CN116901550B - High-heat-dissipation liquid crystal epoxy resin copper-clad plate and preparation method thereof - Google Patents

High-heat-dissipation liquid crystal epoxy resin copper-clad plate and preparation method thereof Download PDF

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CN116901550B
CN116901550B CN202310822801.5A CN202310822801A CN116901550B CN 116901550 B CN116901550 B CN 116901550B CN 202310822801 A CN202310822801 A CN 202310822801A CN 116901550 B CN116901550 B CN 116901550B
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epoxy resin
liquid crystal
clad plate
crystal epoxy
parts
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CN116901550A (en
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周培峰
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Jiangmen Kingboard Electronic Development Co ltd
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Jiangmen Kingboard Electronic Development Co ltd
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    • 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
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
    • B29C43/20—Making multilayered or multicoloured articles
    • B29C43/203—Making multilayered articles
    • 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
    • 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
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
    • H05K1/0203—Cooling of mounted components
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • 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
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—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
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/302—Conductive
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/02—Polyglycidyl ethers of bis-phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2463/10—Epoxy resins modified by unsaturated compounds
    • 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
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    • C08K3/34—Silicon-containing compounds
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    • C08K7/02—Fibres or whiskers
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    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/06—Lamination

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Abstract

The invention provides a high-heat-dissipation liquid crystal epoxy resin copper-clad plate, which is prepared from the following raw materials in parts by weight: 15-20 parts of bisphenol A type epoxy resin, 5-8 parts of dicyclopentadiene phenol epoxy resin, 8-12 parts of liquid crystal epoxy resin monomer, 6-9 parts of curing agent, 0.05-0.1 part of curing accelerator, 55-60 parts of filler and 65-70 parts of solvent. The invention also provides a preparation method of the high-heat-dissipation liquid crystal epoxy resin copper-clad plate. The high-heat-dissipation liquid crystal epoxy resin copper-clad plate provided by the invention has better heat-dissipation performance, heat-resistant performance and toughness.

Description

High-heat-dissipation liquid crystal epoxy resin copper-clad plate and preparation method thereof
Technical Field
The invention relates to a copper-clad plate, in particular to a high-heat-dissipation liquid crystal epoxy resin copper-clad plate and a preparation method thereof.
Background
The copper clad laminate is a plate-shaped composite material prepared by immersing electronic glass fiber cloth or other reinforcing materials in resin liquid, coating copper foil on one or both sides, and hot-pressing at a certain temperature and pressure, and is called copper clad laminate (CopperClad Laminate, CCL), which is called copper clad laminate for short. Copper-clad laminates are substrates for processing Printed Circuit Boards (PCBs), the development of which is basically attached to the development of the PCB industry, and PCBs have become an indispensable major component for most electronic products to reach circuit interconnection. As electronic products become smaller, packaging density of electronic devices is higher and higher, and requirements on heat dissipation performance of copper-clad plates are also higher and higher.
Most of the resin liquid used by the existing copper-clad plate is a resin composition taking epoxy resin as a main body, and the epoxy resin is a thermosetting polymer and has the advantages of good bonding property, high mechanical strength, good electrical insulation, small curing shrinkage and the like, but the cured product is a three-dimensional network structure with high crosslinking density, so that the crack expansibility and toughness of the epoxy resin material are poor, and the heat resistance is also not ideal. Therefore, development of a novel copper-clad plate with high heat dissipation is needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-heat-dissipation liquid crystal epoxy resin copper-clad plate which has better heat dissipation performance, heat resistance and toughness.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the resin glue solution used for preparing the high-heat-dissipation liquid crystal epoxy resin copper-clad plate is prepared from the following raw materials in parts by weight: 15-20 parts of bisphenol A type epoxy resin, 5-8 parts of dicyclopentadiene phenol epoxy resin, 8-12 parts of liquid crystal epoxy resin monomer, 6-9 parts of curing agent, 0.05-0.1 part of curing accelerator, 55-60 parts of filler and 65-70 parts of solvent.
Further, the liquid crystal epoxy resin monomer of the invention is prepared by the following steps:
mixing 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide, performing ultrasonic treatment for 30-40 minutes to obtain a mixed solution, heating the mixed solution to 85 ℃ under the protection of nitrogen, stirring and refluxing for reaction for 10-12 hours to obtain a reactant, cooling the reactant to room temperature, respectively washing the reactant with absolute ethyl alcohol and dimethyl sulfoxide for 3 times, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the liquid crystal epoxy resin monomer.
Further, in the preparation step of the liquid crystal epoxy resin monomer, the proportion of 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide is 1.2g:1g:250mL, the ultrasonic power is 300W, the drying temperature is 85 ℃, and the drying time is 10 hours.
Further, the curing agent disclosed by the invention consists of 4,4 '-bis (4-aminophenoxy) diphenyl sulfone and 4,4' -methylenedianiline in a mass ratio of 3:2.
Further, the curing accelerator of the present invention is 2-ethyl-4-methylimidazole.
Further, the filler of the present invention is composed of equal mass of boron nitride and silicon nitride.
Further, the solvent disclosed by the invention comprises the following components in percentage by mass: 2, acetone and propylene glycol methyl ether.
The invention aims to provide a preparation method of the high-heat-dissipation liquid crystal epoxy resin copper-clad plate.
In order to solve the technical problems, the technical scheme is as follows:
a preparation method of a high-heat-dissipation liquid crystal epoxy resin copper-clad plate comprises the following steps:
s1, weighing raw materials according to parts by weight, mixing bisphenol A epoxy resin, dicyclopentadiene epoxy resin, liquid crystal epoxy resin monomer, curing agent, curing accelerator, filler and solvent, and uniformly stirring to obtain resin glue solution;
s2, dipping the glass fiber cloth in the resin glue solution obtained in the step S1 for 10-20 minutes, taking out, and then transferring into an oven to bake for 6-10 minutes to obtain a prepreg;
s3, 8 prepregs obtained in the step S2 are stacked together, the two sides of the prepregs are covered with copper foil after being cut neatly, and the prepregs are placed in a hot press for hot pressing for 2-4 hours to obtain the high-heat-dissipation liquid crystal epoxy resin copper-clad plate.
Further, in the step S2, the baking temperature is 130-160 ℃.
Further, in the step S3, the hot pressing temperature is 210-240 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) The filler used in the invention is boron nitride and silicon nitride, and has higher heat conductivity, so that the heat conductivity of the copper-clad plate can be effectively improved, and the heat dissipation performance of the copper-clad plate is improved.
(2) The Liquid Crystal Epoxy Resin (LCER) is an epoxy compound containing rigid rod-shaped (rib rod) liquid crystal elements, liquid crystal is easy to orient spontaneously or along the external field direction in the curing reaction process, the order degree of the system is increased, the ordered irreversible reaction can be fixed through the curing reaction, a local ordered self-reinforced structure is formed, the toughness of a cured product is improved, but the heat dissipation property is also not ideal, therefore, the liquid crystal epoxy resin monomer is prepared by grafting reaction of aminopropyl isobutyl silsesquioxane with a cage structure and an epoxy compound containing liquid crystal elements, namely 4,4' -biphenol diglycidyl ether, and can form an ordered lattice structure after curing and form a heat conducting network chain with a filler, and the structural orientation of the liquid crystal epoxy resin monomer and the filler is consistent with the heat transfer direction, so that the heat conductivity and the heat dissipation property of a copper clad plate are further provided; in addition, the liquid crystal epoxy resin monomer also has better high temperature resistance, so that the heat resistance of the copper-clad plate can be effectively improved.
(3) The invention also uses dicyclopentadiene phenol epoxy resin, which has good toughness and heat resistance, thus further improving the heat resistance and toughness of the copper-clad plate.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments of the present invention and the descriptions thereof are provided for the purpose of illustrating the present invention, but are not to be construed as limiting the present invention.
Example 1
The high-heat-dissipation liquid crystal epoxy resin copper-clad plate is prepared from the following raw materials in parts by weight: 17 parts of bisphenol A epoxy resin, 7 parts of dicyclopentadiene phenol epoxy resin, 10 parts of liquid crystal epoxy resin monomer, 8 parts of curing agent consisting of 4,4 '-bis (4-aminophenoxy) diphenyl sulfone and 4,4' -methylenedianiline in a mass ratio of 3:2, 0.06 part of 2-ethyl-4-methylimidazole, 58 parts of filler consisting of boron nitride and silicon nitride in an equal mass ratio, and 69 parts of solvent consisting of acetone and propylene glycol methyl ether in a mass ratio of 3:2.
The liquid crystal epoxy resin monomer is prepared by the following steps:
mixing 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide in the ratio of 1.2g to 1g to 250mL, performing ultrasonic treatment for 35 minutes under 300W power to obtain a mixed solution, heating the mixed solution to 85 ℃ under the protection of nitrogen, stirring and refluxing for 11 hours to obtain a reactant, cooling the reactant to room temperature, respectively washing the reactant with absolute ethyl alcohol and dimethyl sulfoxide for 3 times, performing suction filtration to obtain a filter cake, and drying the filter cake at 85 ℃ for 10 hours to obtain the liquid crystal epoxy resin monomer.
The preparation method of the embodiment comprises the following steps:
s1, weighing raw materials according to parts by weight, mixing bisphenol A epoxy resin, dicyclopentadiene epoxy resin, liquid crystal epoxy resin monomer, curing agent, 2-ethyl-4-methylimidazole, filler and solvent, and uniformly stirring to obtain resin glue solution;
s2, dipping the glass fiber cloth in the resin glue solution obtained in the step S1 for 15 minutes, taking out, and then transferring the glass fiber cloth into an oven to bake for 7 minutes at 150 ℃ to obtain a prepreg;
s3, 8 prepregs obtained in the step S2 are stacked together, the two sides of the prepregs are covered with copper foil after being cut neatly, and the prepregs are placed in a hot press for hot pressing for 3 hours at 220 ℃ to obtain the high-heat-dissipation liquid crystal epoxy resin copper-clad plate.
Example 2
The high-heat-dissipation liquid crystal epoxy resin copper-clad plate is prepared from the following raw materials in parts by weight: 18 parts of bisphenol A epoxy resin, 6 parts of dicyclopentadiene phenol epoxy resin, 12 parts of liquid crystal epoxy resin monomer, 6 parts of curing agent consisting of 4,4 '-bis (4-aminophenoxy) diphenyl sulfone and 4,4' -methylenedianiline in a mass ratio of 3:2, 0.05 part of 2-ethyl-4-methylimidazole, 60 parts of filler consisting of boron nitride and silicon nitride in an equal mass ratio, and 66 parts of solvent consisting of acetone and propylene glycol methyl ether in a mass ratio of 3:2.
The liquid crystal epoxy resin monomer is prepared by the following steps:
mixing 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide according to the ratio of 1.2g to 1g to 250mL, performing ultrasonic treatment for 30 minutes under 300W power to obtain a mixed solution, heating the mixed solution to 85 ℃ under the protection of nitrogen, stirring and refluxing for reaction for 10 hours to obtain a reactant, cooling the reactant to room temperature, respectively washing the reactant with absolute ethyl alcohol and dimethyl sulfoxide for 3 times, performing suction filtration to obtain a filter cake, and drying the filter cake at 85 ℃ for 10 hours to obtain the liquid crystal epoxy resin monomer.
The preparation method of the embodiment comprises the following steps:
s1, weighing raw materials according to parts by weight, mixing bisphenol A epoxy resin, dicyclopentadiene epoxy resin, liquid crystal epoxy resin monomer, curing agent, 2-ethyl-4-methylimidazole, filler and solvent, and uniformly stirring to obtain resin glue solution;
s2, dipping the glass fiber cloth in the resin glue solution obtained in the step S1 for 10 minutes, taking out, and then transferring the glass fiber cloth into an oven to bake for 10 minutes at 130 ℃ to obtain a prepreg;
s3, 8 prepregs obtained in the step S2 are stacked together, the two sides of the prepregs are covered with copper foil after being cut neatly, and the prepregs are placed in a hot press for hot pressing for 4 hours at 210 ℃ to obtain the high-heat-dissipation liquid crystal epoxy resin copper-clad plate.
Example 3
The high-heat-dissipation liquid crystal epoxy resin copper-clad plate is prepared from the following raw materials in parts by weight: 15 parts of bisphenol A epoxy resin, 8 parts of dicyclopentadiene phenol epoxy resin, 9 parts of liquid crystal epoxy resin monomer, 7 parts of curing agent consisting of 4,4 '-bis (4-aminophenoxy) diphenyl sulfone and 4,4' -methylenedianiline in a mass ratio of 3:2, 0.09 part of 2-ethyl-4-methylimidazole, 56 parts of filler consisting of boron nitride and silicon nitride in an equal mass ratio, and 70 parts of solvent consisting of acetone and propylene glycol methyl ether in a mass ratio of 3:2.
The liquid crystal epoxy resin monomer is prepared by the following steps:
mixing 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide according to the ratio of 1.2g to 1g to 250mL, performing ultrasonic treatment for 35 minutes under 300W power to obtain a mixed solution, heating the mixed solution to 85 ℃ under the protection of nitrogen, stirring and refluxing for 10.5 hours to obtain a reactant, cooling the reactant to room temperature, respectively washing the reactant with absolute ethyl alcohol and dimethyl sulfoxide for 3 times, performing suction filtration to obtain a filter cake, and drying the filter cake at 85 ℃ for 10 hours to obtain the liquid crystal epoxy resin monomer.
The preparation method of the embodiment comprises the following steps:
s1, weighing raw materials according to parts by weight, mixing bisphenol A epoxy resin, dicyclopentadiene epoxy resin, liquid crystal epoxy resin monomer, curing agent, 2-ethyl-4-methylimidazole, filler and solvent, and uniformly stirring to obtain resin glue solution;
s2, dipping the glass fiber cloth in the resin glue solution obtained in the step S1 for 16 minutes, taking out, and then transferring the glass fiber cloth into an oven to bake for 8 minutes at 140 ℃ to obtain a prepreg;
s3, 8 prepregs obtained in the step S2 are stacked together, the two sides of the prepregs are covered with copper foil after being cut neatly, and the prepregs are placed in a hot press for hot pressing for 2.5 hours at 230 ℃ to obtain the high-heat-dissipation liquid crystal epoxy resin copper-clad plate.
Example 4
The high-heat-dissipation liquid crystal epoxy resin copper-clad plate is prepared from the following raw materials in parts by weight: 20 parts of bisphenol A epoxy resin, 5 parts of dicyclopentadiene phenol epoxy resin, 8 parts of liquid crystal epoxy resin monomer, 9 parts of curing agent consisting of 4,4 '-bis (4-aminophenoxy) diphenyl sulfone and 4,4' -methylenedianiline in a mass ratio of 3:2, 0.1 part of 2-ethyl-4-methylimidazole, 55 parts of filler consisting of boron nitride and silicon nitride in an equal mass ratio, and 65 parts of solvent consisting of acetone and propylene glycol methyl ether in a mass ratio of 3:2.
The liquid crystal epoxy resin monomer is prepared by the following steps:
mixing 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide according to the ratio of 1.2g to 1g to 250mL, performing ultrasonic treatment at 300W power for 40 minutes to obtain a mixed solution, heating the mixed solution to 85 ℃ under the protection of nitrogen, stirring and refluxing for 12 hours to obtain a reactant, cooling the reactant to room temperature, washing the reactant with absolute ethyl alcohol and dimethyl sulfoxide for 3 times respectively, performing suction filtration to obtain a filter cake, and drying the filter cake at 85 ℃ for 10 hours to obtain the liquid crystal epoxy resin monomer.
The preparation method of the embodiment comprises the following steps:
s1, weighing raw materials according to parts by weight, mixing bisphenol A epoxy resin, dicyclopentadiene epoxy resin, liquid crystal epoxy resin monomer, curing agent, 2-ethyl-4-methylimidazole, filler and solvent, and uniformly stirring to obtain resin glue solution;
s2, dipping the glass fiber cloth in the resin glue solution obtained in the step S1 for 20 minutes, taking out, and then transferring the glass fiber cloth into an oven to bake for 6 minutes at 160 ℃ to obtain a prepreg;
s3, 8 prepregs obtained in the step S2 are stacked together, the two sides of the prepregs are covered with copper foil after being cut neatly, and the prepregs are placed in a hot press for hot pressing for 2 hours at 240 ℃ to obtain the high-heat-dissipation liquid crystal epoxy resin copper-clad plate.
Comparative example 1
The difference from example 1 is that: the liquid crystal epoxy resin monomer in the raw materials is replaced by 4,4' -biphenol diglycidyl ether, and the preparation step of the liquid crystal epoxy resin monomer is omitted.
Comparative example 2
Unlike example 1, the following is: the raw materials do not include dicyclopentadiene phenol epoxy resin.
Comparative example 3
Unlike example 1, the following is: the filler in the feedstock is replaced by silica.
Experimental example one: test of heat dissipation performance
Test reference standard/method: ASTM D5470-2006 standard.
Test instrument: and a thermal conductivity analyzer.
Test object, target: thermal conductivity of the copper clad laminate prepared in examples 1 to 4, comparative example 1, comparative example 3.
The higher thermal conductivity indicates better heat dissipation performance, and the test results are shown in table 1:
thermal conductivity (W/m.k)
Example 1 1.58
Example 2 1.61
Example 3 1.56
Example 4 1.55
Comparative example 1 1.24
Comparative example 3 1.09
TABLE 1
As can be seen from Table 1, the thermal conductivities of examples 1-4 of the present invention are all higher, indicating that the present invention has better heat dissipation performance. The partial raw materials and the preparation steps used in the comparative examples 1 and 3 are different from those in the example 1, and compared with the example 1, the thermal conductivity of the comparative example 1 is reduced, which shows that compared with the 4,4' -biphenol diglycidyl ether which is not subjected to grafting reaction, the liquid crystal epoxy resin prepared by the invention has better effect of improving the heat dissipation performance of the copper-clad plate; compared with the example 1, the thermal conductivity of the comparative example 3 is greatly reduced, which shows that the filler composed of boron nitride and silicon nitride used in the invention is a main factor for improving the heat dissipation performance of the copper-clad plate.
Experimental example two: heat resistance test
Test reference standard/method: DSC method.
Test instrument: differential scanning calorimeter.
Test object, target: glass transition temperatures of the copper clad laminates prepared in examples 1 to 4 and comparative examples 1 to 2.
The higher the glass transition temperature, the better the heat resistance, and the test results are shown in table 2:
glass transition temperature (. Degree. C.)
Example 1 201
Example 2 206
Example 3 203
Example 4 198
Comparative example 1 192
Comparative example 2 191
TABLE 2
As can be seen from Table 2, the glass transition temperatures of examples 1 to 4 of the present invention are all higher, indicating that the present invention has better heat resistance. The partial raw materials and the preparation steps used in comparative examples 1-2 are different from those in example 1, and compared with example 1, the glass transition temperature of comparative example 1 is reduced, which shows that compared with 4,4' -biphenol diglycidyl ether which is not subjected to grafting reaction, the liquid crystal epoxy resin prepared by the invention has better effect of improving the heat resistance of the copper-clad plate; compared with the example 1, the glass transition temperature of the comparative example 2 is also reduced, which shows that the dicyclopentadiene phenol epoxy resin used in the invention can also improve the heat resistance of the copper-clad plate.
Experimental example three: toughness testing
The testing method comprises the following steps: drop hammer impact method.
Test instrument: drop hammer impact testing machine.
Test object, target: the copper clad laminates prepared in examples 1 to 4 and comparative examples 1 to 2 had drop weight impact areas, drop weight heights of 1m and drop weights of 1kg.
The smaller the drop hammer impact area, the better the toughness. The test results are shown in table 3:
drop hammer impact area (mm) 2 )
Example 1 165
Example 2 158
Example 3 161
Example 4 169
Comparative example 1 182
Comparative example 2 180
TABLE 3 Table 3
As can be seen from Table 3, the drop hammer impact areas of examples 1-4 of the present invention are all smaller, indicating that the present invention has better toughness. The part of raw materials used in comparative examples 1-2 and the preparation steps are different from those in example 1, and compared with example 1, the drop hammer impact area of comparative example 1 is increased, which shows that compared with 4,4' -biphenol diglycidyl ether which is not subjected to grafting reaction, the liquid crystal epoxy resin prepared by the invention has better effect of improving the toughness of a copper-clad plate; compared with the example 1, the drop hammer impact area of the comparative example 2 is also increased, which shows that the dicyclopentadiene phenol epoxy resin used in the invention can also improve the toughness of the copper-clad plate.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.

Claims (9)

1. The utility model provides a high heat dissipation liquid crystal epoxy copper-clad plate which characterized in that: the resin glue solution used for preparing the high-heat-dissipation liquid crystal epoxy resin copper-clad plate is prepared from the following raw materials in parts by weight: 15-20 parts of bisphenol A type epoxy resin, 5-8 parts of dicyclopentadiene phenol epoxy resin, 8-12 parts of liquid crystal epoxy resin monomer, 6-9 parts of curing agent, 0.05-0.1 part of curing accelerator, 55-60 parts of filler and 65-70 parts of solvent;
the liquid crystal epoxy resin monomer is prepared by the following steps:
mixing 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide, performing ultrasonic treatment for 30-40 minutes to obtain a mixed solution, heating the mixed solution to 85 ℃ under the protection of nitrogen, stirring and refluxing for reaction for 10-12 hours to obtain a reactant, cooling the reactant to room temperature, respectively washing the reactant with absolute ethyl alcohol and dimethyl sulfoxide for 3 times, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the liquid crystal epoxy resin monomer.
2. The high heat dissipation liquid crystal epoxy resin copper-clad plate according to claim 1, wherein: in the preparation step of the liquid crystal epoxy resin monomer, the proportion of 4,4' -biphenol diglycidyl ether, aminopropyl isobutyl silsesquioxane and dimethyl sulfoxide is 1.2g:1g:250mL, the ultrasonic power is 300W, the drying temperature is 85 ℃, and the drying time is 10 hours.
3. The high heat dissipation liquid crystal epoxy resin copper-clad plate according to claim 1, wherein: the curing agent consists of 4,4 '-bis (4-aminophenoxy) diphenylsulfone and 4,4' -methylenedianiline in a mass ratio of 3:2.
4. The high heat dissipation liquid crystal epoxy resin copper-clad plate according to claim 1, wherein: the curing accelerator is 2-ethyl-4-methylimidazole.
5. The high heat dissipation liquid crystal epoxy resin copper-clad plate according to claim 1, wherein: the filler consists of equal mass of boron nitride and silicon nitride.
6. The high heat dissipation liquid crystal epoxy resin copper-clad plate according to claim 1, wherein: the solvent consists of acetone and propylene glycol methyl ether in a mass ratio of 3:2.
7. The method for preparing the high-heat-dissipation liquid crystal epoxy resin copper-clad plate according to any one of claims 1 to 6, which is characterized in that: the method comprises the following steps:
s1, weighing raw materials according to parts by weight, mixing bisphenol A epoxy resin, dicyclopentadiene phenol epoxy resin, liquid crystal epoxy resin monomer, curing agent, curing accelerator, filler and solvent, and uniformly stirring to obtain resin glue solution;
s2, dipping the glass fiber cloth in the resin glue solution obtained in the step S1 for 10-20 minutes, taking out, and then transferring into an oven to bake for 6-10 minutes to obtain a prepreg;
s3, 8 prepregs obtained in the step S2 are stacked together, the two sides of the prepregs are covered with copper foil after being cut neatly, and the prepregs are placed in a hot press for hot pressing for 2-4 hours to obtain the high-heat-dissipation liquid crystal epoxy resin copper-clad plate.
8. The method for preparing the high-heat-dissipation liquid crystal epoxy resin copper-clad plate according to claim 7, which is characterized in that: in the step S2, the baking temperature is 130-160 ℃.
9. The method for preparing the high-heat-dissipation liquid crystal epoxy resin copper-clad plate according to claim 7, which is characterized in that: in the step S3, the hot pressing temperature is 210-240 ℃.
CN202310822801.5A 2023-07-05 2023-07-05 High-heat-dissipation liquid crystal epoxy resin copper-clad plate and preparation method thereof Active CN116901550B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102492116A (en) * 2011-11-27 2012-06-13 吉林大学 Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method
CN102504202A (en) * 2011-10-10 2012-06-20 中科院广州化学有限公司 Liquid crystal epoxy resin with shape memory effect and preparation method and application thereof
CN105437668A (en) * 2015-12-25 2016-03-30 广东生益科技股份有限公司 Ultrathin copper clad laminate and production method thereof
CN115141463A (en) * 2021-03-31 2022-10-04 华为技术有限公司 Heat conduction material and manufacturing method thereof, prepreg, laminated board and circuit board

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504202A (en) * 2011-10-10 2012-06-20 中科院广州化学有限公司 Liquid crystal epoxy resin with shape memory effect and preparation method and application thereof
CN102492116A (en) * 2011-11-27 2012-06-13 吉林大学 Epoxy resin and polyhedral silsesquioxane nano hybrid material and its preparation method
CN105437668A (en) * 2015-12-25 2016-03-30 广东生益科技股份有限公司 Ultrathin copper clad laminate and production method thereof
CN115141463A (en) * 2021-03-31 2022-10-04 华为技术有限公司 Heat conduction material and manufacturing method thereof, prepreg, laminated board and circuit board

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