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
- Publication number
- CN112250999A CN112250999A CN202011134410.7A CN202011134410A CN112250999A CN 112250999 A CN112250999 A CN 112250999A CN 202011134410 A CN202011134410 A CN 202011134410A CN 112250999 A CN112250999 A CN 112250999A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- free
- halogen
- copper
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2463/04—Epoxynovolacs
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
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)
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.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011134410.7A CN112250999A (en) | 2020-10-21 | 2020-10-21 | Heat-resistant epoxy resin composition, halogen-free middle-Tg copper-clad plate and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011134410.7A CN112250999A (en) | 2020-10-21 | 2020-10-21 | Heat-resistant epoxy resin composition, halogen-free middle-Tg copper-clad plate and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112250999A true CN112250999A (en) | 2021-01-22 |
Family
ID=74263451
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011134410.7A Pending CN112250999A (en) | 2020-10-21 | 2020-10-21 | Heat-resistant epoxy resin composition, halogen-free middle-Tg copper-clad plate and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112250999A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113038696A (en) * | 2021-03-02 | 2021-06-25 | 广德新三联电子有限公司 | High-bending-resistance circuit board for automobile and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140322541A1 (en) * | 2013-04-24 | 2014-10-30 | Elite Electronic Material (Kunshan) Co., Ltd | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same |
US20160002390A1 (en) * | 2013-01-07 | 2016-01-07 | Toray Industries, Inc. | Epoxy resin composition, prepreg, fiber reinforced plastic material, and manufacturing method for fiber reinforced plastic material |
CN106009514A (en) * | 2016-06-20 | 2016-10-12 | 山东欧铂新材料有限公司 | Preparation method for graphene/epoxy resin composite material |
CN106916418A (en) * | 2015-12-25 | 2017-07-04 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and printed circuit board |
CN109627689A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of preparation method of graphene-epoxy resin composite material |
CN109762301A (en) * | 2018-12-28 | 2019-05-17 | 苏州博瑞达高分子材料有限公司 | A kind of preparation method of polymer graphite alkene modified epoxy |
-
2020
- 2020-10-21 CN CN202011134410.7A patent/CN112250999A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160002390A1 (en) * | 2013-01-07 | 2016-01-07 | Toray Industries, Inc. | Epoxy resin composition, prepreg, fiber reinforced plastic material, and manufacturing method for fiber reinforced plastic material |
US20140322541A1 (en) * | 2013-04-24 | 2014-10-30 | Elite Electronic Material (Kunshan) Co., Ltd | Halogen-free resin composition, copper clad laminate using the same, and printed circuit board using the same |
CN106916418A (en) * | 2015-12-25 | 2017-07-04 | 广东生益科技股份有限公司 | A kind of compositions of thermosetting resin, prepreg, metal-clad laminate and printed circuit board |
CN106009514A (en) * | 2016-06-20 | 2016-10-12 | 山东欧铂新材料有限公司 | Preparation method for graphene/epoxy resin composite material |
CN109627689A (en) * | 2018-11-23 | 2019-04-16 | 贵州航天天马机电科技有限公司 | A kind of preparation method of graphene-epoxy resin composite material |
CN109762301A (en) * | 2018-12-28 | 2019-05-17 | 苏州博瑞达高分子材料有限公司 | A kind of preparation method of polymer graphite alkene modified epoxy |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113038696A (en) * | 2021-03-02 | 2021-06-25 | 广德新三联电子有限公司 | High-bending-resistance circuit board for automobile and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101538397B (en) | Epoxy resin composition, glue film made of same and preparation method | |
CN1200970C (en) | Modified dimaleimide resin and its preparation method and application in cladding copper plate | |
CN105172297A (en) | Flame-resistant and heat-resistant copper clad laminate preparation method | |
CN103298882A (en) | Heat-curable resin composition, and prepreg and metal foil-stacked plate using same | |
CN100999145A (en) | Preparation method of glass transition temperature halogenless fire retardant glass cloth laminated board | |
CN1170908C (en) | Interlamellar insulation adhesive using for multilayer printed circuit board | |
CN112778702B (en) | Epoxy resin composite material and laminated board as well as preparation method and application thereof | |
CN112175354A (en) | Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof | |
CN112250997A (en) | Heat-resistant epoxy resin composition, lead-free middle-Tg copper-clad plate and preparation method thereof | |
CN1296433C (en) | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process | |
CN114410046A (en) | Preparation method of hydrocarbon resin base plate material for high-frequency copper-clad plate | |
CN103724997B (en) | A kind of Halogen low water suction thermoset fire-proof resin composition and application | |
CN109575523A (en) | A kind of highly thermal-conductive resin composition for copper-clad plate | |
CN105082669B (en) | A kind of production method of epoxy glass-fiber-fabric copper-clad plate | |
CN115139589A (en) | High-thermal-conductivity copper-clad plate and preparation method thereof | |
CN112063111A (en) | Modified epoxy resin composition, high-Tg low-loss laminated copper-clad plate and preparation method thereof | |
CN112250999A (en) | Heat-resistant epoxy resin composition, halogen-free middle-Tg copper-clad plate and preparation method thereof | |
CN114591580A (en) | Fluorine-containing resin mixture, prepreg and high-heat-conductivity high-frequency copper-clad plate | |
CN102936396A (en) | Toughening epoxy resin composition | |
CN111605269A (en) | FR4 copper-clad plate with high relative tracking index and high heat resistance and preparation method thereof | |
CN116604917A (en) | Preparation method of CAF-resistant FR-4 copper-clad plate | |
CN103200772B (en) | A kind of pcb board of high CTI and preparation method thereof | |
CN114987005A (en) | Epoxy resin-based copper-clad plate filled with aluminum oxide and preparation method thereof | |
CN106364122A (en) | Manufacturing method of high-Tg lead-free low-dielectric copper-foil-coated board | |
KR20000028796A (en) | Thermosetting resin compositions for build-up method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination |