CN112063111A - Modified epoxy resin composition, high-Tg low-loss laminated copper-clad plate and preparation method thereof - Google Patents

Modified epoxy resin composition, high-Tg low-loss laminated copper-clad plate and preparation method thereof Download PDF

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CN112063111A
CN112063111A CN202010965028.4A CN202010965028A CN112063111A CN 112063111 A CN112063111 A CN 112063111A CN 202010965028 A CN202010965028 A CN 202010965028A CN 112063111 A CN112063111 A CN 112063111A
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epoxy resin
modified epoxy
mixture
resin composition
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陈伟福
李亚涛
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Guangde Longtai Electronic Sci Tech Co ltd
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Guangde Longtai Electronic Sci Tech Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C08L63/04—Epoxynovolacs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The invention relates to a modified epoxy resin composition, a high Tg low-loss laminated copper-clad plate and a preparation method thereof, wherein the composition comprises styrene-maleic anhydride, an organic solvent, an inorganic filler, modified epoxy resin, a catalyst, a curing agent and a curing accelerator, an epoxy resin composition glue solution is prepared firstly, then the glue solution is coated on a copper foil, the semi-curing is carried out, the heating, hot pressing and laminating are carried out to obtain the TG low-loss laminated copper-clad plate, the method of acid anhydride and modified epoxy resin is adopted to grind the high TG low-loss laminated copper-clad plate, the Tg can reach more than 180 ℃, the Td can reach more than 370 ℃ (TGA 5% loss), the Dk (3.64@10GHz) and the Df (0.0065@10GHz), the performance is excellent, the practicability is strong, the composition is not only suitable for a standard multilayer printed circuit board, but also suitable for radar application, and, has wide market value and application prospect.

Description

Modified epoxy resin composition, high-Tg low-loss laminated copper-clad plate and preparation method thereof
Technical Field
The invention relates to the technical field of copper-clad plate manufacturing, in particular to a modified epoxy resin composition, a high-Tg low-loss press-fit copper-clad plate and a preparation method thereof.
Background
With the rapid development of electronic products in the direction of light weight, thinness, small size, high density, multiple functions and microelectronic integration technology, the volumes of electronic elements and logic circuits are reduced by times, the working frequency is increased rapidly, the power consumption is increased continuously, and the working environment of components is changed in the direction of high temperature. The requirement on the heat dissipation performance of the PCB substrate is more and more urgent, and if the heat dissipation performance of the substrate is not good, components on the printed circuit board are overheated, so that the reliability of the whole machine is reduced. How to find the best solution for heat dissipation and structural design has become a big problem in the design of current electronic products. The research and development of the metal-based copper-clad plate with high heat conductivity and high performance is undoubtedly the most effective means for solving the problems of heat dissipation and structural design. The core and key technical point of the metal-based copper-clad plate lies in the insulating layer material, and the heat conductivity coefficient of the insulating layer material is improved to meet the heat dissipation requirement of a high-power product.
The metal-based copper-clad plate is a mainstream substrate used by a high-power supply, military electronics and high-frequency microelectronic equipment as a novel substrate, has excellent performances of thermal conductivity which is nearly 10 times or more, high breakdown voltage, bulk and surface resistivity, excellent high temperature resistance and the like compared with an FR-4 and a common copper-clad plate, and meets the development trend and the demand of high-frequency microelectronics.
The halogen-containing organic matter is added into the existing metal-based copper-clad plate insulating layer, so that the combustion resistance of the product can be greatly improved. However, the halogen-containing materials generate a large amount of toxic gases during combustion, damage the environment and threaten human health. Therefore, various halogen-based regulations are continuously issued by various countries and organizations in the world to limit the use of halogen-based products, and the requirement of no halogenation is an inevitable trend of global development. Due to the limitations of all aspects, the metal-based copper-clad plate industry in China is still at a relatively lagged level in the aspects of software and hardware, and the produced products have low reliability, poor stability and uneven performance, and particularly have a plurality of defects in the aspects of heat conductivity, insulativity, bending resistance, thickness uniformity of insulating layers and the like.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
The invention aims to provide a modified epoxy resin composition, a high-Tg low-loss laminated copper-clad plate and a preparation method thereof, wherein the high-TG low-loss copper-clad plate is researched by adopting an anhydride and modified epoxy resin method, the Tg can reach 180 ℃, the Td can reach 370 ℃ (TGA 5% loss), the Dk (3.64@10GHz) and the Df (0.0065@10GHz) are low, and the modified epoxy resin composition is not only suitable for a standard multilayer printed circuit board, but also suitable for radar application and 3S (server/storage/switch) application.
The invention is realized by the following technical scheme:
the modified epoxy resin composition comprises the following components in parts by weight:
Figure BDA0002681964330000021
preferably, the modified epoxy resin is a mixture of two or more of graphene modified high-bromine epoxy resin, cyanate ester modified epoxy resin, graphene modified bisphenol S type epoxy resin, dimer acid modified epoxy resin, carboxyl-terminated nitrile rubber modified novolac epoxy resin, polyurethane modified bisphenol A epoxy resin, thermoplastic polyurethane modified epoxy resin or terpene modified epoxy resin.
Preferably, the organic solvent is a mixture of two or more of DM, methyl ethyl ketone, propylene glycol methyl ether, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methanol, ethanol, isopropanol, diethyl ether, propylene oxide, cyclohexane, cyclohexanone or toluene cyclohexanone.
Preferably, the inorganic filler is a mixture of two or more of spherical silica (particle size 2 microns), fused silica (1.6 microns), BASF highly micronized kaolin, zinc oxide, magnesium oxide, aluminum oxide, bismuth oxide, beryllium oxide, magnesium hydroxide, aluminum hydroxide, iron oxide, boron nitride, silicon carbide, diamond or silicon nitride.
Preferably, the catalyst is one or a mixture of two of cobalt acetylacetonate and butyl triphenyl phosphonium bromide.
Preferably, the curing agent is a mixture of two or more of aliphatic polyamine, diacetone acrylamide, alicyclic polyamine, triethanolamine, DMP-30, m-phenylenediamine, diaminodiphenyl sulfone, diaminodiphenylmethane, m-xylylenediamine, imidazoles, acid anhydrides, polyamide, phenol resin, amino resin, dicyandiamide or organic hydrazide.
Preferably, the curing accelerator is a mixture of two or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-phenylimidazole, 1-cyanoethyl-2-ethyl-4-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole or 2-heptadecylimidazole.
A method for preparing a high-Tg low-loss laminated copper-clad plate by using the modified epoxy resin composition specifically comprises the following steps:
s1, starting an ice water circulating system of the glue mixing tank, and setting the temperature of ice water to be 0-10 ℃. Adding styrene-maleic anhydride and an organic solvent, and stirring for 120-300 min until the styrene-maleic anhydride is completely dissolved;
s2, adding an inorganic filler into the mixture obtained in the step 1, starting a homogenizer and a shearing machine to stir for 60-180 min in a circulating manner, and passing through a high-magnetic filter barrel to adsorb impurities in the filler;
s3, adding the modified epoxy resin, the catalyst, the curing agent and the curing accelerator into the mixture obtained in the step 2, circularly stirring for 30-120 min, and preparing to obtain glue solution;
s4, coating the glue solution obtained in the step 3 on the outer surface of a copper foil, and baking the copper foil coated with the glue solution at the baking temperature of 60-150 ℃ for 5-15 min to form a semi-cured continuous glued copper foil;
and S5, laminating the two surfaces of the inner-layer core plate subjected to proper brown blackening treatment with the coated copper foil obtained in the step 4, repeatedly laminating multiple layers according to actual requirements, and preparing the high-Tg low-loss laminated copper-clad plate by adopting hydraulic pressurization in a hot kerosene type heating mode.
A high Tg low-loss laminated copper-clad plate is prepared by the preparation method.
The invention has the beneficial effects that: the epoxy resin composition glue solution prepared by the invention and the laminated copper-clad plate produced by using the glue solution are used for manufacturing the high-TG low-loss laminated copper-clad plate by adopting an anhydride and modified epoxy resin method, the Tg can reach more than 180 ℃, the Td can reach more than 370 ℃ (TGA 5% loss), the Dk (3.64@10GHz) and the Df (0.0065@10GHz) are low, the performance is excellent, the practicability is strong, the creativity is good, the epoxy resin composition glue solution is not only suitable for a standard multilayer printed circuit board, but also suitable for radar application, and is also suitable for 3S (server/storage/switch) application, and the epoxy resin composition glue solution has wide market value and application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the technical solutions in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The modified epoxy resin composition comprises the following components in parts by weight:
Figure BDA0002681964330000051
furthermore, the epoxy resin refers to an organic polymer compound containing two or more than two epoxy groups in the molecule, in the invention, the epoxy resin is preferably a modified epoxy resin, and the modified epoxy resin is a mixture of two or more of graphene modified high-bromine epoxy resin, cyanate ester modified epoxy resin, graphene modified bisphenol S type epoxy resin, dimer acid modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber modified novolac epoxy resin, polyurethane modified bisphenol A epoxy resin, thermoplastic polyurethane modified epoxy resin or terpene modified epoxy resin.
Further, the organic solvent is a mixture of two or more of DM, methyl ethyl ketone, propylene glycol methyl ether, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methanol, ethanol, isopropyl alcohol, diethyl ether, propylene oxide, cyclohexane, cyclohexanone, or toluene cyclohexanone.
Still further, the inorganic filler is a mixture of two or more of spherical silica (particle size 2 microns), fused silica (1.6 microns), BASF highly micronized kaolin, zinc oxide, magnesium oxide, aluminum oxide, bismuth oxide, beryllium oxide, magnesium hydroxide, aluminum hydroxide, iron oxide, boron nitride, silicon carbide, diamond, or silicon nitride.
Further, the catalyst is one or a mixture of two of cobalt acetylacetonate and butyl triphenyl phosphonium bromide.
Further, the curing agent is a mixture of two or more of aliphatic polyamine, diacetone acrylamide, alicyclic polyamine, triethanolamine, DMP-30, m-phenylenediamine, diaminodiphenyl sulfone, diaminodiphenylmethane, m-xylylenediamine, imidazoles, acid anhydrides, polyamide, phenol resin, amino resin, dicyandiamide, or organic hydrazide.
Still further, the curing accelerator is a mixture of two or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-phenylimidazole, 1-cyanoethyl-2-ethyl-4-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, or 2-heptadecylimidazole.
Based on the epoxy resin composition, the invention also provides a method for preparing the high-Tg low-loss laminated copper-clad plate by using the modified epoxy resin composition, which specifically comprises the following steps:
s1, starting an ice water circulating system of the glue mixing tank, and setting the temperature of ice water to be 0-10 ℃. Adding styrene-maleic anhydride and an organic solvent, and stirring for 120-300 min until the styrene-maleic anhydride is completely dissolved;
s2, adding an inorganic filler into the mixture obtained in the step 1, starting a homogenizer and a shearing machine to stir for 60-180 min in a circulating manner, and passing through a high-magnetic filter barrel to adsorb impurities in the filler;
s3, adding the modified epoxy resin, the catalyst, the curing agent and the curing accelerator into the mixture obtained in the step 2, circularly stirring for 30-120 min, and preparing to obtain glue solution;
s4, coating the glue solution obtained in the step 3 on the outer surface of a copper foil, and baking the copper foil coated with the glue solution at the baking temperature of 60-150 ℃ for 5-15 min to form a semi-cured continuous glued copper foil;
and S5, laminating the two surfaces of the inner-layer core plate subjected to proper brown blackening treatment with the coated copper foil obtained in the step 4, repeatedly laminating multiple layers according to actual requirements, and preparing the high-Tg low-loss laminated copper-clad plate by adopting hydraulic pressurization in a hot kerosene type heating mode.
In this step, the continuous glued copper foil can be cut into the required size by using an automatic precise cutting machine; and then, the glued copper foil is attached to the inner core plate after the brown blackening treatment, the inner core plate after the brown blackening treatment is heated and pressurized to be made into a pressed copper-clad plate, and the inner core plate after the brown blackening treatment can be subjected to anodic oxidation or physical roughening treatment and brown blackening treatment so that the laminating effect of lamination is better.
Several specific examples are provided below to illustrate the invention in detail.
Example 1
And (3) starting an ice water circulating system of the glue mixing tank, and setting the temperature of ice water to be 10 ℃. Adding a mixture of 60 parts (by weight, the same below) of styrene-maleic anhydride and 80 parts of DMF (dimethyl formamide), butanone and propylene glycol methyl ether, and stirring for 180min until the styrene-maleic anhydride is completely dissolved; then adding 100 parts of a mixture of boron nitride, silicon carbide, diamond or silicon nitride into the mixture, starting a homogenizer and a shearing machine to circularly stir for 100min, and passing through a high-magnetic filter barrel to adsorb impurities in the filler; adding 150 parts of graphene modified high-bromine epoxy resin, cyanate ester modified epoxy resin, a mixture of graphene modified bisphenol S type epoxy resin, 25 parts of a mixture of cobalt acetylacetonate and butyl triphenyl phosphorus bromide, 50 parts of aliphatic polyamine, diacetone acrylamide, a mixture of alicyclic polyamine and 5 parts of a mixture of 2-methylimidazole, 2-ethylimidazole and 2-phenylimidazole into the obtained mixture, and circularly stirring for 60min to obtain a glue solution after modulation; coating the obtained glue solution on the outer surface of a copper foil, and baking the copper foil coated with the glue solution at the baking temperature of 150 ℃ for 5min to form a semi-cured continuous glued copper foil; and (3) laminating the two surfaces of the inner core plate cut to be properly brownish black to obtain the glued copper foil, repeatedly laminating the glued copper foil in multiple layers according to actual requirements, and preparing the high-Tg low-loss laminated copper-clad plate by adopting hydraulic pressurization in a hot kerosene type heating mode.
The epoxy resin composition glue solution prepared and the laminated copper-clad plate produced by using the glue solution have excellent performance: 1. low Dk (3.64@10GHz) and low Df (0.0065@10GHz), stable Dk/Df under different environments; tg (. degree.C.) differential scanning calorimetry: 180 ℃; t-288 (1 ounce copper containing) TMA: 30 min; td-5% (. degree. C.) TGA 5% loss: 370 ℃; 5. coefficient of thermal expansion (ppm/. degree. C.) a1/a 2: 45/250, respectively; coefficient of thermal expansion (%), 50-260 ℃: 2.6 percent; dk @10 gigahertz (RC 50%): 3.64 of; df @10GHz (RC 50%): 0.0065.
example 2
And (4) starting an ice water circulating system of the glue mixing tank, and setting the temperature of ice water to be 5 ℃. Adding 40 parts (by weight, the same below) of styrene-maleic anhydride and a mixture of 60 parts of acetone, methyl butanone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and ethylene glycol monobutyl ether, and stirring for 240min until the styrene-maleic anhydride is completely dissolved; then adding a mixture of 200 parts of spherical silicon dioxide (particle size of 2 microns), fused silicon dioxide (particle size of 1.6 microns) and Germany BASF highly micronized kaolin into the mixture, starting a homogenizer and a shearing machine to stir for 120min in a circulating way, and passing through a high-magnetic filter barrel to adsorb impurities in the filler; adding 150 parts of dimer acid modified epoxy resin, carboxyl-terminated butadiene-acrylonitrile rubber modified novolac epoxy resin, polyurethane modified bisphenol A epoxy resin, thermoplastic polyurethane modified epoxy resin or terpene modified epoxy resin mixture, 25 parts of cobalt acetylacetonate, butyl triphenyl phosphorus bromide mixture, 50 parts of DMP-30, m-phenylenediamine, diaminodiphenyl sulfone, diaminodiphenyl methane, m-xylylenediamine and imidazole mixture into the obtained mixture, circularly stirring for 60min, and preparing to obtain glue solution; coating the obtained glue solution on the outer surface of a copper foil, and baking the copper foil coated with the glue solution at the baking temperature of 60 ℃ for 15min to form a semi-cured continuous glued copper foil; and (3) laminating the two surfaces of the inner core plate cut to be properly brownish black to obtain the glued copper foil, repeatedly laminating the glued copper foil in multiple layers according to actual requirements, and preparing the high-Tg low-loss laminated copper-clad plate by adopting hydraulic pressurization in a hot kerosene type heating mode.
Example 3
And (3) starting an ice water circulating system of the glue mixing tank, and setting the temperature of ice water to be 3 ℃. Adding a mixture of 30 parts (by weight, the same below) of styrene-maleic anhydride and 50 parts of ethanol, isopropanol, ether, propylene oxide, cyclohexane, cyclohexanone or toluene cyclohexanone, and stirring for 150min until the styrene-maleic anhydride is completely dissolved; then adding a mixture of 200 parts of spherical silicon dioxide (with the particle size of 2 microns), fused silicon dioxide (with the particle size of 1.6 microns) and Germany BASF highly micronized kaolin into the mixture, starting a homogenizer and a shearing machine to circularly stir for 100min, and passing through a high-magnetic filter barrel to adsorb impurities in the filler; adding 150 parts of glue-modified novolac epoxy resin, polyurethane-modified bisphenol A epoxy resin, thermoplastic polyurethane-modified epoxy resin or a mixture of terpene-modified epoxy resins, 25 parts of cobalt acetylacetonate, a mixture of butyltriphenylphosphonium bromide, 50 parts of acid anhydride, polyamide, phenolic resin, amino resin, a mixture of dicyandiamide or organic hydrazide, 5 parts of a mixture of 1-cyanoethyl-2-ethyl-4-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole or 2-heptadecylimidazole into the obtained mixture, and circularly stirring for 90min to obtain glue solution after modulation; coating the obtained glue solution on the outer surface of a copper foil, and baking the copper foil coated with the glue solution at the baking temperature of 100 ℃ for 10min to form a semi-cured continuous glued copper foil; and (3) laminating the two surfaces of the inner core plate cut to be properly brownish black to obtain the glued copper foil, repeatedly laminating the glued copper foil in multiple layers according to actual requirements, and preparing the high-Tg low-loss laminated copper-clad plate by adopting hydraulic pressurization in a hot kerosene type heating mode.
In the invention, the method of adopting anhydride and modified epoxy resin to research the high-TG low-loss press-fit copper-clad plate prepared by the invention has the advantages that the Tg can reach more than 180 ℃, the Td can reach more than 370 ℃ (TGA 5% loss), the Dk (3.64@10GHz) and the Df (0.0065@10GHz) are low, the performance is excellent, the practicability is high, the creativity is good, the method is not only suitable for a standard multilayer printed circuit board, but also suitable for radar application, and is also suitable for 3S (server/storage/switch) application, and the market value and the application prospect are wide.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. The modified epoxy resin composition is characterized by comprising the following components in parts by weight:
Figure FDA0002681964320000011
2. the modified epoxy resin composition of claim 1, wherein the modified epoxy resin is a mixture of two or more of graphene-modified high-bromine epoxy resin, cyanate ester-modified epoxy resin, graphene-modified bisphenol S-type epoxy resin, dimer acid-modified epoxy resin, carboxyl-terminated nitrile rubber-modified novolac epoxy resin, polyurethane-modified bisphenol a epoxy resin, thermoplastic polyurethane-modified epoxy resin, or terpene-modified epoxy resin.
3. The modified epoxy resin composition according to claim 1, wherein the organic solvent is a mixture of two or more selected from the group consisting of DM, methyl ethyl ketone, propylene glycol methyl ether, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, methanol, ethanol, isopropyl alcohol, diethyl ether, propylene oxide, cyclohexane, cyclohexanone and toluene cyclohexanone.
4. The modified epoxy resin composition of claim 1, wherein the inorganic filler is a mixture of two or more of spherical silica (particle size 2 microns), fused silica (1.6 microns), BASF highly micronized kaolin, zinc oxide, magnesium oxide, aluminum oxide, bismuth oxide, beryllium oxide, magnesium hydroxide, aluminum hydroxide, iron oxide, boron nitride, silicon carbide, diamond, or silicon nitride.
5. The modified epoxy resin composition of claim 1, wherein the catalyst is cobalt acetylacetonate or a mixture of two or more of butyltriphenylphosphonium bromide.
6. The modified epoxy resin composition according to claim 1, wherein the curing agent is a mixture of two or more selected from the group consisting of aliphatic polyamine, diacetone acrylamide, alicyclic polyamine, triethanolamine, DMP-30, m-phenylenediamine, diaminodiphenyl sulfone, diaminodiphenylmethane, m-xylylenediamine, imidazoles, acid anhydrides, polyamide, phenol resin, amino resin, dicyandiamide, and organic hydrazide.
7. The modified epoxy resin composition of claim 1, wherein the curing accelerator is a mixture of two or more selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-ethyl-4-phenylimidazole, 1-cyanoethyl-2-ethyl-4-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole and 2-heptadecylimidazole.
8. The method for preparing the high-Tg low-loss laminated copper-clad plate by using the modified epoxy resin composition as claimed in claim 1 is characterized by comprising the following steps:
s1, starting an ice water circulating system of the glue mixing tank, and setting the temperature of ice water to be 0-10 ℃. Adding styrene-maleic anhydride and an organic solvent, and stirring for 120-300 min until the styrene-maleic anhydride is completely dissolved;
s2, adding an inorganic filler into the mixture obtained in the step 1, starting a homogenizer and a shearing machine to stir for 60-180 min in a circulating manner, and passing through a high-magnetic filter barrel to adsorb impurities in the filler;
s3, adding the modified epoxy resin, the catalyst, the curing agent and the curing accelerator into the mixture obtained in the step 2, circularly stirring for 30-120 min, and preparing to obtain glue solution;
s4, coating the glue solution obtained in the step 3 on the outer surface of a copper foil, and baking the copper foil coated with the glue solution at the baking temperature of 60-150 ℃ for 5-15 min to form a semi-cured continuous glued copper foil;
and S5, laminating the two surfaces of the inner-layer core plate subjected to proper brown blackening treatment with the coated copper foil obtained in the step 4, repeatedly laminating multiple layers according to actual requirements, and preparing the high-Tg low-loss laminated copper-clad plate by adopting hydraulic pressurization in a hot kerosene type heating mode.
9. A high Tg low loss laminated copper clad laminate characterized by being prepared by the preparation method of claim 8.
CN202010965028.4A 2020-09-15 2020-09-15 Modified epoxy resin composition, high-Tg low-loss laminated copper-clad plate and preparation method thereof Pending CN112063111A (en)

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CN112644112A (en) * 2020-12-17 2021-04-13 万奔电子科技股份有限公司 Automobile intelligent central control multilayer board and preparation method thereof
CN113801533A (en) * 2021-02-05 2021-12-17 中国科学院兰州化学物理研究所 Dry film lubricant based on dopamine modified pigment filler and application thereof

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CN104559068A (en) * 2014-12-23 2015-04-29 上海南亚覆铜箔板有限公司 Thermosetting resin composition as well as preparation method and application thereof
CN104559888A (en) * 2014-12-23 2015-04-29 上海南亚覆铜箔板有限公司 Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate
CN107953629A (en) * 2017-11-28 2018-04-24 南亚新材料科技股份有限公司 A kind of high speed high reliability halogen-free copper-clad plate and preparation method thereof

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CN104559068A (en) * 2014-12-23 2015-04-29 上海南亚覆铜箔板有限公司 Thermosetting resin composition as well as preparation method and application thereof
CN104559888A (en) * 2014-12-23 2015-04-29 上海南亚覆铜箔板有限公司 Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112644112A (en) * 2020-12-17 2021-04-13 万奔电子科技股份有限公司 Automobile intelligent central control multilayer board and preparation method thereof
CN112644112B (en) * 2020-12-17 2023-04-14 万奔电子科技股份有限公司 Automobile intelligent central control multilayer board and preparation method thereof
CN113801533A (en) * 2021-02-05 2021-12-17 中国科学院兰州化学物理研究所 Dry film lubricant based on dopamine modified pigment filler and application thereof
CN113801533B (en) * 2021-02-05 2022-03-01 中国科学院兰州化学物理研究所 Dry film lubricant based on dopamine modified pigment filler and application thereof

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