CN112250999A - Heat-resistant epoxy resin composition, halogen-free middle-Tg copper-clad plate and preparation method thereof - Google Patents
Heat-resistant epoxy resin composition, halogen-free middle-Tg copper-clad plate and preparation method thereof Download PDFInfo
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
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Abstract
The invention relates to a heat-resistant epoxy resin composition, a halogen-free middle-Tg copper-clad plate and a preparation method thereof, wherein the composition comprises the following components in parts by weight: graphene modified epoxy resin, graphene modified phenolic epoxy resin, MDI modified bromine-free resin, four-functional group epoxy resin, phenolic resin, 4' -dioxydiphenyl sulfone (DDS), composite silica micropowder, aluminum hydroxide, modified graphene oxide, an organic solvent, a curing accelerator and a catalyst, wherein glue solution is prepared firstly, then is soaked on glass fiber cloth and is dried to be semi-cured, and then is heated, hot pressed and laminated to obtain the lead-free middle Tg copper-clad plate; the novel resin is used for improving the viscosity of the glue, so that the resin amount is reduced, the resin content is uniform, and the impregnation effect of the glass fiber cloth is good during gluing; the size stability of the copper clad plate prepared by the novel resin system is improved, and the processing performance of the PCB is better.
Description
Technical Field
The invention relates to the technical field of copper-clad plate manufacturing, in particular to a heat-resistant epoxy resin composition, a halogen-free middle-Tg 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-containing regulations are continuously issued by various countries and organizations in the world to limit the use of halogen-containing and lead-containing products, and the requirement of halogen-free and lead-free products 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 heat-resistant epoxy resin composition, a halogen-free middle Tg copper-clad plate and a preparation method thereof, which are suitable for the process requirements of a PCB halogen-free and lead-free process, meet the IPC standard requirements of product technical indexes, and are mainly applied to the fields of consumer electronics, power supplies, instruments and meters, communication equipment, automotive electronics and the like, and the key technical points of the material are as follows: the Tg of the material is more than or equal to 150 ℃, and the halogen-free and lead-free process is compatible with the plate; the adhesive has excellent peeling strength; low Z-CTE values; excellent CAF resistance; UV Blocking is compatible with AOI; low water absorption; excellent in dimensional stability.
The invention is realized by the following technical scheme:
a heat-resistant epoxy resin composition comprises the following components in percentage by weight:
preferably, the heat-resistant epoxy resin composition further comprises a catalyst, wherein the catalyst is 2-5%; the catalyst is one or a mixture of two of cobalt acetylacetonate or butyl triphenyl phosphonium bromide.
Preferably, the organic solvent is one 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 curing accelerator is a mixture of one 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 halogen-free middle Tg copper-clad plate by using the heat-resistant epoxy resin composition specifically comprises the following steps:
s1, starting an ice water circulating system of the glue mixing tank, setting the temperature of ice water to be 0-10 ℃, adding graphene modified epoxy resin, phenolic epoxy resin, MDI modified bromine-free resin, four-functional group epoxy resin, phenolic resin and an organic solvent, and stirring for 120-240 min until the halogen-free epoxy resin is completely dissolved in the organic solvent;
s2, adding composite silicon micropowder, aluminum hydroxide and modified graphene oxide into the mixed material obtained in the step 1, starting a homogenizer and a shearing machine to circularly stir for 90-120 min, and passing through a molecular sieve filter pressing barrel to adsorb and filter large particles in the mixed material;
s3, adding 4, 4' -dioxydiphenyl sulfone (DDS), a curing accelerator and a catalyst into the mixed material obtained in the step 2, circularly stirring for 30-120 min, and preparing to obtain a glue solution;
s4, dipping the glue solution obtained in the step 3 on glass fiber cloth through a vertical gluing machine, and baking the glass fiber cloth dipped with the glue solution at the baking temperature of 60-120 ℃ for 5-20 min to form a continuous prepreg;
and S5, covering copper foil on the prepreg obtained in the step 4, and performing hot press molding through a hot press to obtain the medium Tg copper clad laminate used in the halogen-free manufacturing process of the PCB.
The halogen-free middle Tg copper-clad plate is prepared by the preparation method.
The invention has the beneficial effects that: the invention adopts a novel halogen-free resin system to improve the heat resistance of the material, so that the material property can meet the requirement of a lead-free process of a PCB; the novel resin is used for improving the viscosity of the glue, so that the resin amount is reduced, the resin content is uniform, and the impregnation effect of the glass fiber cloth is good during gluing; the size stability of the copper clad laminate prepared by the novel resin system can be improved, and the PCB processing performance is better; the prepared copper-clad plate has the following characteristics: the Tg of the material is more than or equal to 150 ℃, and the halogen-free and lead-free process is compatible with the plate; the adhesive has excellent peeling strength; low Z-CTE values; excellent CAF resistance; UV Blocking is compatible with AOI; low water absorption; excellent dimensional stability; the product is suitable for the manufacture procedure requirement of PCB halogen-free and lead-free manufacture procedure, the technical index of the product meets the IPC standard requirement, and the product is mainly applied to the fields of consumer electronics, instruments and meters, communication equipment, automobile electronics and the like.
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.
A heat-resistant epoxy resin composition comprises the following components in percentage by weight:
furthermore, the heat-resistant epoxy resin composition also comprises a catalyst, wherein the catalyst is 2-5%, and the catalyst is one or a mixture of two of cobalt acetylacetonate and butyl triphenyl phosphonium bromide.
Further, the organic solvent is one or more of DM, butanone, propylene glycol methyl ether, benzene, toluene, xylene, acetone, methyl butanone, 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.
Still further, the curing accelerator is one or a mixture of 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 halogen-free middle Tg copper-clad plate by using the heat-resistant 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 graphene modified epoxy resin, novolac epoxy resin, MDI modified bromine-free resin, four-functional group epoxy resin, phenolic resin and an organic solvent, and stirring for 120-240 min until the halogen-free epoxy resin is completely dissolved in the organic solvent;
s2, adding composite silicon micropowder, aluminum hydroxide and modified graphene oxide into the mixed material obtained in the step 1, starting a homogenizer and a shearing machine to circularly stir for 90-120 min, and passing through a molecular sieve filter pressing barrel to adsorb and filter large particles in the mixed material;
s3, adding 4, 4' -dioxydiphenyl sulfone (DDS), a curing accelerator and a catalyst into the mixed material obtained in the step 2, circularly stirring for 30-120 min, and preparing to obtain a glue solution;
s4, dipping the glue solution obtained in the step 3 on glass fiber cloth through a vertical gluing machine, and baking the glass fiber cloth dipped with the glue solution at the baking temperature of 60-120 ℃ for 5-20 min to form a continuous prepreg;
and S5, covering copper foil on the prepreg obtained in the step 4, and performing hot press molding through a hot press to obtain the medium Tg copper clad laminate used in the halogen-free manufacturing process of the PCB.
The halogen-free middle Tg copper-clad plate is prepared by the preparation method.
The epoxy resin curing agent 4, 4' -Dioxy Diphenyl Sulfone (DDS) with excellent heat resistance is adopted, sulfur atoms in the molecular structure of the DDS are already in the highest oxidation state, meanwhile, sulfone groups tend to absorb electrons on benzene rings, but the benzene rings lack electrons, so that the whole diphenyl sulfone groups are in an oxidation-resistant state, in addition, the chemical bond strength of the diphenyl sulfone groups is high, the whole diphenyl sulfone groups are in a high-degree resonance state, and the whole diphenyl sulfone groups can be dissipated through the resonance system without chain breakage and crosslinking when a large amount of heat energy and radiation are absorbed, so that the DDS has outstanding heat resistance and low hygroscopicity.
Several specific examples are provided below to illustrate the invention in detail.
Example 1
Starting an ice water circulating system of the glue mixing tank, setting the temperature of ice water to be 3 ℃, adding 15% of graphene modified epoxy resin, 15% of graphene modified novolac epoxy resin, 8% of MDI modified bromine-free resin, 5% of four-functional group epoxy resin, 15% of phenolic resin and 20% of propylene glycol methyl ether, and stirring for 240min until the halogen-free epoxy resin is completely dissolved in the propylene glycol methyl ether; adding 8% of composite silicon micropowder, 3% of aluminum hydroxide and 5% of modified graphene oxide into the mixed material, starting a homogenizer and a shearing machine to circularly stir for 120min, and passing through a molecular sieve filter pressing barrel to adsorb and filter large particles in the mixed material; adding 1.5% of 4, 4' -Dioxy Diphenyl Sulfone (DDS), 1.5% of 2-ethyl-4-methylimidazole and 3% of cobalt acetylacetonate into the obtained mixed material, circularly stirring for 120min, and preparing to obtain a glue solution; dipping the obtained glue solution on glass fiber cloth through a vertical gluing machine, and baking the glass fiber cloth dipped with the glue solution at the baking temperature of 120 ℃ for 20min to form a continuous prepreg; and covering copper foil on the obtained prepreg, and performing hot press molding through a hot press to obtain the medium Tg copper clad laminate used for the halogen-free manufacture procedure of the PCB.
Example 2
Starting an ice water circulating system of the glue mixing tank, setting the temperature of ice water to be 5 ℃, adding 15% of graphene modified epoxy resin, 10% of graphene modified novolac epoxy resin, 12% of MDI modified bromine-free resin, 10% of four-functional group epoxy resin, 15% of phenolic resin and 20% of ethylene glycol monoethyl ether, and stirring for 200min until the halogen-free epoxy resin is completely dissolved in the ethylene glycol monoethyl ether; adding 8% of composite silicon micropowder, 3% of aluminum hydroxide and 2% of modified graphene oxide into the mixed material, starting a homogenizer and a shearing machine to circularly stir for 100min, passing through a molecular sieve filter pressing barrel, and adsorbing and filtering large particles in the mixed material; adding 1.5% of 4, 4' -Dioxy Diphenyl Sulfone (DDS), 1.5% of 2-heptadecyl imidazole and 2% of cobalt acetylacetonate into the obtained mixed material, and then circularly stirring for 90min to obtain a glue solution after modulation; dipping the obtained glue solution on glass fiber cloth through a vertical gluing machine, and baking the glass fiber cloth dipped with the glue solution at the baking temperature of 100 ℃ for 10min to form a continuous prepreg; and covering copper foil on the obtained prepreg, and performing hot press molding through a hot press to obtain the medium Tg copper clad laminate used for the halogen-free manufacture procedure of the PCB.
Example 3
Starting an ice water circulating system of the glue mixing tank, setting the temperature of ice water to be 10 ℃, adding 15% of graphene modified epoxy resin, 10% of graphene modified novolac epoxy resin, 8% of MDI modified bromine-free resin, 5% of four-functional group epoxy resin, 15% of phenolic resin and 25% of propylene oxide, and stirring for 240min until the halogen-free epoxy resin is completely dissolved in the propylene oxide; adding 8% of composite silicon micropowder, 3% of aluminum hydroxide and 4% of modified graphene oxide into the mixed material, starting a homogenizer and a shearing machine, circularly stirring for 90min, passing through a molecular sieve filter pressing barrel, and adsorbing and filtering large particles in the mixed material; adding 2.5% of 4, 4' -dioxydiphenyl sulfone (DDS), 1.5% of 2-ethyl-4-phenylimidazole and 3% of butyl triphenyl phosphonium bromide into the obtained mixed material, circularly stirring for 30min, and preparing to obtain a glue solution; dipping the obtained glue solution on glass fiber cloth through a vertical gluing machine, and baking the glass fiber cloth dipped with the glue solution at the baking temperature of 120 ℃ for 5min to form a continuous prepreg; and covering copper foil on the obtained prepreg, and performing hot press molding through a hot press to obtain the medium Tg copper clad laminate used for the halogen-free manufacture procedure of the PCB.
Example 4
Starting an ice water circulating system of the glue mixing tank, setting the temperature of ice water to be 0-10 ℃, adding 17% of graphene modified epoxy resin, 10% of graphene modified novolac epoxy resin, 8% of MDI modified bromine-free resin, 5.5% of four-functional group epoxy resin, 15% of phenolic resin and 20% of methyl isobutyl ketone, and stirring for 180min until the halogen-free epoxy resin is completely dissolved in the methyl isobutyl ketone; adding 12% of composite silicon powder, 3% of aluminum hydroxide and 2% of modified graphene oxide into the mixed material, starting a homogenizer and a shearing machine to circularly stir for 100min, passing through a molecular sieve filter pressing barrel, and adsorbing and filtering large particles in the mixed material; adding 3% of 4, 4' -dioxydiphenyl sulfone (DDS), 1.5% of 2-ethylimidazole, 3% of cobalt acetylacetonate and butyl triphenyl phosphonium bromide into the obtained mixed material in a ratio of 1:1, circularly stirring for 90min, and preparing to obtain a glue solution; dipping the obtained glue solution on glass fiber cloth through a vertical gluing machine, and baking the glass fiber cloth dipped with the glue solution at the baking temperature of 80 ℃ for 16min to form a continuous prepreg; and covering copper foil on the obtained prepreg, and performing hot press molding through a hot press to obtain the medium Tg copper clad laminate used for the halogen-free manufacture procedure of the PCB.
In the invention, the novel halogen-free resin system is adopted to improve the heat resistance of the material, so that the material property can meet the requirement of a PCB lead-free process; the novel resin is used for improving the viscosity of the glue, so that the resin amount is reduced, the resin content is uniform, and the impregnation effect of the glass fiber cloth is good during gluing; the size stability of the copper clad laminate prepared by the novel resin system can be improved, and the PCB processing performance is better; the prepared copper-clad plate has the following characteristics: the Tg of the material is more than or equal to 150 ℃, and the halogen-free and lead-free process is compatible with the plate; the adhesive has excellent peeling strength; low Z-CTE values; excellent CAF resistance; UV Blocking is compatible with AOI; low water absorption; excellent dimensional stability; the product is suitable for the manufacture procedure requirement of PCB halogen-free and lead-free manufacture procedure, the technical index of the product meets the IPC standard requirement, and the product is mainly applied to the fields of consumer electronics, instruments and meters, communication equipment, automobile electronics and the like.
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 (7)
1. The heat-resistant epoxy resin composition is characterized by comprising the following components in percentage by weight:
2. the heat-resistant epoxy resin composition according to claim 1, further comprising a catalyst in an amount of 2 to 5%.
3. The heat-resistant epoxy resin composition according to claim 2, wherein the catalyst is one or a mixture of two of cobalt acetylacetonate and butyltriphenylphosphonium bromide.
4. The heat-resistant epoxy resin composition according to claim 1, wherein the organic solvent is one 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.
5. The modified epoxy resin composition of claim 1, wherein the curing accelerator is one 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.
6. The method for preparing the halogen-free middle Tg copper clad laminate by using the heat-resistant epoxy resin composition as claimed in claim 1 or 2 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 graphene modified epoxy resin, novolac epoxy resin, MDI modified bromine-free resin, four-functional group epoxy resin, phenolic resin and an organic solvent, and stirring for 120-240 min until the halogen-free epoxy resin is completely dissolved in the organic solvent;
s2, adding composite silicon micropowder, aluminum hydroxide and modified graphene oxide into the mixed material obtained in the step 1, starting a homogenizer and a shearing machine to circularly stir for 90-120 min, and passing through a molecular sieve filter pressing barrel to adsorb and filter large particles in the mixed material;
s3, adding 4, 4' -dioxydiphenyl sulfone (DDS), a curing accelerator and a catalyst into the mixed material obtained in the step 2, circularly stirring for 30-120 min, and preparing to obtain a glue solution;
s4, dipping the glue solution obtained in the step 3 on glass fiber cloth through a vertical gluing machine, and baking the glass fiber cloth dipped with the glue solution at the baking temperature of 60-120 ℃ for 5-20 min to form a continuous prepreg;
and S5, covering copper foil on the prepreg obtained in the step 4, and performing hot press molding through a hot press to obtain the medium Tg copper clad laminate used in the halogen-free manufacturing process of the PCB.
7. A halogen-free middle Tg copper-clad plate is characterized by being prepared by the preparation method of claim 6.
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