanate ester resin systems, such as copper-clad laminates, sometimes lack toughening and sometimes use high-temperature resistant thermoplastic elastomers to toughen and form a semi-interpenetrating network (IPN) structure. Due to limitations in the amount of polymeric elastomer added, copper-clad laminates exhibit significant white edges (microscopically, this indicates delamination of a certain length) during circuit board processing. This is because the composite material lacks sufficient toughness and is too rigid. Toughening with polymeric materials requires a certain mass ratio of the toughening resin in the composite material to form a continuous phase. However, due to the large molecular weight of these polymers, when added at a mass ratio of 10% or higher, the high viscosity of the mixed resin hinders the penetration of cyanate ester resin into the glass fibers during impregnation (smaller molecular weights result in stronger resin penetration). This reduces the resin's penetration into the glass fibers, thus limiting the amount of toughening resin added and leading to insufficient toughness in the composite material. This results in significant white edges during circuit board processing.

[0007] ② The composite material has high water absorption. The molecular structure of cyanate resin contains a large number of nitrogen atoms and carbon-oxygen double bonds. Both of these structures have strong water absorption. Therefore, the water absorption of copper clad laminates based on cyanate resin is above 0.25% (tested according to IPC standards), and the highest can even reach 0.5%. High water absorption will lead to a significant increase in the dielectric loss and dielectric constant of cyanate resin composite materials, which will seriously affect the stability of signal transmission. High water absorption is a major weakness of cyanate resin composite materials. Summary of the Invention

[0008] The purpose of this invention is to provide a method for manufacturing high-performance cyanate ester resin glass cloth bonding sheets and copper-clad laminates, thereby solving the problems of poor rigidity and toughness of existing cyanate ester copper-clad laminate composite materials, large white edges at the cut edges during circuit board processing and cutting, and high water absorption.

[0009] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0010] A method for manufacturing an adhesive sheet and a high-performance cyanate ester copper-clad laminate includes the following steps: a) preparing a resin solution using dicyclopentadiene cyanate ester resin and medium molecular weight polyphenylene ether resin containing nitrile groups at both ends of the molecule as the main materials; b) coating the resin solution prepared in step a onto glass cloth and drying it to form a qualified prepreg for later use; c) when manufacturing the copper-clad laminate, stacking the qualified prepreg obtained in step b in the required quantity, covering the top and bottom surfaces with electrolytic copper foil, fixing the top and bottom with stainless steel plates, and placing it in a press for curing at a set temperature and pressure.

[0011] This solution mainly focuses on improving the toughness of cyanate ester copper-clad laminate composites, reducing the water absorption requirements of the composites, and ensuring the low dielectric properties of the cyanate ester copper-clad laminate. This invention improves the toughening of cyanate ester copper-clad laminate composites by using two materials. One is a medium-molecular-weight polyphenylene ether resin with nitrile groups at both ends of the cyanate ester resin system. The medium-molecular-weight polyphenylene ether resin can both toughen and react with the nitrile groups of the cyanate ester resin, while not affecting the impregnation of the resin system and glass fibers. This increases the mass ratio of the toughening material in the composite material, thereby improving the problem of large white edges when cutting cyanate ester copper-clad laminate composites. The other material is high-molecular-weight nitrile rubber. Rubber has the best toughening effect among all polymer materials due to its elasticity. Nitrile rubber contains the same nitrile groups as the cyanate ester resin, which can react with the main resin, rather than the currently widely used thermoplastic elastomers and cyanate ester resins physically mixing during curing to form a semi-interpenetrating network. The reactive toughening material can form an integrated structure with the main resin, significantly increasing the toughness of the composite material. This combination of two high- and medium-molecular-weight toughening materials effectively solves the "white edge" problem of copper-clad laminate composites when cutting. Meanwhile, since the introduced medium molecular weight polyphenylene ether resin has very low water absorption, it can effectively reduce the water absorption of the composite material. According to the addition ratio of this patent, the water absorption of the composite material can be reduced to below 0.15%, while maintaining the high Tg, low expansion coefficient, and low dielectric properties of cyanate ester resin. The glass cloth can be selected from models such as 1080, 2116, 106, 104, and 7628.

[0012] As a further preferred embodiment of the present invention, the preparation of the resin solution using dicyclopentadiene cyanate resin and medium molecular weight polyphenylene ether resin in step a includes the following steps: a1. Prepare a medium molecular weight polyphenylene ether resin solution with nitrile groups at both ends of the molecule for later use, and prepare a high molecular weight nitrile rubber solution for later use; a2. Dissolve one of the naphthenic acid compounds of zinc, manganese or copper in butanone, then add a compound containing phenolic hydroxyl groups and continue stirring. After stirring, add 70% of dicyclopentadiene cyanate resin to obtain solution x; a3. Add the medium molecular weight polyphenylene ether resin solution with nitrile groups at both ends of the molecule and the high molecular weight nitrile rubber solution prepared in step a1 to solution x, then add flame retardant and silane coupling agent and stir; a4. After stirring, add spherical silica filler, then add cyclohexanone solvent to adjust the solid content of the resin to 70-73%, and then stir for 3 hours to obtain the final solution; all the above operations are carried out at room temperature.

[0013] Cyanate ester resins are characterized by a symmetrical molecular structure after curing, forming numerous rigid six-membered ring structures. This results in excellent heat resistance and dielectric properties, with a glass transition temperature reaching approximately 270℃. Furthermore, due to their highly symmetrical molecular structure, they exhibit a low dielectric constant, particularly low dielectric loss (around 3.0, 0.007). However, they have relatively high water absorption (around 0.3%), making them one of the ideal high-frequency dielectric materials. Therefore, their composites are frequently used in environments with high dielectric performance requirements and harsh operating conditions. Secondly, medium-molecular-weight polyphenylene ether resins also possess good heat resistance, low water absorption, and extremely low dielectric constant and dielectric loss (around 0.08%, 2.7, 0.005). These properties effectively improve the toughness and water absorption of cured cyanate ester resins.

[0014] Spherical silica exhibits extremely low dielectric loss, reaching 0.0002, making it one of the inorganic materials with the lowest dielectric loss currently available. It can effectively reduce the dielectric loss of composite materials. Composite materials used in the electronics field require flame retardancy and must meet UL 94-V0 standards; the purpose of adding flame retardants is to achieve these performance requirements. Coupling agents can improve the interfacial compatibility between organic and inorganic materials. Treating inorganic fillers with hydrophobic organosilicon coupling agents can effectively reduce the water absorption of inorganic fillers, allowing organic polymer materials to uniformly coat the surface of inorganic fillers, reducing porosity, and improving electrical and physical properties.

[0015] Toughening materials improve the toughness of composite materials. Materials that are too rigid will experience crack propagation during cutting, leading to micro-delamination and large white edges in the insulation material. Therefore, adding highly tough nitrile rubber effectively improves the rigidity of the material, achieving the goal of toughening. When these materials are combined with a curing agent and a curing accelerator, they can be cured under high temperature and pressure into a highly adhesive solid material with excellent dielectric properties, heat resistance, and water absorption. Furthermore, it outperforms similar foreign materials in terms of water absorption and resistance to white edges after cutting, making it a complete replacement for foreign products.

[0016] As a further preferred embodiment of the present invention, the medium molecular weight polyphenylene ether resin solution containing nitrile groups at both ends of the molecule in step a1 is prepared by dissolving a polyphenylene ether resin with a molecular weight of 2000 containing nitrile groups at both ends of the molecule in cyclohexanone solvent. The mass fraction of the medium molecular weight polyphenylene ether resin containing nitrile groups at both ends of the molecule is 50-60 parts, and the mass fraction of the cyclohexanone solvent is 10-25 parts.

[0017] As a further preferred embodiment of the present invention, the high molecular weight nitrile rubber solution in step a1 is prepared by dissolving high molecular weight nitrile rubber in methyl ethyl ketone (MEK) solvent. The mass fraction of the high molecular weight nitrile rubber is 15-30 parts, and the concentration of the prepared solution is 15%. The high molecular weight nitrile rubber contains nitrile rubber with a molecular weight of 18,000-21,000 and a nitrile group content of 10-18%.

[0018] The addition of such materials can improve the toughness of composite materials and reduce delamination of copper-clad laminates during shearing.

[0019] As a further preferred embodiment of the present invention, in step a2, the mass fraction of the zinc, manganese, or copper naphthenic acid compound is 1-3 parts, the mass fraction of butanone is 30-32 parts, and the butanone solution requires stirring for 30-60 minutes. The mass fraction of the added phenolic hydroxyl-containing compound is 5-10 parts, and the stirring time is continued for 60 minutes. The mass fraction of the added 70% dicyclopentadiene cyanate resin is 150-200 parts. Organic compounds of manganese, zinc, and copper are selected as curing accelerators for the main resin, and compounds containing phenolic hydroxyl groups are used as curing agents. These compounds include tetrabromobisphenol A, allyl bisphenol A, phenol, etc. The dicyclopentadiene cyanate resin uses domestically produced raw materials, generally a butanone solution, and the materials are widely available.

[0020] As a further preferred embodiment of the present invention, the dicyclopentadiene cyanate resin in step a2 comprises a monomeric resin or a dicyclopentadiene cyanate polymerized at less than 30%.

[0021] As a further preferred embodiment of the present invention, in step a3, the mass fractions of the flame retardant and the silane coupling agent added are 50-80 parts and 2-8 parts, respectively, and the stirring time is 60 minutes. The flame retardant is one or both of bromine-containing or phosphorus-containing flame retardants. The flame retardant is required to have a thermal decomposition temperature above 350°C. If a bromine-containing flame retardant is selected, it should be a flame retardant with good thermal shock resistance and a bromine content of more than 66%. If a phosphorus-containing flame retardant is selected, it should be a flame retardant with good thermal shock resistance and a phosphorus content of more than 14%. The flame retardant can be selected from decabromodiphenyl ethane, brominated polystyrene, tetrabromostyrene, diethylaluminum hypophosphite, DOPO, and hexaphenoxycyclotriphosphazene. The coupling agent includes KH-550 and KH-570.

[0022] As a further preferred embodiment of the present invention, the mass fraction of spherical silica filler added in step a4 is 250-400 parts.

[0023] The addition of spherical silica can effectively reduce the dielectric loss and thermal expansion coefficient of composite materials, increase the stability of high-speed signal transmission, and also reduce costs. After being treated with coupling agents, spherical silica has very low water absorption, which can effectively reduce the water absorption of copper clad laminate composite materials. There are many professional suppliers in China that can provide this product.

[0024] As a further preferred embodiment of the present invention, when forming a qualified prepreg in step b, the resin content is controlled at 54%, the flow rate at 10-16%, and the resin gelation time of the prepreg is controlled at 120-160 seconds.

[0025] As a further preferred embodiment of the present invention, in step c, the maximum temperature and pressure of the press are set to 250°C and 40 kg / cm2, respectively, and the curing time is 2 hours.

[0026] Compared with the prior art, the present invention can achieve at least one of the following beneficial effects:

[0027] 1. This solution primarily focuses on improving the toughness of cyanate ester resin-coated copper clad laminate composites (solving the white edge phenomenon during PCB cutting) and reducing the water absorption requirements of the composite material, while ensuring the lowest possible dielectric loss. Therefore, a combination of medium-molecular-weight polyphenylene ether resin with nitrile-terminated groups and high-molecular-weight nitrile rubber is introduced into the cyanate ester resin system for toughening. The medium-molecular-weight polyphenylene ether resin provides toughening without affecting the resin system or the impregnation of glass fibers, thus improving the toughness of the composite material. Furthermore, the high-molecular-weight nitrile rubber possesses elasticity and exhibits the best toughening effect among all polymer materials. Okay, nitrile rubber contains the same nitrile groups as cyanate ester resin, which can react with the main resin and significantly increase the toughness of the composite material. The combination of two high and medium molecular weight toughness materials can effectively solve the delamination problem of copper clad laminate during cutting. In addition, since the introduced medium molecular weight nitrile-terminated polyphenylene ether resin has very low water absorption, it can effectively reduce the water absorption of the composite material. Secondly, polyphenylene ether resin also has good dielectric properties. According to the addition ratio of this patent, the water absorption of the composite material can be reduced to below 0.15%, while maintaining the high Tg, low expansion coefficient, and low dielectric properties of cyanate ester resin copper clad laminate.

[0028] 2. Cyanate ester resins are characterized by a symmetrical molecular structure after curing, forming numerous rigid six-membered ring structures. This results in excellent heat resistance and dielectric properties, with a glass transition temperature reaching approximately 270℃. Furthermore, due to its highly symmetrical molecular structure, it has a low dielectric constant, especially a very low dielectric loss (around 3.0, 0.007). However, it has relatively high water absorption (around 0.3%), making it an ideal high-frequency dielectric material. Therefore, its composites are more commonly used in environments with high dielectric performance requirements and harsh operating conditions. Secondly, medium-molecular-weight polyphenylene ether resins also possess good heat resistance, low water absorption, extremely low dielectric constant and dielectric loss, and can react with the host resin. Polyphenylene ether resin has a water absorption of approximately 0.08%, a dielectric constant of 2.7, and a dielectric loss of 0.005, effectively improving the toughness and water absorption of cyanate ester resin composites.

[0029] 3. Spherical silica exhibits very low dielectric loss, reaching 0.0002, making it one of the inorganic materials with the lowest dielectric loss currently available. It can effectively reduce the dielectric loss of composite materials. Composite materials used in the electronics field require flame retardancy and must meet the UL 94-V0 standard; the purpose of adding flame retardants is to achieve this performance requirement. Coupling agents can improve the interfacial compatibility between organic and inorganic materials. Spherical silica treated with coupling agents has very low water absorption, effectively reducing the water absorption of copper-clad laminate composites. It also allows organic polymer materials to uniformly coat the surface of inorganic fillers, reducing voids and improving electrical and physical properties.

[0030] 4. Toughening materials improve the toughness of composite materials. Composite materials with excessive rigidity are prone to crack propagation and delamination during cutting. Therefore, the addition of medium-molecular-weight polyphenylene ether and high-toughness nitrile rubber effectively improves the material's rigidity. When these materials are combined with a curing agent and curing accelerator, they can be cured under high temperature and pressure into a highly adhesive solid material with excellent dielectric properties, heat resistance, and water absorption. Furthermore, it outperforms similar foreign materials in terms of water absorption and resistance to white edges after cutting, making it a complete replacement for foreign products. Detailed Implementation

[0031] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The embodiments of the present invention described and shown herein can generally be designed with different material weight ratios.

[0032] Therefore, the following detailed description of the embodiments of the invention provided in the appendix is ​​not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the invention without inventive effort are within the scope of protection of the invention.

[0033] It should be noted that, unless otherwise specified, the embodiments and features described in this invention can be combined with each other. Specific Implementation Example 1:

[0035] A method for manufacturing an adhesive sheet and a high-performance cyanate ester copper-clad laminate includes the following steps: a) preparing a resin solution using dicyclopentadiene cyanate ester resin and medium molecular weight polyphenylene ether resin containing nitrile groups at both ends of the molecule as the main materials; b) coating the resin solution prepared in step a onto glass cloth and drying it to form a qualified prepreg for later use; c) when manufacturing the copper-clad laminate, stacking the qualified prepreg obtained in step b in the required quantity, covering the top and bottom surfaces with electrolytic copper foil, fixing the top and bottom with stainless steel plates, and placing it in a press for curing at a set temperature and pressure.

[0036] This solution primarily focuses on improving the toughness of cyanate ester copper-clad laminates to address delamination during cutting and reducing the water absorption requirements of the composite material, while ensuring the lowest possible dielectric loss. Medium molecular weight polyphenylene ether resin is introduced into the cyanate ester resin system. Polyphenylene ether resin has low dielectric loss characteristics, which can play a toughening role without affecting the impregnation of the resin system and glass fiber, thus improving the heat resistance of the composite material. Furthermore, the introduced medium molecular weight polyphenylene ether resin has very low water absorption, effectively reducing the water absorption of the composite material. Secondly, polyphenylene ether resin also has excellent dielectric properties. According to the addition ratio of this patent, the water absorption of the composite material can be reduced to below 0.15%, while maintaining the high Tg, low expansion coefficient, and low dielectric properties of the cyanate ester resin. Glass cloth of grades 1080, 2116, 106, 104, and 7628 can be selected. Specific Implementation Example 2:

[0038] The preparation of the resin solution using dicyclopentadiene cyanate resin and medium molecular weight polyphenylene ether resin in step a includes the following steps: a1. Prepare a medium molecular weight polyphenylene ether resin solution with nitrile groups at both ends of the molecule, and prepare a high molecular weight nitrile rubber solution; a2. Dissolve one of the naphthenic acid compounds of zinc, manganese or copper in butanone, then add a compound containing phenolic hydroxyl groups and continue stirring. After stirring, add 70% dicyclopentadiene cyanate resin to obtain solution x; a3. Add the medium molecular weight polyphenylene ether resin solution with nitrile groups at both ends of the molecule and the high molecular weight nitrile rubber solution prepared in step a1 to solution x, then add flame retardant and silane coupling agent and stir; a4. After stirring, add spherical silica filler, then add cyclohexanone solvent to adjust the solid content of the resin to 70-73%, and stir for 3 hours to obtain the final solution; all the above operations are carried out at room temperature.

[0039] Dicyclopentadiene cyanate resins, after curing, exhibit a symmetrical molecular structure and form numerous rigid six-membered ring structures. This results in excellent heat resistance and dielectric properties, with a glass transition temperature reaching approximately 270℃. Due to its highly symmetrical molecular structure, it possesses a very low dielectric constant, particularly a dielectric loss of 3.0 and 0.007. However, it has relatively high water absorption (around 0.8%), making it an ideal high-frequency dielectric material. Therefore, its composites are frequently used in environments with high dielectric performance requirements and harsh operating conditions. Medium-molecular-weight polyphenylene ether resins containing nitrile-terminated groups also possess good heat resistance, low water absorption, and extremely low dielectric constant and dielectric loss. Polyphenylene ether resin has a water absorption of approximately 0.05%, a dielectric constant of 2.7, and a dielectric loss of 0.005, making it another ideal high-frequency dielectric material.

[0040] Spherical silica exhibits extremely low dielectric loss, reaching 0.0002, making it one of the inorganic materials with the lowest dielectric loss currently available. It can effectively reduce the dielectric loss of composite materials. Composite materials used in the electronics field require flame retardancy and must meet UL 94-V0 standards; the purpose of adding flame retardants is to achieve these performance requirements. Coupling agents can improve the interfacial compatibility between organic and inorganic materials. Spherical silica treated with coupling agents has very low water absorption, effectively reducing the water absorption of copper-clad laminate composites. It also allows organic polymer materials to uniformly coat the surface of inorganic fillers, reducing voids and improving electrical, physical, and water absorption properties.

[0041] Toughening materials improve the toughness of composite materials. Materials that are too rigid will experience crack propagation and delamination when cut. Therefore, the addition of highly tough nitrile rubber effectively improves the rigidity of the material. When these materials are combined with a curing agent and a curing accelerator, they can be cured under high temperature and pressure into a highly adhesive solid material with excellent dielectric properties, heat resistance, shear strength, and water absorption. Furthermore, it outperforms similar foreign materials in both water absorption and toughness, and can completely replace foreign products. Specific Implementation Example 3:

[0043] This embodiment further explains step a1 based on specific embodiment 2. In step a1, the medium molecular weight polyphenylene ether resin solution containing nitrile groups at both ends of the molecule is prepared by dissolving a polyphenylene ether resin with a molecular weight of 2000 containing nitrile groups at both ends of the molecule in cyclohexanone solvent. The mass fraction of the medium molecular weight polyphenylene ether resin containing nitrile groups at both ends of the molecule is 54 parts, and the mass fraction of the cyclohexanone solvent is 10 parts. Specific Implementation Example 4:

[0045] This embodiment further explains step a1 based on specific embodiment 2. In step a1, the medium molecular weight polyphenylene ether resin solution containing nitrile groups at both ends of the molecule is prepared by dissolving a polyphenylene ether resin with a molecular weight of 2000 containing nitrile groups at both ends of the molecule in cyclohexanone solvent. The mass fraction of the medium molecular weight polyphenylene ether resin containing nitrile groups at both ends of the molecule is 50 parts, and the mass fraction of the cyclohexanone solvent is 15 parts. Specific Implementation Example 5:

[0047] This embodiment further explains step a1 based on specific embodiment 2. In step a1, the medium molecular weight polyphenylene ether resin solution containing nitrile groups at both ends of the molecule is prepared by dissolving a polyphenylene ether resin with a molecular weight of 2000 containing nitrile groups at both ends of the molecule in cyclohexanone solvent. The mass fraction of the medium molecular weight polyphenylene ether resin containing nitrile groups at both ends of the molecule is 60 parts, and the mass fraction of the cyclohexanone solvent is 25 parts. Specific Implementation Example 6:

[0049] This embodiment further explains step a1 based on specific embodiment 2. In step a1, the high molecular weight nitrile rubber solution is prepared by dissolving high molecular weight nitrile rubber with methyl ethyl ketone solvent. The mass fraction of the high molecular weight nitrile rubber is 15-30 parts, and the concentration of the prepared solution is 15%. The high molecular weight nitrile rubber contains nitrile rubber with a molecular weight of 18000-21000 and a nitrile group content of 10-18%.

[0050] The addition of such materials can improve the toughness of composite materials and reduce the delamination phenomenon of whitening at the plate edges during shearing. Specific example 7:

[0051] This embodiment further explains step a2 based on specific embodiment 2. In step a2, the mass fraction of the zinc, manganese or copper naphthenic acid compound is 1-3 parts, the mass fraction of butanone is 30-32 parts, and the butanone is stirred for 30-60 minutes when dissolved. The mass fraction of the compound containing phenolic hydroxyl groups added is 5-10 parts, and the stirring time is continued for 60 minutes. The mass fraction of the 70% dicyclopentadiene cyanate resin added is 150-200 parts.

[0052] Organic compounds containing manganese, zinc, and copper are selected as curing accelerators for the main resin, while compounds containing phenolic hydroxyl groups are used as curing agents. These compounds include tetrabromobisphenol A, allyl bisphenol A, and phenol. The dicyclopentadiene cyanate resin uses domestically produced raw materials, typically a 70% butanone solution, and the materials are widely available. Specific Implementation Example 8:

[0054] This embodiment further explains step a2 based on specific embodiment 2. The dicyclopentadiene cyanate resin in step a2 includes monomer resin or dicyclopentadiene cyanate polymerized at less than 30%. Specific Implementation Example 9:

[0056] This embodiment further explains step a3 based on specific embodiment 2. In step a3, the mass fractions of flame retardant and silane coupling agent added are 50-80 parts and 2-8 parts, respectively, and the stirring time is 60 minutes. The flame retardant is one or both of bromine-containing or phosphorus-containing flame retardants. The flame retardant is required to have a thermal decomposition temperature above 350°C. If a bromine-containing flame retardant is selected, it should have a bromine content of more than 66% and good thermal shock resistance. If a phosphorus-containing flame retardant is selected, it should have a phosphorus content of more than 14% and good thermal shock resistance. The flame retardant can be selected from decabromodiphenyl ethane, brominated polystyrene, tetrabromostyrene, diethylaluminum hypophosphite, DOPO, and hexaphenoxycyclotriphosphazene. The coupling agent includes KH-550 and KH-570. Specific Implementation Example 10:

[0058] This embodiment further explains step a4 based on specific embodiment 2, wherein the mass fraction of spherical silica filler added in step a4 is 250-400 parts.

[0059] The addition of spherical silica can effectively reduce the dielectric loss of composite materials, increase the stability of high-speed signal transmission, and also reduce costs. Spherical silica treated with hydrophobic organosilicon coupling agents has very low water absorption, which can effectively reduce the water absorption of composite materials. There are many professional suppliers in China that can provide spherical silica. Specific Implementation Example 11:

[0061] This embodiment further explains step b based on specific embodiment 1. In step c, the maximum temperature and pressure set on the press when making the copper-clad laminate are 250℃ and 40Kg / cm2, respectively, and the curing time is 2 hours. Specific Implementation Example 12:

[0063] This embodiment further explains step c based on specific embodiment 1. In step c, the maximum temperature and pressure set on the press when making the copper-clad laminate are 250℃ and 40Kg / cm2, respectively, and the curing time is 2 hours. Specific Implementation Example 13:

[0065] Under otherwise unchanged conditions, bonding sheets and high-performance cyanate ester resin copper-clad laminates were prepared using the raw materials from the following four control groups. Control groups 1 and 3 were prepared by adding toughening polymers to form an interpenetrating network structure according to the traditional cyanate ester resin toughening method to verify its toughening effect, and the amount added was the maximum amount without affecting the resin's impregnation of glass fibers. Control groups 2 and 4 were copper-clad laminate composite materials produced using two reactive toughening material formulations with medium and high molecular weights used in this invention. Two flame retardant schemes were used: halogen-containing and phosphorus-containing. The phosphorus-containing flame retardant composite material is more in line with environmental protection requirements and future development directions.

Claims

1. A method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for use in copper-clad laminates, characterized in that: The process includes the following steps: a) preparing a resin solution using dicyclopentadiene cyanate resin and medium molecular weight polyphenylene ether resin with nitrile groups at both ends of the molecule as the main materials; b) coating the resin solution prepared in step a onto glass cloth and drying it to form a qualified prepreg for later use. c. When making copper-clad laminate, the qualified prepreg obtained in step b is stacked in the required quantity, and then electrolytic copper foil is applied to the top and bottom surfaces. The laminate is then fixed with stainless steel plates and placed in a press for curing at the set temperature and pressure. The preparation of the resin solution using dicyclopentadiene cyanate resin and medium molecular weight polyphenylene ether resin in step a includes the following steps: a1. Prepare a medium molecular weight polyphenylene ether resin solution with nitrile groups at both ends of the molecule for later use, and at the same time prepare a high molecular weight nitrile rubber solution for later use; a2. Dissolve one of the naphthenic acid compounds of zinc, manganese or copper in butanone, then add a compound containing phenolic hydroxyl groups and continue stirring. After stirring is completed, add 70% dicyclopentadiene cyanate resin to obtain solution x; a3. Add the medium molecular weight polyphenylene ether resin solution with nitrile groups at both ends prepared in step a1 and the high molecular weight nitrile rubber solution to solution x, then add flame retardant and silane coupling agent and stir; a4. After stirring, add spherical silica filler, then add cyclohexanone solvent to adjust the solid content of the resin to 70-73%, and then stir for 3 hours to obtain the final solution; steps a1 to a4 are all carried out at room temperature.

2. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: The medium molecular weight polyphenylene ether resin solution containing nitrile groups at both ends of the molecule in step a1 is prepared by dissolving a polyphenylene ether resin with a molecular weight of 2000 containing nitrile groups at both ends of the molecule in cyclohexanone solvent. The mass fraction of the medium molecular weight polyphenylene ether resin containing nitrile groups at both ends of the molecule is 50-60 parts, and the mass fraction of the cyclohexanone solvent is 10-25 parts.

3. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: In step a1, the high molecular weight nitrile rubber solution is prepared by dissolving high molecular weight nitrile rubber in methyl ethyl ketone (MEK) solvent. The mass fraction of the high molecular weight nitrile rubber is 15-30 parts, and the concentration of the prepared solution is 15%. The high molecular weight nitrile rubber is nitrile rubber with a nitrile group content of 10-18% and a molecular weight of 18,000-21,000.

4. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: In step a2, the mass fraction of the zinc, manganese, or copper naphthenic acid compound is 1-3 parts, the mass fraction of butanone is 30-32 parts, and the butanone is stirred for 30-60 minutes when dissolved. The mass fraction of the compound containing phenolic hydroxyl groups added is 5-10 parts, and the stirring time is continued for 60 minutes. The mass fraction of the 70% dicyclopentadiene cyanate resin added is 150-200 parts.

5. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: The dicyclopentadiene cyanate resin in step a2 includes monomeric resin or dicyclopentadiene cyanate polymerized at less than 30%.

6. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: The flame retardant includes decabromodiphenyl ethane, brominated polystyrene, tetrabromostyrene, diethylaluminum hypophosphite, DOPO, and hexaphenoxycyclotriphosphazene; the coupling agent includes KH-550 and KH-570.

7. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: The mass fraction of spherical silica filler added in step a4 is 250-400 parts.

8. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: In step b, when forming a qualified semi-cured sheet, the resin content is controlled at 54%, the flow rate at 10-16%, and the resin gelation time at 120-160 seconds.

9. The method for manufacturing a high-performance cyanate ester resin glass cloth bonding sheet for copper-clad laminates according to claim 1, characterized in that: In step c, the maximum temperature and pressure set on the press during the copper-clad laminate production are 250℃ and 40Kg / cm2, respectively, and the curing time is 2 hours.