CN117500151A - Copper-clad plate with high Tg - Google Patents

Copper-clad plate with high Tg Download PDF

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Publication number
CN117500151A
CN117500151A CN202311463676.XA CN202311463676A CN117500151A CN 117500151 A CN117500151 A CN 117500151A CN 202311463676 A CN202311463676 A CN 202311463676A CN 117500151 A CN117500151 A CN 117500151A
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CN
China
Prior art keywords
parts
copper
boron nitride
benzimidazole
modified polybutadiene
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Granted
Application number
CN202311463676.XA
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Chinese (zh)
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CN117500151B (en
Inventor
董立波
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An Neng Electronics Co ltd
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An Neng Electronics Co ltd
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    • 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
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
    • B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
    • B29C66/45—Joining of substantially the whole surface of the articles
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
    • B29C66/721—Fibre-reinforced materials
    • B29C66/7212—Fibre-reinforced materials characterised by the composition of the 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/731—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the intensive physical properties of the material of the parts to be joined
    • B29C66/7311—Thermal properties
    • 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
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/74—Joining plastics material to non-plastics material
    • B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
    • B29C66/7428—Transition metals or their alloys
    • B29C66/74281—Copper or alloys of copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • 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
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    • 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
    • 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
    • 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
    • H05K1/036—Multilayers with layers of different types
    • 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
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    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
    • 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
    • H05K3/0011—Working of insulating substrates or insulating layers
    • 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
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    • B29L2007/008—Wide strips, e.g. films, webs
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    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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    • H05K2201/0104—Properties and characteristics in general
    • H05K2201/012—Flame-retardant; Preventing of inflammation
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/06—Thermal details
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/06—Lamination

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Fluid Mechanics (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a high Tg copper-clad plate, which belongs to the technical field of copper-clad plates and comprises the following specific preparation steps: weighing the following raw materials in parts by weight: 95-105 parts of modified polybutadiene, 40-50 parts of styrene-butadiene-styrene copolymer, 6 parts of initiator, 20-30 parts of dicyclopentadiene phenol epoxy resin, 5 parts of triallyl isocyanurate, 50 parts of flame retardant, 40-60 parts of heat conducting composite filler, 70-90 parts of toluene, 20 parts of butanone and 10-20 parts of propylene glycol monomethyl ether; uniformly mixing the raw materials to obtain hydrocarbon resin glue solution; the electronic glass fiber is arranged in hydrocarbon resin glue solution, is taken out and baked after being immersed, so as to obtain a prepreg, the prepreg is cut and attached, and then is overlapped with copper foil, and the copper-clad plate is formed by hot pressing.

Description

Copper-clad plate with high Tg
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a high-Tg copper-clad plate.
Background
The copper clad laminate (copper clad laminate, CCL) is a board which is formed by covering copper foil on one or both sides of raw materials such as reinforcing materials, resin, filler, curing agent and the like through a certain technological process and performing thermal compression, and is also a substrate of a printed circuit board.
The traditional epoxy resin is the main stream of the market until the 5G age comes on the basis of low price and mature process, but the high dielectric constant and the high dielectric loss of the traditional epoxy resin cannot meet the requirements of the existing market. Polyphenylene ether has excellent properties such as low polarity, high heat resistance, etc., but has difficulty in application because polyphenylene sulfide having too large a molecular weight has poor fluidity and is not easy to process and mold. The hydrocarbon resin gradually goes into the field of view of people due to the characteristics of excellent dielectric property, good processability, low water absorption rate and the like, but the hydrocarbon polymer has the defects of low peeling strength, low glass transition temperature (Tg), low heat conductivity coefficient and the like, and the prepared copper clad laminate copper foil has weak bonding force, poor heat resistance and poor heat dissipation, and especially along with the development of high frequency and high speed of signal transmission, the heat management of the copper clad laminate is more and more important, the heat conductivity coefficient of the copper clad laminate is definitely required in certain application occasions, the higher the heat conductivity coefficient is, the faster the heat dissipation of the components is, the heat generated by the plate in the use process can be timely released, the performance change caused by the overhigh temperature rise of the plate is prevented, the substrate is better protected, and the service life of the copper clad laminate with high peeling resistance and heat conductivity coefficient is necessary.
Disclosure of Invention
The invention aims to provide a high-Tg copper-clad plate, which solves the problems of low peeling strength, low glass transition temperature (Tg) and low heat conductivity of the existing hydrocarbon resin copper-clad plate.
The aim of the invention can be achieved by the following technical scheme:
a copper-clad plate with high Tg comprises an electronic glass fiber cloth, hydrocarbon resin glue solution and a copper foil, wherein the hydrocarbon resin glue solution is coated on the electronic glass fiber cloth, and then the copper foil is coated on the electronic glass fiber cloth, and the copper-clad plate is obtained through hot pressing.
The preparation method of the high Tg copper-clad plate comprises the following specific steps:
s1, weighing the following raw materials in parts by weight: 95-105 parts of modified polybutadiene, 40-50 parts of styrene-butadiene-styrene copolymer, 6 parts of initiator, 20-30 parts of dicyclopentadiene phenol epoxy resin, 5 parts of triallyl isocyanurate, 50 parts of flame retardant, 40-60 parts of heat conducting composite filler, 70-90 parts of toluene, 20 parts of butanone and 10-20 parts of propylene glycol monomethyl ether; uniformly mixing the raw materials to obtain hydrocarbon resin glue solution;
s2, arranging the electronic glass fiber in hydrocarbon resin glue solution, immersing for 20-30min, taking out, and baking for 3-5min in a 160 ℃ oven to obtain a prepreg;
s3, cutting the prepreg into a group of pieces with the same size and size, overlapping the pieces with copper foil, and hot-pressing the pieces at the temperature of 250-260 ℃ for 260min under the pressure of 2-7 MPa.
Further, the modified polybutadiene is obtained by the steps of:
adding maleic anhydride modified polybutadiene and glacial acetic acid into a flask, stirring for 10-15min, adding amino-terminated benzimidazole siloxane, stirring for 1-1.5h, heating to 100 ℃, stirring for reacting 12, and removing glacial acetic acid by rotary evaporation to obtain modified polybutadiene;
wherein the dosage ratio of the maleic anhydride modified polybutadiene to the glacial acetic acid to the amino-terminated benzimidazole siloxane is 3g:100mL:1.2-1.5g, maleic anhydride modified polybutadiene (MLPB, number average molecular weight is 5000g/mol, MAH mass fraction is 12%), which is purchased from gram Lei Weili (Cray Valley) limited company, wherein the maleic anhydride modified polybutadiene is a product obtained by chemically modifying low-molecular-weight liquid polybutadiene with maleic anhydride, a polyolefin skeleton in a molecular structure has better flexibility, water resistance and chemical corrosion resistance, unsaturated double bonds contained in the polybutadiene can be subjected to copolymerization with other components to form a crosslinked network, an anhydride group is used as an active reaction point, and an imide ring, a benzimidazole structure and a siloxane structure are introduced into a molecular chain of the polybutadiene by utilizing the reaction of the anhydride group of the maleic anhydride modified polybutadiene with amino groups of amino-terminated benzimidazole siloxane, so that the modified polybutadiene is obtained.
Further, the amino-terminated benzimidazole siloxane is obtained by the steps of:
adding 2-amino-1H-benzimidazole-5-carboxylic acid, anhydrous DMSO, EDC, HCl and NHS into a flask, stirring for 15-30min under the protection of nitrogen, adding 3-aminopropyl triethoxysilane, continuously stirring for 24H, removing DMSO by rotary evaporation after the reaction is finished, washing a rotary evaporation product with anhydrous acetone, and drying to obtain the amino-terminated benzimidazole siloxane, wherein the molar ratio of 2-amino-1H-benzimidazole-5-carboxylic acid, EDC, HCl, NHS and 3-aminopropyl triethoxysilane is 1:1:1:1, EDC and HCl are 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, NHS is N-hydroxysuccinimide, and 2-amino-1H-benzimidazole-5-carboxylic acid and 3-aminopropyl triethoxysilane react under the action of a condensing agent to obtain amino-terminated benzimidazole siloxane.
Further, the heat conductive composite filler is obtained by:
drying hexagonal boron nitride in a blowing drying oven at 110 ℃ for 12 hours, then placing the hexagonal boron nitride in a ball mill for ball milling for 4 hours at 400r/min, then adding the hexagonal boron nitride into deionized water at 80 ℃ for treatment for 2 hours, performing suction filtration, drying to obtain ball-milled boron nitride, placing the ball-milled boron nitride in a reaction kettle, adding copper nitrate trihydrate aqueous solution, uniformly stirring, standing at room temperature for 2 hours, drying at 50 ℃, and finally placing the ball-milled boron nitride in a muffle furnace for roasting for 2 hours at 400 ℃ in air atmosphere to obtain the heat-conducting composite filler, wherein the mass ratio of the ball-milled boron nitride to the copper nitrate trihydrate is 1:0.15-0.3, firstly, stripping boron nitride through ball milling, further, obtaining boron nitride nano-sheets with large specific surface area and rich hydroxyl groups through hot water treatment, and then, taking copper nitrate trihydrate as a copper source, obtaining copper oxide loaded boron nitride nano-sheets, wherein the copper oxide loaded boron nitride nano-sheets have compact three-dimensional structures, the heat transfer efficiency in the flaky boron nitride surface is high, and the nano-copper oxide is embedded into the surface of the flaky boron nitride surface, so that the heat transfer in the out-of-plane direction is facilitated, therefore, the heat conducting composite filler is introduced into hydrocarbon resin glue solution, the effective heat transfer of a three-dimensional heat conducting network is promoted based on the strong interaction between aluminum oxide and boron nitride, and compared with the mixture of aluminum oxide and boron nitride, the overall heat transfer effect of the heat conducting network is higher.
Further, the initiator is 2, 3-dimethyl-2, 3-diphenyl butane and di-tert-butyl isopropyl peroxide with the mass ratio of 1:1.
Further, the flame retardant is hexaphenoxy cyclotriphosphazene and resorcinol bis (2, 6-dimethylphenyl) phosphate with a mass ratio of 1:1.
The invention has the beneficial effects that:
1. the invention provides a high Tg copper-clad plate, which is prepared by preparing hydrocarbon resin glue solution by adopting modified polybutadiene, styrene-butadiene-styrene copolymer, an initiator, dicyclopentadiene phenol epoxy resin, triallyl isocyanurate, a flame retardant and a heat-conducting composite filler, and then obtaining a prepreg, and carrying out hot pressing on the prepreg by laminating copper-clad foil.
2. According to the invention, modified polybutadiene and a styrene-butadiene-styrene copolymer are used as main resins, dicyclopentadiene phenol epoxy resin is used as auxiliary resins, hydrocarbon resin glue solution is obtained through copolymerization reaction, wherein the introduction of dicyclopentadiene phenol epoxy resin effectively improves the peeling resistance of a copper-clad plate, the styrene-butadiene-styrene copolymer has good heat resistance, the modified polybutadiene has good flexibility, and the molecular chain contains an imide ring, a benzimidazole structure and a siloxane structure, the imide ring has high heat stability, the benzimidazole structure has the characteristics of rigidity, aromatic heterocycle and capability of forming intermolecular hydrogen bonds, the intermolecular hydrogen bonds are beneficial to increasing the interaction force between polymer chains in the hydrocarbon resin glue solution, conjugation of the aromatic heterocycle is beneficial to forming an interchain charge transfer complex, so that the heat resistance of the polymer is improved, meanwhile, the rigidity and linearity of the benzimidazole ring are beneficial to improving the dimensional stability of the polymer, the siloxane structure also contains silicon-carbon bonds, the carbon-silicon bonds have high stability and heat resistance, the heat resistance of the polymer is beneficial to improving, and in addition, the siloxane structure can form chemical bonds with metal copper foil in the process, the peeling resistance is enhanced, and the high peeling resistance of the heat-resistant copper-clad plate is realized, and the heat resistance is high in the heat resistance is introduced into the polybutadiene.
3. According to the invention, the hexagonal boron nitride and the copper nitrate trihydrate are used as raw materials to prepare the heat-conducting composite filler, the heat-conducting composite filler has a compact three-dimensional structure, the heat-conducting composite filler is introduced into hydrocarbon resin glue solution, the effective heat transfer of a three-dimensional heat-conducting network is promoted based on the strong interaction between aluminum oxide and boron nitride, compared with an aluminum oxide and boron nitride mixture, the overall heat transfer effect of the heat-conducting network is higher, the heat-conducting composite filler can be subjected to coupling reaction with modified polybutadiene (the hydroxyl groups on the surface of the heat-conducting composite filler and the siloxane structure of the modified polybutadiene), the interface contact thermal resistance between the heat-conducting composite filler and a polymer is effectively reduced, the interface combination between the heat-conducting composite filler and the polymer is enhanced, and the copper-clad plate is endowed with good heat-radiating performance.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The electronic glass cloth in the following examples and comparative examples was supplied by macro and electronic materials technologies, inc., model G122X, copper foil thickness 35 μm, supplied by Luxembo, inc., and the brand of styrene-butadiene-styrene copolymer was YH-802, purchased from Basil petrochemical company.
Example 1
The modified polybutadiene is obtained by the following steps:
3g of maleic anhydride-modified polybutadiene and 100mL of glacial acetic acid were added to a flask, stirred for 10min, then 1.2g of amino-terminated benzimidazole siloxane was added, stirred for 1h, then heated to 100℃and the glacial acetic acid was removed by rotary evaporation after stirring reaction 12 to give modified polybutadiene, maleic anhydride-modified polybutadiene (MLPB, number average molecular weight 5000g/mol, MAH mass fraction 12%) purchased from gram Lei Weili (Cray Valley).
The amino-terminated benzimidazole siloxane is obtained by the following steps:
5mmol of 2-amino-1H-benzimidazole-5-carboxylic acid, 100mL of anhydrous DMSO, 5mmole of EDC.HCl and 5mmole of NHS are added into a flask, under the protection of nitrogen, 5mmole of 3-aminopropyl triethoxysilane is added after stirring for 15min, stirring is continued for 24H, after the reaction is finished, DMSO is removed by rotary evaporation, and a rotary evaporation product is washed by anhydrous acetone and then dried, so that the amino-terminated benzimidazole siloxane is obtained.
Example 2
The modified polybutadiene is obtained by the following steps:
3g of maleic anhydride-modified polybutadiene and 100mL of glacial acetic acid were added to a flask, stirred for 15min, then 1.5g of amino-terminated benzimidazole siloxane was added, stirred for 1.5h, then heated to 100℃and the glacial acetic acid was removed by rotary evaporation after stirring reaction 12, to give modified polybutadiene, maleic anhydride-modified polybutadiene (MLPB, number average molecular weight 5000g/mol, MAH mass fraction 12%) which was purchased from gram Lei Weili (Cray Valley).
The amino-terminated benzimidazole siloxane is obtained by the following steps:
5mmol of 2-amino-1H-benzimidazole-5-carboxylic acid, 100mL of anhydrous DMSO, 5mmole of EDC.HCl and 5mmole of NHS are added into a flask, under the protection of nitrogen, 5mmole of 3-aminopropyl triethoxysilane is added after stirring for 30min, stirring is continued for 24H, after the reaction is finished, DMSO is removed by rotary evaporation, and a rotary evaporation product is washed by anhydrous acetone and then dried, so that the amino-terminated benzimidazole siloxane is obtained.
Comparative example 1
The modified polybutadiene is obtained by the following steps:
3g of maleic anhydride-modified polybutadiene and 100mL of glacial acetic acid are added into a flask, after stirring for 10min, 1.2g of 2-amino-1H-benzimidazole-5-carboxylic acid is added, after stirring for 1H, the temperature is raised to 100 ℃, the glacial acetic acid is removed by rotary evaporation after stirring reaction 12, and the modified polybutadiene is obtained, and the maleic anhydride-modified polybutadiene is obtained in the same manner as in example 1.
Example 3
The heat-conducting composite filler is obtained by the following steps:
drying 20g of hexagonal boron nitride in a blowing drying oven at 110 ℃ for 12 hours, then placing in a ball mill for ball milling at 400r/min for 4 hours, then adding into deionized water at 80 ℃ for 2 hours, performing suction filtration, drying to obtain ball-milled boron nitride, placing 10g of ball-milled boron nitride in a reaction kettle, adding a solution consisting of 1.5g of copper nitrate trihydrate and 15mL of deionized water, uniformly stirring, standing at room temperature for 2 hours, drying at 50 ℃, finally placing in a muffle furnace for roasting at 400 ℃ for 2 hours in an air atmosphere, and obtaining the heat-conducting composite filler.
Example 4
The heat-conducting composite filler is obtained by the following steps:
drying 20g of hexagonal boron nitride in a blowing drying oven at 110 ℃ for 12 hours, then placing in a ball mill for ball milling at 400r/min for 4 hours, then adding into deionized water at 80 ℃ for treatment for 2 hours, performing suction filtration, drying to obtain ball-milled boron nitride, placing 10g of ball-milled boron nitride in a reaction kettle, adding a solution consisting of 3g of copper nitrate trihydrate and 20mL of deionized water, uniformly stirring, standing at room temperature for 2 hours, drying at 50 ℃, finally placing in a muffle furnace for roasting at 400 ℃ for 2 hours in an air atmosphere, and obtaining the heat-conducting composite filler.
Comparative example 2
The heat-conducting composite filler is obtained by the following steps:
hexagonal boron nitride and copper oxide are mixed according to the mass ratio of 10:1, adding the mixture into a stirring tank, and stirring and mixing for 30min at the rotating speed of 300r/min to obtain the heat-conducting composite filler.
Example 5
The preparation method of the high Tg copper-clad plate comprises the following steps:
s1, weighing the following raw materials in parts by weight: example 1 modified polybutadiene 95 parts, styrene-butadiene-styrene copolymer 40 parts, initiator 6 parts, dicyclopentadiene phenol epoxy resin 20 parts, triallyl isocyanurate 5 parts, flame retardant 50 parts, example 3 heat-conducting composite filler 40 parts, toluene 70 parts, butanone 20 parts, propylene glycol monomethyl ether 10 parts; uniformly mixing the raw materials to obtain hydrocarbon resin glue solution;
s2, arranging the electronic glass fiber in hydrocarbon resin glue solution, immersing for 20min, taking out, and baking for 3min in a 160 ℃ oven to obtain a prepreg;
s3, cutting the prepreg into a group of 8 pieces with the same size, overlapping the prepreg with copper foil, and hot-pressing the prepreg at the temperature of 250 ℃ under the pressure of 2MPa for 260 minutes.
Wherein the initiator is 2, 3-dimethyl-2, 3-diphenyl butane and di-tert-butyl isopropyl peroxide with the mass ratio of 1:1, wherein the flame retardant is hexaphenoxy cyclotriphosphazene and resorcinol bis (2, 6-dimethylphenyl) phosphate with the mass ratio of 1:1.
Example 6
The preparation method of the high Tg copper-clad plate comprises the following steps:
s1, weighing the following raw materials in parts by weight: 100 parts of modified polybutadiene, 45 parts of styrene-butadiene-styrene copolymer, 6 parts of initiator, 25 parts of dicyclopentadiene phenol epoxy resin, 5 parts of triallyl isocyanurate, 50 parts of flame retardant, 50 parts of heat-conducting composite filler of example 4, 80 parts of toluene, 20 parts of butanone and 15 parts of propylene glycol monomethyl ether; uniformly mixing the raw materials to obtain hydrocarbon resin glue solution;
s2, arranging the electronic glass fiber in hydrocarbon resin glue solution, immersing for 25min, taking out, and baking for 4min in a 160 ℃ oven to obtain a prepreg;
s3, cutting the prepreg into a group of 8 prepregs with the same size, overlapping the prepregs with copper foil, and hot-pressing the prepregs at 255 ℃ under the pressure of 5MPa for 260 min.
Wherein the initiator is 2, 3-dimethyl-2, 3-diphenyl butane and di-tert-butyl isopropyl peroxide with the mass ratio of 1:1, wherein the flame retardant is hexaphenoxy cyclotriphosphazene and resorcinol bis (2, 6-dimethylphenyl) phosphate with the mass ratio of 1:1.
Example 7
The preparation method of the high Tg copper-clad plate comprises the following steps:
s1, weighing the following raw materials in parts by weight: 105 parts of modified polybutadiene, 50 parts of styrene-butadiene-styrene copolymer, 6 parts of initiator, 30 parts of dicyclopentadiene phenol epoxy resin, 5 parts of triallyl isocyanurate, 50 parts of flame retardant, 60 parts of heat-conducting composite filler of example 4, 90 parts of toluene, 20 parts of butanone and 20 parts of propylene glycol monomethyl ether; uniformly mixing the raw materials to obtain hydrocarbon resin glue solution;
s2, arranging the electronic glass fiber in hydrocarbon resin glue solution, immersing for 30min, taking out, and baking for 5min in a 160 ℃ oven to obtain a prepreg;
s3, cutting the prepreg into a group of 8 pieces with the same size, overlapping the prepreg with copper foil, and hot-pressing the prepreg at the temperature of 260 ℃ under the pressure of 7MPa for 260 minutes.
Wherein the initiator is 2, 3-dimethyl-2, 3-diphenyl butane and di-tert-butyl isopropyl peroxide with the mass ratio of 1:1, wherein the flame retardant is hexaphenoxy cyclotriphosphazene and resorcinol bis (2, 6-dimethylphenyl) phosphate with the mass ratio of 1:1.
Comparative example 3
In comparison with example 7, the modified polybutadiene of example 7 was replaced with the material of comparative example 1, and the remaining raw materials and the production process were the same as in example 7.
Comparative example 4
Compared with example 7, the heat conductive composite filler in example 7 was replaced with the material in comparative example 2, and the rest of the raw materials and the preparation process were the same as in example 7.
Comparative example 5
Compared with example 7, the modified polybutadiene of example 7 was replaced with polybutadiene having a number average molecular weight of 5000, and the rest of the raw materials and the preparation process were the same as in example 7.
The copper clad laminates obtained in examples 5 to 7 and comparative examples 3 to 5 were tested as follows:
peel strength test: testing according to the test method of 2.4.8 copper-clad plate peel strength in IPC-TM-650;
thermal conductivity coefficient: according to the standard ASTM D5470, selecting a plurality of prepregs in the examples and the comparative examples, pressing to prepare samples with the thickness of 1.5mm (+ -5%), baking at 135 ℃ for 20min, sampling by using a round die with the diameter of 3mm to be tested, setting the hot pole temperature to 70 ℃ (referring to Rogers test method), reading the heat flow Q, the sample surface area A, the temperature TH of the contact surface with the hot pole and the cold pole contact temperature TC according to test software, and calculating the thermal impedance theta as shown in the formula (1):
θ＝A/Q×(TH－TC) (1)
the thermal conductivity coefficient in the z-axis direction can be calculated according to the ratio of the thermal impedance theta to the thickness of the sample;
peel transition temperature (Tg): adopting a differential scanning calorimeter (differential scanning calorimetry, DSC) instrument, and heating at a rate of 20 ℃/min under nitrogen atmosphere;
the test results are shown in table 1:
TABLE 1
Project Example 5 Example 6 Example 7 Comparative example 3 Comparative example 4 Comparative example 5
Peel strength/N.mm -1 1.89 1.84 1.78 1.68 1.67 1.59
Thermal conductivity/Wm -1 K -1 1.48 1.56 1.67 1.53 1.39 1.51
Tg/℃ 225 223 220 217 219 210
As can be seen from the data recorded in Table 1, the copper-clad plates obtained in examples 5 to 7 have higher Tg values, high peel strength, large thermal conductivity and application potential of the high-frequency high-speed copper-clad plate compared with the copper-clad plates obtained in comparative examples 3 to 5.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein 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 high Tg copper-clad plate is characterized by comprising the following specific preparation steps:
s1, weighing the following raw materials in parts by weight: 95-105 parts of modified polybutadiene, 40-50 parts of styrene-butadiene-styrene copolymer, 6 parts of initiator, 20-30 parts of dicyclopentadiene phenol epoxy resin, 5 parts of triallyl isocyanurate, 50 parts of flame retardant, 40-60 parts of heat conducting composite filler, 70-90 parts of toluene, 20 parts of butanone and 10-20 parts of propylene glycol monomethyl ether; uniformly mixing the raw materials to obtain hydrocarbon resin glue solution;
s2, arranging the electronic glass fiber in hydrocarbon resin glue solution, immersing for 20-30min, taking out, and baking for 3-5min in a 160 ℃ oven to obtain a prepreg;
s3, cutting the prepreg into a group of pieces with the same size and size, overlapping the pieces with copper foil, and hot-pressing the pieces at the temperature of 250-260 ℃ for 260min under the pressure of 2-7 MPa.
2. The high Tg copper clad laminate of claim 1, wherein the modified polybutadiene is obtained by:
adding maleic anhydride modified polybutadiene and glacial acetic acid into a flask, stirring for 10-15min, adding amino-terminated benzimidazole siloxane, stirring for 1-1.5h, heating to 100 ℃, stirring for reaction, and removing glacial acetic acid by rotary evaporation to obtain modified polybutadiene.
3. The high Tg copper clad laminate of claim 2, wherein the ratio of maleic anhydride modified polybutadiene, glacial acetic acid, and amino terminated benzimidazole siloxane is 3g:100mL:1.2-1.5g.
4. The high Tg copper clad laminate of claim 2, wherein the amino terminated benzimidazole siloxane is obtained by:
adding 2-amino-1H-benzimidazole-5-carboxylic acid, anhydrous DMSO, EDC, HCl and NHS into a flask, stirring for 15-30min under the protection of nitrogen, adding 3-aminopropyl triethoxysilane, continuously stirring for 24H, removing DMSO by rotary evaporation after the reaction is finished, washing the rotary evaporation product with anhydrous acetone, and drying to obtain the amino-terminated benzimidazole siloxane.
5. The high Tg copper clad laminate of claim 4, wherein the molar ratio of 2-amino-1H-benzimidazole-5-carboxylic acid, edc.hcl, NHS, and 3-aminopropyl triethoxysilane is 1:1:1:1.
6. the high Tg copper clad laminate of claim 1, wherein the thermally conductive composite filler is obtained by:
drying hexagonal boron nitride in a blowing drying oven at 110 ℃ for 12 hours, then placing the hexagonal boron nitride in a ball mill for ball milling at 400r/min for 4 hours, then adding the hexagonal boron nitride into deionized water at 80 ℃ for treatment for 2 hours, performing suction filtration, drying to obtain ball-milled boron nitride, placing the ball-milled boron nitride in a reaction kettle, adding copper nitrate trihydrate aqueous solution, uniformly stirring, standing at room temperature for 2 hours, drying at 50 ℃, finally placing the dried hexagonal boron nitride in a muffle furnace, and roasting at 400 ℃ for 2 hours in an air atmosphere to obtain the heat-conducting composite filler.
7. The high Tg copper clad laminate of claim 6, wherein the mass ratio of ball milled boron nitride to copper nitrate trihydrate is 1:0.15-0.3.
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JP2006051687A (en) * 2004-08-11 2006-02-23 Hitachi Chem Co Ltd Metal foil with adhesive layer and metal-clad laminate
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