CN114437435B - High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same - Google Patents

High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same Download PDF

Info

Publication number
CN114437435B
CN114437435B CN202210170426.6A CN202210170426A CN114437435B CN 114437435 B CN114437435 B CN 114437435B CN 202210170426 A CN202210170426 A CN 202210170426A CN 114437435 B CN114437435 B CN 114437435B
Authority
CN
China
Prior art keywords
hydrocarbon resin
parts
heat
silicon carbide
based prepreg
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.)
Active
Application number
CN202210170426.6A
Other languages
Chinese (zh)
Other versions
CN114437435A (en
Inventor
向中荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuxi Relong New Material Technology Co ltd
Original Assignee
Wuxi Relong New Material Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wuxi Relong New Material Technology Co ltd filed Critical Wuxi Relong New Material Technology Co ltd
Priority to CN202210170426.6A priority Critical patent/CN114437435B/en
Publication of CN114437435A publication Critical patent/CN114437435A/en
Application granted granted Critical
Publication of CN114437435B publication Critical patent/CN114437435B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C08J5/18—Manufacture of films or sheets
    • 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
    • B32B5/02—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 structural features of 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
    • 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
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • 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
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/08—Copolymers of styrene
    • C08J2325/10—Copolymers of styrene with conjugated dienes
    • 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
    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
    • C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • 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
    • C08K7/10—Silicon-containing 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

Landscapes

  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Fluid Mechanics (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a high-heat-conductivity hydrocarbon resin-based prepreg which comprises a reinforced cloth core and a hydrocarbon resin layer coated outside the reinforced cloth core; the reinforced cloth core is silicon carbide fiber cloth which is formed by polar weaving of modified silicon carbide fibers; the hydrocarbon resin layer is obtained by solidifying hydrocarbon resin glue liquid, and the hydrocarbon resin glue liquid comprises the following components in parts by weight: 20-40 parts of hydrocarbon resin, 10-20 parts of bismaleimide resin, 5-10 parts of benzoxazine, 5-10 parts of heat conducting filler, 1-5 parts of curing agent and 50-120 parts of solvent; the high-frequency copper-clad plate prepared from the high-heat-conductivity hydrocarbon resin-based prepreg has the advantages of low dielectric constant, low dielectric loss, high heat-conducting property, high peel strength and the like.

Description

High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same
Technical Field
The invention belongs to the field of communication materials, and particularly relates to a high-heat-conductivity hydrocarbon resin-based prepreg and a high-frequency copper-clad plate prepared from the prepreg.
Background
The 5G communication technology is the 5 th generation technology of the mobile communication technology, and is developed to meet the requirements of mobile Internet and everything Internet business after 2020. Compared with the 4G communication technology, the 5G communication technology has the characteristics of faster information transmission rate, stronger spectrum utilization efficiency, lower delay, more reliable information transmission, higher link density and the like.
The high-frequency polycarbonate-based copper-clad plate has the properties of low dielectric constant, low dielectric loss, low thermal expansion coefficient, low water absorption and the like, and is widely used as a high-frequency electronic communication material. Along with the development of high frequency and high speed of signal transmission, the heat management of the PCB is also receiving more and more attention, so that in some application occasions, the heat conductivity coefficient of the PCB core component copper-clad plate has clear requirements, and the higher the heat conductivity coefficient, the faster the heat dissipation of the component and the smaller the temperature rise of the PCB. Because the heat conduction of the hydrocarbon-based polymer or copolymer is very poor and is between 0.01 and 0.03, the carbon-hydrogen copper-clad plate has higher heat conduction coefficient through the selective modification of the filler, and is one of the common using methods of copper-clad plate researchers. The common heat conducting filler comprises aluminum oxide, boron nitride, silicon nitride and the like, and under the limitation of high requirements of high-frequency materials on dielectric property, water absorption and the like, the requirements on the selection and collocation of various heat conducting fillers and the like are higher.
The invention provides a high-frequency copper-clad plate prepared from a high-heat-conductivity hydrocarbon composition and a preparation method thereof, wherein an electronic grade E-grade glass fiber cloth is impregnated with a dimethylbenzene dispersion liquid of the high-heat-conductivity hydrocarbon composition to prepare a film, and the two sides of the film are pressed together to prepare the high-frequency copper-clad plate, so that the prepared copper-clad plate has low dielectric constant, low dielectric loss and high copper foil peel strength, but the heat conductivity coefficient is 0.65-0.78, and the heat conductivity coefficient still needs to be improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the high-heat-conductivity hydrocarbon resin-based prepreg, and the high-frequency copper-clad plate prepared from the high-heat-conductivity hydrocarbon resin-based prepreg has the advantages of low dielectric constant, low dielectric loss, high heat-conductivity, high peel strength and the like.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a high-heat-conductivity hydrocarbon resin-based prepreg comprises a reinforced cloth core and a hydrocarbon resin layer coated outside the reinforced cloth core;
the reinforced cloth core is silicon carbide fiber cloth which is formed by polar weaving of modified silicon carbide fibers;
the hydrocarbon resin layer is obtained by solidifying hydrocarbon resin glue liquid, and the hydrocarbon resin glue liquid comprises the following components in parts by weight: 20-40 parts of hydrocarbon resin, 10-20 parts of bismaleimide resin, 5-10 parts of benzoxazine, 5-10 parts of heat conducting filler, 1-5 parts of curing agent and 50-120 parts of solvent.
The further preferable technical scheme is as follows: the preparation method of the modified silicon carbide fiber comprises the following steps: immersing the silicon carbide fiber in 0.2-2 mg/mL polyphenol water solution for 10-30 min, vacuumizing, introducing oxygen, performing ultraviolet irradiation reaction for 8-24 h, and performing filtration, washing and drying treatment to obtain the modified silicon carbide fiber.
The further preferable technical scheme is as follows: the mass ratio of the polyphenol to the silicon carbide fiber is 1:0.1 to 10.
The further preferable technical scheme is as follows: the polyphenol is one or more of tannic acid, pyrogallol, caffeic acid and gallic acid.
The further preferable technical scheme is as follows: the wavelength of the ultraviolet light is less than or equal to 340nm, and the light intensity of the ultraviolet light is more than or equal to 1mW/cm 2 The ambient temperature during ultraviolet irradiation is less than or equal to 50 ℃, and the distance between an ultraviolet light source and an irradiated object is less than or equal to 100cm.
The further preferable technical scheme is as follows: the heat conducting filler is one or more of hexagonal boron nitride, aluminum oxide, spherical aluminum nitride and boron aluminate whisker, and the particle size of the heat conducting filler is 10-100 um.
The further preferable technical scheme is as follows: the curing agent is at least one of 2-ethyl-4-methylimidazole, 1-methylimidazole, imidazole and benzimidazole.
The further preferable technical scheme is as follows: the hydrocarbon resin is selected from one or more of styrene-butadiene resin, polybutadiene resin, poly-iso-butadiene resin, polystyrene, styrene-butadiene copolymer or styrene-iso-butadiene copolymer.
The further preferable technical scheme is as follows: the high-heat-conductivity hydrocarbon resin-based prepreg is prepared by the following steps:
(1) Adding 20-40 parts by weight of hydrocarbon resin into a solvent with the temperature of 80-100 ℃ for full dissolution, adding 10-20 parts by weight of bismaleimide resin after the temperature is raised to 110-130 ℃, stirring until the two are uniformly mixed, sequentially adding 5-10 parts by weight of benzoxazine, 5-10 parts by weight of heat conducting filler, 1-5 parts by weight of curing agent and the rest solvent, keeping the temperature at 110-130 ℃, and stirring until the mixture is uniform to obtain hydrocarbon resin glue solution;
(2) And (3) immersing the reinforced cloth core in the hydrocarbon resin glue solution obtained in the step (1) for 10-30 min, solidifying for 1-10 h at the temperature of 120-200 ℃, and cooling to room temperature after solidification to obtain the high-heat-conductivity hydrocarbon resin-based prepreg.
The invention also provides a high-frequency copper-clad plate prepared from the high-heat-conductivity hydrocarbon resin-based prepreg, which is prepared by the following steps: symmetrically overlapping the high-heat-conductivity hydrocarbon resin-based prepreg and the copper foil, then placing the prepreg and the copper foil into a hot press, setting the hot press temperature to be 150-300 ℃ and the pressure to be 50-150 kg/cm 2 And the lamination time is 12-24 hours, and the high-frequency copper-clad plate is obtained.
From the above description, it can be seen that the present invention has the following advantages:
1. the high-heat-conductivity hydrocarbon resin-based prepreg is composed of the reinforced cloth core and the hydrocarbon resin layer, wherein the reinforced cloth core is formed by polar weaving of silicon carbide fibers, the high-heat-conductivity hydrocarbon resin-based prepreg has excellent performances of high specific strength, high temperature resistance, oxidation resistance, low thermal expansion coefficient and the like of the silicon carbide fibers, and the reinforced cloth core obtained by adopting a polar weaving mode can disperse external acting force and remarkably improve the mechanical property of the prepreg.
2. After the silicon carbide fiber is subjected to the modification treatment of the polyphenol, the polyphenol is attached to the surface of the silicon carbide fiber, and when the prepreg is prepared, the polyphenol on the surface of the silicon carbide fiber participates in the crosslinking and curing reaction of hydrocarbon resin, bismaleimide resin and benzoxazine, so that the compatibility and the cohesiveness between the silicon carbide fiber and matrix resin, between the heat conducting filler and the matrix resin and between the heat conducting filler and the silicon carbide fiber can be improved, the peeling strength of the prepreg and the copper foil can be improved, and the heat conductivity coefficient of the high-frequency copper-clad plate can also be improved.
3. According to the invention, through the curing and blending of hydrocarbon resin, bismaleimide resin and benzoxazine, a three-dimensional cross-linked network structure and a hydrogen bond network structure can be generated, and the cross-linked and hydrogen bond network structure is beneficial to improving the heat resistance and toughness of hydrocarbon resin and reducing the curing shrinkage rate of the material.
Drawings
FIG. 1 is a cross-sectional view of a high thermal conductivity hydrocarbon resin-based prepreg of the present invention;
fig. 2 is a schematic polar weave view of a reinforcing fabric core of the present invention.
Reference numerals: 1. hydrocarbon resin layer, 2, reinforcing cloth core.
Detailed Description
The features of the invention are further illustrated by the following examples, without limiting the scope of the claims.
Example 1
The embodiment provides a high-heat-conductivity hydrocarbon resin-based prepreg which comprises a reinforced cloth core 2 and a hydrocarbon resin layer 1 coated outside the reinforced cloth core, as shown in fig. 1;
the reinforced cloth core 2 is silicon carbide fiber cloth which is formed by weaving modified silicon carbide fibers in polarity, as shown in figure 2;
the hydrocarbon resin layer 1 is obtained by solidifying hydrocarbon resin glue solution, and the hydrocarbon resin glue solution comprises the following components in parts by weight: 20 parts of hydrocarbon resin, 10 parts of bismaleimide resin, 5 parts of benzoxazine, 5 parts of heat conducting filler, 1 part of curing agent and 50 parts of solvent.
The preparation method of the modified silicon carbide fiber comprises the following steps: immersing the silicon carbide fiber in 0.2mg/mL polyphenol water solution for 10min, vacuumizing, introducing oxygen, performing ultraviolet irradiation reaction for 8h, and performing filtration, washing and drying treatment to obtain the modified silicon carbide fiber.
Wherein the wavelength of the ultraviolet light is 340nm, and the light intensity of the ultraviolet light is 1mW/cm 2 The ambient temperature during ultraviolet irradiation is 50 ℃, and the distance between the ultraviolet light source and the irradiated object is 100cm.
The high-heat-conductivity hydrocarbon resin-based prepreg is prepared by the following steps:
(1) Adding 20 parts by weight of styrene-butadiene resin into a solvent with the temperature of 80 ℃ for full dissolution, adding 10 parts by weight of bismaleimide resin after the temperature is raised to 110 ℃, stirring until the mixture is uniform, sequentially adding 5 parts by weight of benzoxazine, 5 parts by weight of hexagonal boron nitride with the particle size of 10um, 1 part by weight of 2-ethyl-4-methylimidazole and the rest solvent, keeping the temperature at 110 ℃, and stirring until the mixture is uniform to obtain hydrocarbon resin glue solution;
(2) And (3) immersing the reinforced cloth core in the hydrocarbon resin glue solution in the step (1) for 10min, solidifying for 10h at the temperature of 120 ℃, and cooling to room temperature after solidification to obtain the high-heat-conductivity hydrocarbon resin-based prepreg.
The embodiment also provides a high-frequency copper-clad plate prepared from the high-heat-conductivity hydrocarbon resin-based prepreg, which is prepared by the following steps: symmetrically overlapping the high-heat-conductivity hydrocarbon resin-based prepreg and the copper foil, and then placing the prepreg and the copper foil into a hot press, wherein the hot press temperature is set to be 150 ℃ and the pressure is set to be 50kg/cm 2 And the lamination time is 12h, and the high-frequency copper-clad plate is obtained.
Example 2
The embodiment provides a high-heat-conductivity hydrocarbon resin-based prepreg which comprises a reinforced cloth core 2 and a hydrocarbon resin layer 1 coated outside the reinforced cloth core, as shown in fig. 1;
the reinforced cloth core 2 is silicon carbide fiber cloth which is formed by weaving modified silicon carbide fibers in polarity, as shown in figure 2;
the hydrocarbon resin layer 1 is obtained by solidifying hydrocarbon resin glue solution, and the hydrocarbon resin glue solution comprises the following components in parts by weight: 40 parts of hydrocarbon resin, 20 parts of bismaleimide resin, 10 parts of benzoxazine, 10 parts of heat conducting filler, 5 parts of curing agent and 120 parts of solvent.
The preparation method of the modified silicon carbide fiber comprises the following steps: immersing the silicon carbide fiber in 0.2mg/mL pyrogallol aqueous solution (the mass ratio of polyphenol to the silicon carbide fiber is 1:10), immersing for 10min, vacuumizing, introducing oxygen, performing ultraviolet irradiation reaction for 8h, and performing filtration, washing and drying treatment to obtain the modified silicon carbide fiber.
Wherein the wavelength of the ultraviolet light is 280nm, and the light intensity of the ultraviolet light is 5mW/cm 2 The ambient temperature during ultraviolet irradiation is 30 ℃, and the distance between the ultraviolet light source and the irradiated object is 50cm.
The high-heat-conductivity hydrocarbon resin-based prepreg is prepared by the following steps:
(1) Adding 40 parts by weight of polybutadiene resin into a solvent with the temperature of 100 ℃ for full dissolution, adding 20 parts by weight of bismaleimide resin after the temperature is raised to 130 ℃, stirring until the mixture is uniform, sequentially adding 10 parts by weight of benzoxazine, 10 parts by weight of spherical aluminum nitride with the particle size of 100um, 5 parts by weight of 1-methylimidazole and the rest solvent, keeping the temperature at 130 ℃, and stirring until the mixture is uniform to obtain hydrocarbon resin glue solution;
(2) And (3) immersing the reinforced cloth core in the hydrocarbon resin glue solution in the step (1) for 30min, solidifying for 1h at the temperature of 200 ℃, and cooling to room temperature after solidification to obtain the high-heat-conductivity hydrocarbon resin-based prepreg.
The embodiment also provides a high-frequency copper-clad plate prepared from the high-heat-conductivity hydrocarbon resin-based prepreg, which is prepared by the following steps: symmetrically overlapping the high-heat-conductivity hydrocarbon resin-based prepreg and the copper foil, and then placing the prepreg and the copper foil into a hot press, wherein the hot press temperature is set to 300 ℃ and the pressure is set to 150kg/cm 2 And the lamination time is 12h, and the high-frequency copper-clad plate is obtained.
Example 3
The embodiment provides a high-heat-conductivity hydrocarbon resin-based prepreg which comprises a reinforced cloth core 2 and a hydrocarbon resin layer 1 coated outside the reinforced cloth core, as shown in fig. 1;
the reinforced cloth core 2 is silicon carbide fiber cloth which is formed by weaving modified silicon carbide fibers in polarity, as shown in figure 2;
the hydrocarbon resin layer 1 is obtained by solidifying hydrocarbon resin glue solution, and the hydrocarbon resin glue solution comprises the following components in parts by weight: 30 parts of hydrocarbon resin, 15 parts of bismaleimide resin, 8 parts of benzoxazine, 8 parts of heat conducting filler, 3 parts of curing agent and 80 parts of solvent.
The preparation method of the modified silicon carbide fiber comprises the following steps: immersing the silicon carbide fiber in 1mg/mL gallic acid aqueous solution (the mass ratio of polyphenol to the silicon carbide fiber is 1:5), immersing for 10min, vacuumizing, introducing oxygen, performing ultraviolet irradiation reaction for 8h, and performing filtration, washing and drying treatment to obtain the modified silicon carbide fiber.
Wherein the wavelength of the ultraviolet light is 100nm, and the light intensity of the ultraviolet light is 10mW/cm 2 The ambient temperature during ultraviolet irradiation is 20 ℃, and the distance between the ultraviolet light source and the irradiated object is 10cm.
The high-heat-conductivity hydrocarbon resin-based prepreg is prepared by the following steps:
(1) Adding 30 parts by weight of a styrene-butadiene copolymer into a solvent with the temperature of 90 ℃ for full dissolution, adding 15 parts by weight of bismaleimide resin after the temperature is raised to 120 ℃, stirring until the mixture is uniform, sequentially adding 8 parts by weight of benzoxazine, 8 parts by weight of boron aluminate whisker with the particle size of 50um, 3 parts by weight of benzimidazole and the rest solvent, keeping the temperature at 120 ℃, and stirring until the mixture is uniform to obtain hydrocarbon resin glue solution;
(2) And (3) immersing the reinforced cloth core in the hydrocarbon resin glue solution in the step (1) for 20min, solidifying for 5h at 160 ℃, and cooling to room temperature after solidification to obtain the high-heat-conductivity hydrocarbon resin-based prepreg.
The embodiment also provides a high-frequency copper-clad plate prepared from the high-heat-conductivity hydrocarbon resin-based prepreg, which is prepared by the following steps: symmetrically overlapping the high-heat-conductivity hydrocarbon resin-based prepreg and the copper foil, then placing the prepreg into a hot press, setting the hot press temperature to 240 ℃,the pressure is 120kg/cm 2 And the lamination time is 18h, and the high-frequency copper-clad plate is obtained.
Example 4
The embodiment provides a high-heat-conductivity hydrocarbon resin-based prepreg which comprises a reinforced cloth core 2 and a hydrocarbon resin layer 1 coated outside the reinforced cloth core, as shown in fig. 1;
the reinforced cloth core 2 is silicon carbide fiber cloth which is formed by weaving modified silicon carbide fibers in polarity, as shown in figure 2;
the hydrocarbon resin layer 1 is obtained by solidifying hydrocarbon resin glue solution, and the hydrocarbon resin glue solution comprises the following components in parts by weight: 30 parts of hydrocarbon resin, 15 parts of bismaleimide resin, 8 parts of benzoxazine, 8 parts of heat conducting filler, 3 parts of curing agent and 80 parts of solvent.
The preparation method of the modified silicon carbide fiber comprises the following steps: immersing the silicon carbide fiber in 1mg/mL of aqueous solution of coffee acid (the mass ratio of polyphenol to the silicon carbide fiber is 1:5), immersing for 20min, vacuumizing, introducing oxygen, performing ultraviolet irradiation reaction for 12h, and performing filtration, washing and drying treatment to obtain the modified silicon carbide fiber.
Wherein the wavelength of the ultraviolet light is 300nm, and the light intensity of the ultraviolet light is 8mW/cm 2 The ambient temperature during ultraviolet irradiation is 25 ℃, and the distance between the ultraviolet light source and the irradiated object is 40cm.
The high-heat-conductivity hydrocarbon resin-based prepreg is prepared by the following steps:
(1) Adding 30 parts by weight of a styrene-butadiene copolymer into a solvent with the temperature of 90 ℃ for full dissolution, adding 15 parts by weight of bismaleimide resin after the temperature is raised to 120 ℃, stirring until the mixture is uniform, sequentially adding 8 parts by weight of benzoxazine, 8 parts by weight of aluminum oxide with the particle size of 50um, 3 parts by weight of benzimidazole and the rest solvent, keeping the temperature at 120 ℃, and stirring until the mixture is uniform to obtain hydrocarbon resin glue solution;
(2) And (3) immersing the reinforced cloth core in the hydrocarbon resin glue solution in the step (1) for 20min, solidifying for 5h at 160 ℃, and cooling to room temperature after solidification to obtain the high-heat-conductivity hydrocarbon resin-based prepreg.
The embodiment also provides a high-frequency copper-clad plate prepared from the high-heat-conductivity hydrocarbon resin-based prepreg, which is prepared by the following steps: symmetrically overlapping the high-heat-conductivity hydrocarbon resin-based prepreg and the copper foil, and then placing the prepreg and the copper foil into a hot press, wherein the hot press temperature is set to be 200 ℃ and the pressure is set to be 80kg/cm 2 And the lamination time is 15h, and the high-frequency copper-clad plate is obtained.
Comparative example 1
The comparative example is a commercially available high frequency copper clad laminate.
Comparative example 2
The comparative example was prepared according to the preparation method of patent CN202110863695.6 to obtain a high-frequency copper-clad plate.
Test case
The high frequency copper clad laminates prepared in examples 1-4 and comparative examples 1-2 were compared for overall performance, wherein the thermal conductivity was tested according to GB/T36476-2018, the peel strength, dielectric constant and dielectric loss were tested according to GB4722-2017 pair, the Coefficient of Thermal Expansion (CTE) was tested using a Diamond static thermo-mechanical Analyzer, and the water absorption was measured using the IPC-TM-6502.5.6 method, the results of which are shown in the following Table.
Figure BDA0003517871710000111
It is to be understood that the foregoing detailed description of the invention is merely illustrative of the invention and is not limited to the embodiments of the invention. It will be understood by those of ordinary skill in the art that the present invention may be modified or substituted for elements thereof to achieve the same technical effects; as long as the use requirement is met, the invention is within the protection scope of the invention.

Claims (8)

1. The high-heat-conductivity hydrocarbon resin-based prepreg is characterized by comprising a reinforced cloth core and a hydrocarbon resin layer coated outside the reinforced cloth core;
the reinforced cloth core is silicon carbide fiber cloth which is formed by polar weaving of modified silicon carbide fibers;
the hydrocarbon resin layer is obtained by solidifying hydrocarbon resin glue liquid, and the hydrocarbon resin glue liquid comprises the following components in parts by weight: 20-40 parts of hydrocarbon resin, 10-20 parts of bismaleimide resin, 5-10 parts of benzoxazine, 5-10 parts of heat conducting filler, 1-5 parts of curing agent and 50-120 parts of solvent;
the preparation method of the modified silicon carbide fiber comprises the following steps: immersing the silicon carbide fiber in 0.2-2 mg/mL polyphenol water solution for 10-30 min, vacuumizing, introducing oxygen, performing ultraviolet irradiation reaction for 8-24 h, and performing filtration, washing and drying treatment to obtain the modified silicon carbide fiber;
the mass ratio of the polyphenol to the silicon carbide fiber is 1:0.1 to 10.
2. The high thermal conductivity hydrocarbon resin based prepreg according to claim 1, wherein the polyphenol is one or a mixture of tannic acid, pyrogallol acid, caffeic acid, gallic acid.
3. The high thermal conductivity hydrocarbon resin based prepreg according to claim 1, wherein the wavelength of ultraviolet light is less than or equal to 340nm, and the light intensity of ultraviolet light is more than or equal to 1mW/cm 2 The ambient temperature during ultraviolet irradiation is less than or equal to 50 ℃, and the distance between an ultraviolet light source and an irradiated object is less than or equal to 100cm.
4. The high-heat-conductivity hydrocarbon resin-based prepreg according to claim 1, wherein the heat-conducting filler is one or more of hexagonal boron nitride, aluminum oxide, spherical aluminum nitride and boron aluminate whisker, and the particle size of the heat-conducting filler is 10-100 um.
5. The high thermal conductivity hydrocarbon resin based prepreg of claim 1, wherein the curing agent is at least one of 2-ethyl-4-methylimidazole, 1-methylimidazole, imidazole and benzimidazole.
6. The high thermal conductivity hydrocarbon resin based prepreg of claim 1, wherein the hydrocarbon resin is selected from one or more of styrene-butadiene resin, polybutadiene resin, poly-iso-butadiene resin, polystyrene, styrene-butadiene copolymer or styrene-iso-butadiene copolymer.
7. The high thermal conductivity hydrocarbon resin based prepreg of claim 1, wherein the prepreg is prepared by:
(1) Adding 20-40 parts by weight of hydrocarbon resin into a solvent with the temperature of 80-100 ℃ for full dissolution, adding 10-20 parts by weight of bismaleimide resin after the temperature is raised to 110-130 ℃, stirring until the two are uniformly mixed, sequentially adding 5-10 parts by weight of benzoxazine, 5-10 parts by weight of heat conducting filler, 1-5 parts by weight of curing agent and the rest solvent, keeping the temperature at 110-130 ℃, and stirring until the mixture is uniform to obtain hydrocarbon resin glue solution;
(2) And (3) immersing the reinforced cloth core in the hydrocarbon resin glue solution obtained in the step (1) for 10-30 min, solidifying for 1-10 h at the temperature of 120-200 ℃, and cooling to room temperature after solidification to obtain the high-heat-conductivity hydrocarbon resin-based prepreg.
8. A high frequency copper clad laminate prepared from the high thermal conductivity hydrocarbon resin based prepreg according to claim 1, which is characterized by being prepared by the following steps: symmetrically overlapping the high-heat-conductivity hydrocarbon resin-based prepreg and the copper foil, then placing the prepreg and the copper foil into a hot press, setting the hot press temperature to be 150-300 ℃ and the pressure to be 50-150 kg/cm 2 And the lamination time is 12-24 hours, and the high-frequency copper-clad plate is obtained.
CN202210170426.6A 2022-02-24 2022-02-24 High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same Active CN114437435B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210170426.6A CN114437435B (en) 2022-02-24 2022-02-24 High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210170426.6A CN114437435B (en) 2022-02-24 2022-02-24 High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same

Publications (2)

Publication Number Publication Date
CN114437435A CN114437435A (en) 2022-05-06
CN114437435B true CN114437435B (en) 2023-04-21

Family

ID=81373594

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210170426.6A Active CN114437435B (en) 2022-02-24 2022-02-24 High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same

Country Status (1)

Country Link
CN (1) CN114437435B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115926224B (en) * 2022-10-20 2024-05-14 电子科技大学 Prepreg for packaging carrier plate with high heat conductivity and manufacturing of copper-clad plate using prepreg

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107791617B (en) * 2017-10-27 2020-08-04 苏州欣天新精密机械有限公司 Preparation process of low-dielectric-loss copper-clad plate
CN110605880B (en) * 2019-08-07 2021-09-10 常州中英科技股份有限公司 Thermosetting hydrocarbon polymer composition, prepreg prepared from thermosetting hydrocarbon polymer composition and thermosetting copper-clad plate
CN111055585B (en) * 2019-12-26 2021-12-24 艾蒙特成都新材料科技有限公司 Flame-retardant low-dielectric copper-clad plate and preparation method thereof
CN111072979B (en) * 2019-12-30 2022-03-08 四川东材科技集团股份有限公司 Modified hydrocarbon resin prepolymer, copper-clad plate and preparation method thereof
CN111959063A (en) * 2020-08-27 2020-11-20 上海材料研究所 Low-dielectric halogen-free flame-retardant copper-clad plate and manufacturing method thereof

Also Published As

Publication number Publication date
CN114437435A (en) 2022-05-06

Similar Documents

Publication Publication Date Title
CN106853966A (en) The method for preparing high heat conduction graphite film using Graphene doping polyamic acid resin
CN114437435B (en) High-heat-conductivity hydrocarbon resin-based prepreg and high-frequency copper-clad plate prepared from same
TW201528900A (en) Circuit substrate and preparation method thereof
CN111925697B (en) Graphene/water-soluble polymer composite material and preparation method thereof
CN103287032A (en) Laminated material and preparation method and hollow glass microsphere application thereof
CN110077088A (en) A kind of preparation method of composite heat-conducting copper-clad plate
CN113043680A (en) High-heat-dissipation aluminum-based copper-clad plate
CN112622366A (en) Organic substrate composite material and preparation method thereof
CN103554909B (en) Carbon nano tube compound material, its preparation method, prepreg and copper-clad base plate that polymer-silica is coated
TW202030260A (en) Resin composition, prepreg, and laminated plate
CN113044834B (en) Graphene macroscopic body material, graphene/polymer composite material, preparation method and application thereof
CN114525036B (en) Wave-absorbing thermal gasket and preparation method thereof
CN112175354A (en) Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof
CN114561073B (en) Non-fiber-reinforced fluorine-containing resin-based high-frequency copper-clad plate and preparation method thereof
CN110775969A (en) Graphene composite membrane and preparation method thereof
CN112982023B (en) High-strength thin carbon paper and preparation method thereof
CN107522961B (en) Polystyrene-based high-heat-conductive composite material and preparation method thereof
CN114103306B (en) Halogen-free lead-free high-Tg copper-clad plate and processing technology thereof
WO2023115695A1 (en) Wave-absorbing thermally-conductive composite material, and preparation method therefor and use thereof
CN108467511A (en) The recovery method of carbon fiber in a kind of discarded carbon carbon composite
Xia et al. Multilayer cross‐linking polyetherimide/Ti3C2Tx MXenes material with pores channel structure for electromagnetic interference shielding
CN111574938B (en) Self-heat-absorption core-shell toughening material, heat-breaking structure adhesive film containing self-heat-absorption core-shell toughening material, and preparation method and application of heat-breaking structure adhesive film
CN114702783A (en) Transparent glass fiber mobile phone cover plate and preparation method thereof
CN114163867A (en) Preparation method and application of efficient heat-conducting UV-LED ink
CN115926224B (en) Prepreg for packaging carrier plate with high heat conductivity and manufacturing of copper-clad plate using prepreg

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
GR01 Patent grant
GR01 Patent grant