CN110239164B - High-heat-resistance middle-Tg copper-clad plate and preparation method thereof - Google Patents

High-heat-resistance middle-Tg copper-clad plate and preparation method thereof Download PDF

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CN110239164B
CN110239164B CN201910509041.6A CN201910509041A CN110239164B CN 110239164 B CN110239164 B CN 110239164B CN 201910509041 A CN201910509041 A CN 201910509041A CN 110239164 B CN110239164 B CN 110239164B
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parts
weight
epoxy resin
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copper
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CN110239164A (en
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李洪彬
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Chongqing Dekai Industry Co ltd
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Chongqing Dekai Industry Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—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
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/098—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/205—Preparation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B32B2307/306—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

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Abstract

The invention provides a high-heat-resistance middle-Tg copper-clad plate and a preparation method thereof, belonging to the field of layered products. The high-heat-resistance middle-Tg copper-clad plate provided by the invention comprises a prepreg and a copper foil, wherein the single side or double sides of the prepreg are coated with the copper foil. The preparation method of the prepreg comprises the steps of immersing the glass fiber cloth into the glue and drying to obtain the prepreg. Wherein, the raw materials of the glue comprise 50-300 parts of filler, 1500-4000 parts of epoxy resin, 200-400 parts of curing agent, 1-10 parts of catalyst and 100-300 parts of solvent by weight. The preparation process of the laminated board comprises the following steps: and stacking 1-10 layers of prepregs, covering copper foil on one side or two sides, and pressing by using a hot press to obtain the prepreg. The high-heat-resistance middle-Tg copper-clad plate provided by the invention has excellent heat resistance, low Z thermal expansion coefficient and excellent through hole capability, and meets the specification requirements of IPC-4101/99.

Description

High-heat-resistance middle-Tg copper-clad plate and preparation method thereof
Technical Field
The invention belongs to the field of layered products, and particularly relates to a high-heat-resistance middle-Tg copper-clad plate and a preparation method thereof.
Background
Copper-clad plate, also known as substrate. The reinforcing material is soaked with resin, one side or two sides of the reinforcing material are covered with copper foil, and the reinforcing material is hot-pressed to form a plate-shaped material which is called a copper-clad laminate. It is a basic material for printed circuit boards, often called a substrate. When it is used for the production of multilayer boards, it is also called a core board.
The copper-clad plate is a basic material in the electronic industry, is mainly used for processing and manufacturing printed circuit boards, and is widely applied to electronic products such as televisions, radios, computers, mobile communication and the like. The substrate is an insulating laminate composed of polymer synthetic resin and a reinforcing material; the surface of the substrate is covered with a layer of pure copper foil with higher conductivity and good weldability; the copper clad laminate with the copper foil covering one side of the substrate is called a single-sided copper clad laminate, and the copper clad laminate with the copper foil covering both sides of the substrate is called a double-sided copper clad laminate; the copper foil is bonded firmly to the substrate with an adhesive. The thickness of the common copper clad plate is 1.0mm, 1.5mm and 2.0 mm. The copper-clad plates are also of various types. The insulating material can be divided into paper substrate, glass cloth substrate and synthetic fiber board; according to different binder resins, the adhesive is divided into phenolic aldehyde, epoxy, polyester, polytetrafluoroethylene and the like; it can be divided into general type and special type according to the application.
The copper-clad plate comprises the following components: 1. substrate: the insulating laminate composed of the polymer synthetic resin and the reinforcing material can be used as a substrate of the copper clad laminate. The synthetic resins are widely used, and phenol resin, epoxy resin, polytetrafluoroethylene, etc. are commonly used. The reinforcing material is generally paper or cloth, and determines the mechanical properties of the substrate, such as dip soldering resistance, bending strength and the like. 2. Copper foil: it is a key material for manufacturing copper clad laminate, and must have high electric conductivity and good weldability. The surface of the copper foil is required not to have scratches, blisters and wrinkles, the metal purity is not lower than 99.8 percent, and the thickness error is not more than +/-5 mu m. The nominal series of copper foil thicknesses is 18, 25, 35, 70 and 105um, as specified by the ministered standard. At present, copper foils with the thickness of 35um are gradually popularized and used in China. The thinner the copper foil is, the easier it is to etch and drill, and it is particularly suitable for manufacturing high-density printed boards with complicated wiring. 3. Copper-clad plate adhesive: the adhesive is an important factor for firmly attaching the copper foil to the substrate. The peel strength of the copper clad laminate is largely dependent on the properties of the adhesive.
In the prior art, the thermal stress of the copper-clad plate is mostly about 10Sec, and the thermal decomposition index is about 325 ℃, so that the increasing requirements cannot be met.
Disclosure of Invention
Due to the defects in the prior art, the invention provides the high-heat-resistance middle-Tg copper-clad plate and the production process thereof, the raw materials and the preparation method of the glue are comprehensively improved, and the epoxy resin, the curing agent, the filler and the like are improved, so that the finally prepared copper-clad plate has excellent heat resistance, low Z thermal expansion coefficient and excellent through hole capability, and perfectly meets the specification requirements of IPC-4101/99.
Specifically, the invention is realized by the following technical scheme:
the high-heat-resistance middle-Tg copper-clad plate comprises a prepreg and copper foil, wherein the prepreg is coated with the copper foil on one side or two sides, and the preparation method of the prepreg comprises the following steps:
soaking the glass fiber cloth into the glue, and drying to obtain the glass fiber cloth;
the raw materials of the glue comprise a filler, epoxy resin, a curing agent, a catalyst and a solvent;
the raw materials of the glue comprise, by weight, 50-300 parts of a filler, 1500-4000 parts of epoxy resin, 200-400 parts of a curing agent, 1-10 parts of a catalyst and 100-300 parts of a solvent;
the epoxy resin consists of an epoxy resin A and an epoxy resin B, wherein the epoxy resin A is selected from any one of o-cresol type epoxy resin, multifunctional group epoxy resin or cardanol group epoxy resin;
the epoxy resin B is selected from any one of o-cresol type epoxy resin, polyfunctional group epoxy resin or cardanol group epoxy resin, and the type of the epoxy resin A is different from that of the epoxy resin B.
Preferably, the curing agent is a phenolic resin curing agent;
the phenolic resin is selected from any one or more of phenol type phenolic resin, o-phenol type phenolic resin, multifunctional phenolic resin, linear bisphenol A phenolic resin or bisphenol F phenolic resin.
Further preferably, the curing agent is a multifunctional phenolic resin.
More preferably, the curing agent is a phenolic resin curing agent and/or a polyamine curing agent;
preferably, the polyamine curing agent is a ferrocenyl-containing diamine derivative;
more preferably, the diamine derivative of ferrocene is N, N' -bis [ di (ferrocenyl) methyl ] ethylenediamine.
Preferably, the preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 100-150 parts by weight of cardanol and 1-3 parts by weight of oxalic acid under the protection of inert gas, heating to 90-100 ℃, adding 20-25 parts of 30-40 wt% formaldehyde aqueous solution, reacting for 2-3 hours, heating to 110-120 ℃, adding 550 parts of epichlorohydrin and 1-3 parts of alkyl dimethyl ammonium chloride, reacting for 3-5 hours, cooling to 50-70 ℃, adding 20-30 parts of solid sodium hydroxide, continuing to react for 1-3 hours, washing twice with water at 50-70 ℃, and combining organic phases to obtain an intermediate A;
s2, mixing 65-75 parts of the intermediate A, 65-75 parts of alkyl siloxane and 0.001-0.005 part of Karstedt catalyst in parts by weight, heating to 100-120 ℃, reacting for 5-8 hours, cooling to 70-80 ℃, adding 2-5 parts of activated carbon, reacting for 1-3 hours, naturally cooling to room temperature, and filtering to remove solids.
Preferably, the alkyl dimethyl ammonium chloride in the preparation method of the cardanol-based epoxy resin is selected from any one or more of dodecyl dimethyl benzyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, hexadecyl dimethyl benzyl ammonium chloride or octadecyl dimethyl benzyl ammonium chloride.
Preferably, the alkyl siloxane in the preparation method of the cardanol-based epoxy resin is selected from any one or more of tetramethyl disiloxane, pentamethyl disiloxane, hexaethyl disiloxane, hexamethyl trisiloxane, heptamethyl trisiloxane or octamethyl tetrasiloxane.
Preferably, the filler is any one or more of silicon micropowder, carbon nanosphere or graphite foam powder.
Preferably, the filler is a mixed filler consisting of 1-3 parts by weight of the carbon nanoball and 1-3 parts by weight of the graphite foam powder.
Preferably, the method for preparing the carbon nanoball includes the steps of:
s1, adding 3-8 parts by weight of 0.1-0.3g/mL ethyl orthosilicate ethanol solution into a solution consisting of 5-12 parts by weight of ethanol, 0.1-1 part by weight of water and 1-3 parts by weight of ammonia water, stirring for 1-3 hours, centrifuging, and taking a solid to obtain crude silicon dioxide;
s2, dissolving 1-3 parts by weight of crude silicon dioxide in 60-80 parts by weight of ethanol, heating to 60-80 ℃, adding 1-3 parts by weight of silane coupling agent, stirring for 24-36 hours, centrifuging to obtain solid, and drying at the temperature of 100 ℃ and 120 ℃ for 4-8 hours to obtain a silicon dioxide template;
s3, dispersing 1-3 parts by weight of silicon dioxide template in 3-8 parts of 0.2-0.8mol/L sucrose aqueous solution, transferring the solution to a high-pressure reaction kettle, heating to 180 ℃ and keeping the temperature for 2-3 hours, centrifuging, taking solid, drying, and carbonizing at 850 ℃ and 900 ℃ for 1-3 hours under the atmosphere of inert gas to obtain carbonized polysaccharide-silicon dioxide spheres;
s4, soaking 1-3 parts by weight of carbonized polysaccharide-silicon dioxide balls in 2-5 parts by weight of 5-20 wt% hydrofluoric acid aqueous solution for 1-3 hours, centrifuging to obtain a solid, and drying to obtain the silicon dioxide/silicon dioxide/silicon.
Preferably, the preparation method of the graphite foam powder comprises the following steps:
s1, dissolving 0.2-0.8 part by weight of PAN-based carbon fiber in 10-30 parts by weight of DMF, heating to 70-90 ℃, adding 2-5 parts by weight of magnesium powder, removing liquid by rotary evaporation, grinding the obtained solid, sieving with a 100-fold and 500-mesh sieve, placing the obtained solid in a chemical vapor deposition device, heating to 900-fold and 1000 ℃ at a heating rate of 5-10 ℃/min in an argon/hydrogen atmosphere, keeping at 900-fold and 1000 ℃ for 20-60 minutes, cooling to room temperature along with a furnace, and taking out to obtain an intermediate;
s2, soaking 1-3 parts of the intermediate in parts by weight in 3-5 parts of 1mol/L ferric chloride aqueous solution for 24-72 hours, filtering, taking the solid, washing with water for 1-3 times, and drying to obtain the product.
Preferably, in the preparation method S1, the flow rate of argon gas in the chemical vapor deposition device is 400-600sccm, and the flow rate of hydrogen is 100-300 sccm.
Preferably, the catalyst is selected from any one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole or 2-phenylimidazole.
Preferably, the solvent is any one or more of propylene glycol methyl ether acetate, acetone or butanone.
Preferably, the preparation method of the glue comprises the following steps:
s1, filler dispersion: adding the epoxy resin A and the solvent into a stirrer, stirring at a rotating speed of more than 1000rpm, adding the filler while stirring, and after the filler is added, continuously stirring at a rotating speed of more than 1000rpm for 4-5 hours to obtain an intermediate product A;
s2, adding the epoxy resin A and the epoxy resin B into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding a curing agent and a catalyst, sampling and detecting the curing time of the glue solution after stirring for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 1-10 layers of prepregs, coating copper foil on one side or two sides, adding a die, and pressing by using a hot press to obtain the prepreg.
Preferably, the hot press parameters of the preparation method of the high-heat-resistance medium-Tg copper-clad plate are as follows:
the initial stage is as follows: the duration is 25-35 minutes, the temperature is kept at 80-140 ℃, and the pressure is 50-70 psi;
a heating stage: the heating rate is 1.2-2.0 ℃/min, the temperature is raised to 170-180 ℃, and the temperature is stopped, and the pressure is 50-70 psi;
and (3) hot pressing: the time duration is more than or equal to 45 minutes, the constant temperature is 170 ℃ and 180 ℃, and the pressure is 280 ℃ and 370 psi;
and (3) a cooling stage: cooling at a rate of less than 2.5 deg.C/min to room temperature under a pressure of 30-50 psi.
Preferably, the die is alloy steel 4Cr5Mo 2V.
The invention has the advantages that: the copper-clad sheet provided by the invention uses novel glue, the glue uses various epoxy resins, the filler is improved, and a multifunctional phenolic resin is used as a curing agent. Physical stress relaxation in thermoset polymers is limited by crosslinking, which hinders segmental motion and limits relaxation of network defects. At the same time, the curing shrinkage associated with thermosetting polymerization leads to the development of internal residual stresses that cannot be effectively relaxed. And the multifunctional phenolic resin is used as a curing agent, so that the curing stress can be effectively reduced, and the use of dicy curing is avoided. The finally prepared copper-clad sheet has excellent heat resistance, low Z thermal expansion coefficient and excellent through hole capacity.
Detailed Description
The present invention is further illustrated by the following specific examples, which are provided only for the purpose of illustration and are not to be construed as further limiting the invention.
Specifically, the raw material sources in the following examples are as follows:
an o-cresol type epoxy resin having a type of 704K80 and an epoxy equivalent of 215g/eq, manufactured by south Asia electronic materials (Kunshan) Co., Ltd.
The type of the multifunctional epoxy resin is 485HA80, the epoxy equivalent is 400g/eq, and the resin is produced by south Asia electronic materials (Kunshan) Limited.
A multifunctional phenol resin, model number 710HK65, epoxy equivalent 107g/eq, manufactured by south Asia electronic materials (Kunshan) Co.
Glass fiber cloth, electronic grade, model 7628M-127, gram weight 210g/M2Thickness 0.18mm, manufactured by Mount Taishan glass fibers Zhongji Co.
Copper foil, 1 ounce in thickness, produced by lingbao jinyuan Kogyo GmbH.
The silicon powder with the granularity of 1250 meshes is purchased from a processing plant of Zetong mineral products in Lingshou county.
Karstedt's catalyst, Shenzhen, Aucky organosilicon materials Limited.
Activated carbon, 200 mesh coconut shell activated carbon produced by Shanghai Song environmental protection science and technology Limited.
PAN-based carbon fiber, 1.5D PAN-based carbon fiber available from Qidong carbon materials, Inc., Binzhou.
Magnesium powder with a particle size of 3 μm, produced by Gerania magnesium industries, Ltd.
The silane coupling agent KH560 is a chemical name of gamma- (2, 3-glycidoxy) propyl trimethoxy silane, and is produced by Wako pure chemical industries, Ltd.
The die material is alloy steel 4Cr5Mo2V, available from die Steel, Zhongshan Fahrenheit, Inc.
All fillers were 1250 mesh sieved prior to use.
Example 1
The high-heat-resistance middle-Tg copper-clad plate consists of a prepreg and copper foil, wherein the two sides of the prepreg are coated with the copper foil, and the preparation method of the prepreg comprises the following steps:
soaking glass fiber cloth into glue, placing the electronic grade glass fiber cloth on a cloth rack of an impregnator, enabling the glass fiber cloth to pass through an impregnation groove full of the glue, and placing the glass fiber cloth soaked with the glue into an oven to be dried for 1min at 170 ℃ to obtain the glass fiber cloth;
the glue comprises the following raw materials, by weight, 140 parts of a filler, 2500 parts of epoxy resin, 300 parts of a curing agent, 4 parts of a catalyst and 250 parts of a solvent;
the epoxy resin consists of 1250 parts of epoxy resin A and 1250 parts of epoxy resin B according to parts by weight, wherein the epoxy resin A is o-cresol type epoxy resin; the epoxy resin B is multifunctional epoxy resin;
the filler is silicon micropowder;
the curing agent is multifunctional phenolic resin;
the catalyst is 2-methylimidazole;
the solvent is propylene glycol methyl ether acetate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 1000 parts by weight of o-cresol epoxy resin and 250 parts by weight of propylene glycol methyl ether acetate into a stirrer, stirring at the rotating speed of 1200rpm, adding 140 parts by weight of silicon micropowder while stirring, and after the addition is finished, continuing to stir at the rotating speed of 1200rpm for 4 hours to obtain an intermediate product A;
s2, adding 250 parts by weight of o-cresol epoxy resin and 1250 parts by weight of polyfunctional epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding 300 parts by weight of multifunctional phenolic resin and 4 parts by weight of 2-methylimidazole, stirring at 500rpm for 5 hours, sampling and detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280 plus 320 seconds to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 7 layers of prepregs, covering copper foils on two sides, adding a die, pressing by using a hot press, and cutting according to needs to obtain the prepreg;
the hot press parameters were as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 2
The high-heat-resistance middle-Tg copper-clad plate consists of a prepreg and copper foil, wherein the two sides of the prepreg are coated with the copper foil, and the preparation method of the prepreg comprises the following steps:
soaking glass fiber cloth into glue, placing the electronic grade glass fiber cloth on a cloth rack of an impregnation machine, and putting the glass fiber cloth soaked with the glue into an oven for drying at 170 ℃ for 1min through an impregnation groove full of the glue;
the glue comprises the following raw materials, by weight, 140 parts of a filler, 2500 parts of epoxy resin, 300 parts of a curing agent, 4 parts of a catalyst and 250 parts of a solvent;
the epoxy resin consists of 1250 parts of epoxy resin A and 1250 parts of epoxy resin B according to parts by weight, wherein the epoxy resin A is o-cresol type epoxy resin; the epoxy resin B is cardanol-based epoxy resin;
the filler is silicon micropowder;
the curing agent is multifunctional phenolic resin;
the catalyst is 2-methylimidazole;
the solvent is propylene glycol methyl ether acetate.
The preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 120 parts by weight of cardanol and 2 parts by weight of oxalic acid under the protection of nitrogen, heating to 90 ℃, adding 22 parts of 35 wt% formaldehyde aqueous solution, reacting for 2 hours, heating to 115 ℃, adding 480 parts of epichlorohydrin and 2 parts of tetradecyl dimethyl benzyl ammonium chloride, reacting for 4 hours, cooling to 70 ℃, adding 23 parts of solid sodium hydroxide, continuing to react for 2 hours, washing twice with 60 ℃ water, wherein the amount of the 60 ℃ water is equal to the volume of the to-be-washed liquid, and combining organic phases to obtain an intermediate A;
s2, mixing 70 parts of the intermediate A, 70 parts of hexamethyltrisiloxane and 0.0013 part of Karstedt catalyst in parts by weight, heating to 115 ℃, reacting for 6 hours, cooling to 75 ℃, adding 3 parts of activated carbon, reacting for 1 hour, naturally cooling to room temperature, sieving with a 100-mesh sieve, and removing solids to obtain the intermediate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 1000 parts by weight of o-cresol epoxy resin and 250 parts by weight of propylene glycol methyl ether acetate into a stirrer, stirring at the rotating speed of 1200rpm, adding 140 parts by weight of silicon micropowder while stirring, and after the addition is finished, continuing to stir at the rotating speed of 1200rpm for 4 hours to obtain an intermediate product A;
s2, adding 250 parts by weight of o-cresol type epoxy resin and 1250 parts by weight of cardanol based epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding 300 parts by weight of multifunctional phenolic resin and 4 parts by weight of 2-methylimidazole, stirring at 500rpm for 5 hours, sampling and detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280 plus 320 seconds to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 7 layers of prepregs, covering copper foils on two sides, adding a die, pressing by using a hot press, and cutting according to needs to obtain the prepreg;
the hot press parameters were as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 3
The high-heat-resistance middle-Tg copper-clad plate consists of a prepreg and copper foil, wherein the two sides of the prepreg are coated with the copper foil, and the preparation method of the prepreg comprises the following steps:
soaking glass fiber cloth into glue, placing the electronic grade glass fiber cloth on a cloth rack of an impregnation machine, and putting the glass fiber cloth soaked with the glue into an oven for drying at 170 ℃ for 1min through an impregnation groove full of the glue;
the glue comprises the following raw materials, by weight, 140 parts of a filler, 2500 parts of epoxy resin, 300 parts of a curing agent, 4 parts of a catalyst and 250 parts of a solvent;
the epoxy resin consists of 1250 parts of epoxy resin A and 1250 parts of epoxy resin B according to parts by weight, wherein the epoxy resin A is multifunctional epoxy resin; the epoxy resin B is cardanol-based epoxy resin;
the filler is silicon micropowder;
the curing agent is multifunctional phenolic resin;
the catalyst is 2-methylimidazole;
the solvent is propylene glycol methyl ether acetate.
The preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 120 parts by weight of cardanol and 2 parts by weight of oxalic acid under the protection of nitrogen, heating to 90 ℃, adding 22 parts of 35 wt% formaldehyde aqueous solution, reacting for 2 hours, heating to 115 ℃, adding 480 parts of epichlorohydrin and 2 parts of tetradecyl dimethyl benzyl ammonium chloride, reacting for 4 hours, cooling to 70 ℃, adding 23 parts of solid sodium hydroxide, continuing to react for 2 hours, washing twice with 60 ℃ water, wherein the amount of the 60 ℃ water is equal to the volume of the to-be-washed liquid, and combining organic phases to obtain an intermediate A;
s2, mixing 70 parts of the intermediate A, 70 parts of hexamethyltrisiloxane and 0.0013 part of Karstedt catalyst in parts by weight, heating to 115 ℃, reacting for 6 hours, cooling to 75 ℃, adding 3 parts of activated carbon, reacting for 1 hour, naturally cooling to room temperature, sieving with a 100-mesh sieve, and removing solids to obtain the intermediate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 1000 parts by weight of multifunctional epoxy resin and 250 parts by weight of propylene glycol monomethyl ether acetate into a stirrer, stirring at the rotation speed of 1200rpm, adding 140 parts by weight of silicon micropowder while stirring, and after the addition is finished, continuing to stir at the rotation speed of 1200rpm for 4 hours to obtain an intermediate product A;
s2, adding 250 parts by weight of multifunctional epoxy resin and 1250 parts by weight of cardanol epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding 300 parts by weight of multifunctional phenolic resin and 4 parts by weight of 2-methylimidazole, stirring at 500rpm for 5 hours, sampling and detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280 plus 320 seconds to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 7 layers of prepregs, covering copper foils on two sides, adding a die, pressing by using a hot press, and cutting according to needs to obtain the prepreg;
the hot press parameters were as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 4
The high-heat-resistance middle-Tg copper-clad plate consists of a prepreg and copper foil, wherein the two sides of the prepreg are coated with the copper foil, and the preparation method of the prepreg comprises the following steps:
soaking glass fiber cloth into glue, placing the electronic grade glass fiber cloth on a cloth rack of an impregnation machine, and putting the glass fiber cloth soaked with the glue into an oven for drying at 170 ℃ for 1min through an impregnation groove full of the glue;
the glue comprises the following raw materials, by weight, 140 parts of a filler, 2500 parts of epoxy resin, 300 parts of a curing agent, 4 parts of a catalyst and 250 parts of a solvent;
the epoxy resin consists of 1250 parts of epoxy resin A and 1250 parts of epoxy resin B according to parts by weight, wherein the epoxy resin A is o-cresol type epoxy resin; the epoxy resin B is cardanol-based epoxy resin;
the filler is silicon micropowder;
the curing agent consists of 270 parts of multifunctional phenolic resin and 30 parts of N, N' -bis (ferrocenyl) methyl ethylenediamine in parts by weight;
the catalyst is 2-methylimidazole;
the solvent is propylene glycol methyl ether acetate.
The preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 120 parts by weight of cardanol and 2 parts by weight of oxalic acid under the protection of nitrogen, heating to 90 ℃, adding 22 parts of 35 wt% formaldehyde aqueous solution, reacting for 2 hours, heating to 115 ℃, adding 480 parts of epichlorohydrin and 2 parts of tetradecyl dimethyl benzyl ammonium chloride, reacting for 4 hours, cooling to 70 ℃, adding 23 parts of solid sodium hydroxide, continuing to react for 2 hours, washing twice with 60 ℃ water, wherein the amount of the 60 ℃ water is equal to the volume of the to-be-washed liquid, and combining organic phases to obtain an intermediate A;
s2, mixing 70 parts of the intermediate A, 70 parts of hexamethyltrisiloxane and 0.0013 part of Karstedt catalyst in parts by weight, heating to 115 ℃, reacting for 6 hours, cooling to 75 ℃, adding 3 parts of activated carbon, reacting for 1 hour, naturally cooling to room temperature, sieving with a 100-mesh sieve, and removing solids to obtain the intermediate.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 1000 parts by weight of o-cresol epoxy resin and 250 parts by weight of propylene glycol methyl ether acetate into a stirrer, stirring at the rotating speed of 1200rpm, adding 140 parts by weight of silicon micropowder while stirring, and after the addition is finished, continuing to stir at the rotating speed of 1200rpm for 4 hours to obtain an intermediate product A;
s2, adding 250 parts by weight of o-cresol type epoxy resin and 1250 parts by weight of cardanol based epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding 270 parts by weight of multifunctional phenolic resin, 30 parts by weight of N, N' -bis (di (ferrocenyl) methyl) ethylenediamine and 4 parts by weight of 2-methylimidazole, stirring at 500rpm for 5 hours, sampling, detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280-320 seconds to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 7 layers of prepregs, covering copper foils on two sides, adding a die, pressing by using a hot press, and cutting according to needs to obtain the prepreg;
the hot press parameters were as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 5
The high-heat-resistance middle-Tg copper-clad plate consists of a prepreg and copper foil, wherein the two sides of the prepreg are coated with the copper foil, and the preparation method of the prepreg comprises the following steps:
soaking glass fiber cloth into glue, placing the electronic grade glass fiber cloth on a cloth rack of an impregnation machine, and putting the glass fiber cloth soaked with the glue into an oven for drying at 170 ℃ for 1min through an impregnation groove full of the glue;
the glue comprises the following raw materials, by weight, 140 parts of a filler, 2500 parts of epoxy resin, 300 parts of a curing agent, 4 parts of a catalyst and 250 parts of a solvent;
the epoxy resin consists of 1250 parts of epoxy resin A and 1250 parts of epoxy resin B according to parts by weight, wherein the epoxy resin A is o-cresol type epoxy resin; the epoxy resin B is cardanol-based epoxy resin;
the filler is graphite foam powder;
the curing agent consists of 270 parts of multifunctional phenolic resin and 30 parts of N, N' -bis (ferrocenyl) methyl ethylenediamine in parts by weight;
the catalyst is 2-methylimidazole;
the solvent is propylene glycol methyl ether acetate.
The preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 120 parts by weight of cardanol and 2 parts by weight of oxalic acid under the protection of nitrogen, heating to 90 ℃, adding 22 parts of 35 wt% formaldehyde aqueous solution, reacting for 2 hours, heating to 115 ℃, adding 480 parts of epichlorohydrin and 2 parts of tetradecyl dimethyl benzyl ammonium chloride, reacting for 4 hours, cooling to 70 ℃, adding 23 parts of solid sodium hydroxide, continuing to react for 2 hours, washing twice with 60 ℃ water, wherein the amount of the 60 ℃ water is equal to the volume of the to-be-washed liquid, and combining organic phases to obtain an intermediate A;
s2, mixing 70 parts of the intermediate A, 70 parts of hexamethyltrisiloxane and 0.0013 part of Karstedt catalyst in parts by weight, heating to 115 ℃, reacting for 6 hours, cooling to 75 ℃, adding 3 parts of activated carbon, reacting for 1 hour, naturally cooling to room temperature, sieving with a 100-mesh sieve, and removing solids to obtain the intermediate.
The preparation method of the graphite foam powder comprises the following steps:
s1, dissolving 0.4 part by weight of PAN-based carbon fiber in 15 parts by weight of DMF, heating to 80 ℃, adding 3 parts by weight of magnesium powder, performing rotary evaporation to remove liquid, grinding the obtained solid, sieving the ground solid with a 100-mesh sieve, placing the ground solid in a chemical vapor deposition device, and taking out the solid in an argon/hydrogen atmosphere, wherein the argon flow is 500sccm, the hydrogen flow is 200sccm, heating to 1000 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 1000 ℃ for 30 minutes, and cooling to room temperature along with a furnace to obtain an intermediate;
s2, soaking 2 parts of intermediate in parts by weight in 5 parts of 1mol/L ferric chloride aqueous solution for 36 hours, sieving with a 500-mesh sieve, taking the solid, washing with water for 3 times, wherein the amount of washing water is 2 times of the mass of the solid each time, and drying at 60 ℃ for 8 hours to obtain the product.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 1000 parts by weight of o-cresol epoxy resin and 250 parts by weight of propylene glycol methyl ether acetate into a stirrer, stirring at a rotating speed of 1200rpm, adding 140 parts by weight of graphite foam powder while stirring, and after the addition is finished, continuing to stir at the rotating speed of 1200rpm for 4 hours to obtain an intermediate product A;
s2, adding 250 parts by weight of o-cresol type epoxy resin and 1250 parts by weight of cardanol based epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding 270 parts by weight of multifunctional phenolic resin, 30 parts by weight of N, N' -bis (di (ferrocenyl) methyl) ethylenediamine and 4 parts by weight of 2-methylimidazole, stirring at 500rpm for 5 hours, sampling, detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280-320 seconds to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 7 layers of prepregs, covering copper foils on two sides, adding a die, pressing by using a hot press, and cutting according to needs to obtain the prepreg;
the hot press parameters were as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 6
The high-heat-resistance middle-Tg copper-clad plate consists of a prepreg and copper foil, wherein the two sides of the prepreg are coated with the copper foil, and the preparation method of the prepreg comprises the following steps:
soaking glass fiber cloth into glue, placing the electronic grade glass fiber cloth on a cloth rack of an impregnation machine, and putting the glass fiber cloth soaked with the glue into an oven for drying at 170 ℃ for 1min through an impregnation groove full of the glue;
the glue comprises the following raw materials, by weight, 140 parts of a filler, 2500 parts of epoxy resin, 300 parts of a curing agent, 4 parts of a catalyst and 250 parts of a solvent;
the epoxy resin consists of 1250 parts of epoxy resin A and 1250 parts of epoxy resin B according to parts by weight, wherein the epoxy resin A is o-cresol type epoxy resin; the epoxy resin B is cardanol-based epoxy resin;
the filler is carbon nanospheres;
the curing agent comprises 270 parts by weight of multifunctional phenolic resin
The catalyst is 2-methylimidazole;
the solvent is propylene glycol methyl ether acetate.
The preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 120 parts by weight of cardanol and 2 parts by weight of oxalic acid under the protection of nitrogen, heating to 90 ℃, adding 22 parts of 35 wt% formaldehyde aqueous solution, reacting for 2 hours, heating to 115 ℃, adding 480 parts of epichlorohydrin and 2 parts of tetradecyl dimethyl benzyl ammonium chloride, reacting for 4 hours, cooling to 70 ℃, adding 23 parts of solid sodium hydroxide, continuing to react for 2 hours, washing twice with 60 ℃ water, wherein the amount of the 60 ℃ water is equal to the volume of the to-be-washed liquid, and combining organic phases to obtain an intermediate A;
s2, mixing 70 parts of the intermediate A, 70 parts of hexamethyltrisiloxane and 0.0013 part of Karstedt catalyst in parts by weight, heating to 115 ℃, reacting for 6 hours, cooling to 75 ℃, adding 3 parts of activated carbon, reacting for 1 hour, naturally cooling to room temperature, sieving with a 100-mesh sieve, and removing solids to obtain the intermediate.
The preparation method of the carbon nanosphere comprises the following steps:
s1, adding 4 parts by weight of 0.2g/mL ethyl orthosilicate ethanol solution into a solution consisting of 7 parts by weight of ethanol, 0.5 part by weight of water and 2 parts by weight of 25 wt% ammonia water, stirring at 500rpm for 2 hours, centrifuging at 7000rpm for 10 minutes, and taking solid to obtain crude silicon dioxide;
s2, dissolving 1 part of crude silicon dioxide in parts by weight in 70 parts of ethanol, heating to 70 ℃, adding 2 parts of silane coupling agent KH560, stirring at 100rpm for 24 hours, centrifuging at 7000rpm for 10 minutes, taking out the solid, and drying at 110 ℃ for 6 hours to obtain a silicon dioxide template;
s3, dispersing 2 parts by weight of silicon dioxide templates in 6 parts of 0.5mol/L sucrose aqueous solution, transferring the mixture into a high-pressure reaction kettle, heating to 190 ℃, keeping for 2 hours, centrifuging at 5000rpm for 10 minutes, taking out solids, drying at 50 ℃ for 12 hours, and carbonizing at 900 ℃ for 2 hours in a nitrogen atmosphere to obtain carbonized polysaccharide-silicon dioxide spheres;
s4, soaking 1 part of carbonized polysaccharide-silicon dioxide balls in 3 parts of 12 wt% hydrofluoric acid aqueous solution for 3 hours, centrifuging at 5000rpm for 10 minutes, taking the solid, and drying at 70 ℃ for 6 hours to obtain the carbonized polysaccharide-silicon dioxide composite material.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 1000 parts by weight of o-cresol epoxy resin and 250 parts by weight of propylene glycol methyl ether acetate into a stirrer, stirring at the rotating speed of 1200rpm, adding 140 parts by weight of carbon nanospheres while stirring, and after the addition is finished, continuing to stir at the rotating speed of 1200rpm for 4 hours to obtain an intermediate product A;
s2, adding 250 parts by weight of o-cresol type epoxy resin and 1250 parts by weight of cardanol based epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding 270 parts by weight of multifunctional phenolic resin and 4 parts by weight of 2-methylimidazole, stirring at 500rpm for 5 hours, sampling and detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280 plus 320 seconds to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 7 layers of prepregs, covering copper foils on two sides, adding a die, pressing by using a hot press, and cutting according to needs to obtain the prepreg;
the hot press parameters were as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Example 7
The high-heat-resistance middle-Tg copper-clad plate consists of a prepreg and copper foil, wherein the two sides of the prepreg are coated with the copper foil, and the preparation method of the prepreg comprises the following steps:
soaking glass fiber cloth into glue, placing the electronic grade glass fiber cloth on a cloth rack of an impregnation machine, and putting the glass fiber cloth soaked with the glue into an oven for drying at 170 ℃ for 1min through an impregnation groove full of the glue;
the glue comprises the following raw materials, by weight, 140 parts of a filler, 2500 parts of epoxy resin, 300 parts of a curing agent, 4 parts of a catalyst and 250 parts of a solvent;
the epoxy resin consists of 1250 parts of epoxy resin A and 1250 parts of epoxy resin B according to parts by weight, wherein the epoxy resin A is o-cresol type epoxy resin; the epoxy resin B is cardanol-based epoxy resin;
the filler consists of 100 parts of graphite foam powder and 40 parts of carbon nanospheres in parts by weight;
the curing agent comprises 270 parts by weight of multifunctional phenolic resin
The catalyst is 2-methylimidazole;
the solvent is propylene glycol methyl ether acetate.
The preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 120 parts by weight of cardanol and 2 parts by weight of oxalic acid under the protection of nitrogen, heating to 90 ℃, adding 22 parts of 35 wt% formaldehyde aqueous solution, reacting for 2 hours, heating to 115 ℃, adding 480 parts of epichlorohydrin and 2 parts of tetradecyl dimethyl benzyl ammonium chloride, reacting for 4 hours, cooling to 70 ℃, adding 23 parts of solid sodium hydroxide, continuing to react for 2 hours, washing twice with 60 ℃ water, wherein the amount of the 60 ℃ water is equal to the volume of the to-be-washed liquid, and combining organic phases to obtain an intermediate A;
s2, mixing 70 parts of the intermediate A, 70 parts of hexamethyltrisiloxane and 0.0013 part of Karstedt catalyst in parts by weight, heating to 115 ℃, reacting for 6 hours, cooling to 75 ℃, adding 3 parts of activated carbon, reacting for 1 hour, naturally cooling to room temperature, sieving with a 100-mesh sieve, and removing solids to obtain the intermediate.
The preparation method of the graphite foam powder comprises the following steps:
s1, dissolving 0.4 part by weight of PAN-based carbon fiber in 15 parts by weight of DMF, heating to 80 ℃, adding 3 parts by weight of magnesium powder, performing rotary evaporation to remove liquid, grinding the obtained solid, sieving the ground solid with a 100-mesh sieve, placing the ground solid in a chemical vapor deposition device, and taking out the solid in an argon/hydrogen atmosphere, wherein the argon flow is 500sccm, the hydrogen flow is 200sccm, heating to 1000 ℃ at a heating rate of 10 ℃/min, keeping the temperature at 1000 ℃ for 30 minutes, and cooling to room temperature along with a furnace to obtain an intermediate;
s2, soaking 2 parts of intermediate in parts by weight in 5 parts of 1mol/L ferric chloride aqueous solution for 36 hours, sieving with a 500-mesh sieve, taking the solid, washing with water for 3 times, wherein the amount of washing water is 2 times of the mass of the solid each time, and drying at 60 ℃ for 8 hours to obtain the product.
The preparation method of the carbon nanosphere comprises the following steps:
s1, adding 4 parts by weight of 0.2g/mL ethyl orthosilicate ethanol solution into a solution consisting of 7 parts by weight of ethanol, 0.5 part by weight of water and 2 parts by weight of 25 wt% ammonia water, stirring at 500rpm for 2 hours, centrifuging at 7000rpm for 10 minutes, and taking solid to obtain crude silicon dioxide;
s2, adding 1 part of crude silicon dioxide in parts by weight into 70 parts of ethanol, heating to 70 ℃, adding 2 parts of silane coupling agent KH560, stirring at 100rpm for 24 hours, centrifuging at 7000rpm for 10 minutes, taking out a solid, and drying at 110 ℃ for 6 hours to obtain a silicon dioxide template;
s3, dispersing 2 parts by weight of silicon dioxide templates in 6 parts of 0.5mol/L sucrose aqueous solution, transferring the mixture into a high-pressure reaction kettle, heating to 190 ℃, keeping for 2 hours, centrifuging at 5000rpm for 10 minutes, taking out solids, drying at 50 ℃ for 12 hours, and carbonizing at 900 ℃ for 2 hours in a nitrogen atmosphere to obtain carbonized polysaccharide-silicon dioxide spheres;
s4, soaking 1 part of carbonized polysaccharide-silicon dioxide balls in 3 parts of 12 wt% hydrofluoric acid aqueous solution for 3 hours, centrifuging at 5000rpm for 10 minutes, taking the solid, and drying at 70 ℃ for 6 hours to obtain the carbonized polysaccharide-silicon dioxide composite material.
The preparation method of the glue comprises the following steps:
s1, filler dispersion: adding 1000 parts by weight of o-cresol epoxy resin and 250 parts by weight of propylene glycol methyl ether acetate into a stirrer, stirring at the rotating speed of 1200rpm, adding 100 parts by weight of graphite foam powder and 40 parts by weight of carbon nanospheres while stirring, and after the addition is finished, continuing to stir at the rotating speed of 1200rpm for 4 hours to obtain an intermediate product A;
s2, adding 250 parts by weight of o-cresol type epoxy resin and 1250 parts by weight of cardanol based epoxy resin into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding 270 parts by weight of multifunctional phenolic resin, 30 parts by weight of N, N' -bis (di (ferrocenyl) methyl) ethylenediamine and 4 parts by weight of 2-methylimidazole, stirring at 500rpm for 5 hours, sampling, detecting the curing time of the glue solution, and stopping stirring when the curing time of the glue solution is 280-320 seconds to obtain the glue solution.
The preparation method of the high-heat-resistance middle-Tg copper-clad plate comprises the following steps:
stacking 7 layers of prepregs, covering copper foils on two sides, adding a die, pressing by using a hot press, and cutting according to needs to obtain the prepreg;
the hot press parameters were as follows:
the initial stage is as follows: the time is 30 minutes, the temperature is kept at 100 ℃, and the pressure is 60 psi;
a heating stage: the heating rate is 1.5 ℃/min, the temperature is increased to 180 ℃, and the temperature is stopped, and the pressure is 60 psi;
and (3) hot pressing: the time is 45 minutes, the temperature is kept at 180 ℃, and the pressure is 320 psi;
and (3) a cooling stage: the cooling rate was 2 deg.C/min, and cooling to room temperature was stopped at a pressure of 40 psi.
Test example 1
The high heat resistance middle Tg copper clad laminate prepared in example 1 was tested for its main properties according to the requirements of IPC-4101/99, and the test results are shown in Table 1.
Table 1 example 1 properties
Figure BDA0002092811050000191
Figure BDA0002092811050000201
Test example 2
Glass transition temperature
The glass transition temperature of the high heat resistant mid Tg copper clad laminate made in examples 1-7 was tested using a differential scanning calorimeter.
The test results are shown in table 2.
TABLE 2 glass transition temperature (Tg)
GlassMelting temperature/. degree.C
Example 1 155
Example 2 155
Example 3 156
Example 4 156
Example 5 157
Example 6 156
Example 7 157
As can be seen from the table above, the Tg copper clad laminate provided by the invention has a high heat resistance, and the glass transition temperature of the Tg copper clad laminate is more than 150 ℃, and meets the IPC-4101 standard.
Test example 3
Coefficient of thermal expansion in Z direction
The high heat resistance middle Tg copper clad laminate prepared in examples 1 to 7 was subjected to a Z thermal expansion coefficient test using a thermal expansion tester.
The test results are shown in table 3.
TABLE 3Z coefficient of thermal expansion (Z-axis CTE)
Figure BDA0002092811050000211
As can be seen from the table, the high-heat-resistance medium-Tg copper-clad plate provided by the invention has excellent Z-direction thermal expansion coefficient, and particularly has certain influence on the Z-direction expansion coefficient of the copper-clad plate after the filler is changed.
Test example 4
Temperature of thermal decomposition
The high heat resistant mid Tg copper clad laminate prepared in examples 1-7 was tested for thermal decomposition temperature using a differential scanning calorimeter. The test conditions were a temperature rise rate of 10 ℃/min, a nitrogen atmosphere, and a 5% mass loss.
The test results are shown in table 4.
TABLE 4 thermal decomposition temperature
Figure BDA0002092811050000212
Figure BDA0002092811050000221
As can be seen from the above table, the thermal decomposition temperature of the high heat resistance and Tg copper-clad plate provided by the invention is at a higher level, exceeding 325 ℃ specified by the standard, and far exceeding other copper-clad plates in the prior art.
Test example 5
Thermal stress
The unetched high heat resistance mid Tg copper clad laminate made in examples 1-7 was tested for thermal stress with reference to the IPC-4101 standard. The test conditions were float288 ℃/10 Sec.
The test results are shown in table 5.
TABLE 5 thermal stress
Thermal stress/Sec
Example 1 120
Example 2 144
Example 3 125
Example 4 208
Example 5 211
Example 6 220
Example 7 277
As can be seen from the above table, the thermal stress of the high-heat-resistance medium-Tg copper-clad plate provided by the invention is in a higher level, far exceeds the standard value Sec, and can reach 277Sec at most.

Claims (7)

1. The high-heat-resistance middle-Tg copper-clad plate comprises a prepreg and copper foil, wherein the prepreg is coated with the copper foil on one side or two sides, and the preparation method of the prepreg comprises the following steps:
soaking the glass fiber cloth into the glue, and drying to obtain the glass fiber cloth;
the raw materials of the glue comprise, by weight, 50-300 parts of a filler, 1500-4000 parts of epoxy resin, 200-400 parts of a curing agent, 1-10 parts of a catalyst and 100-300 parts of a solvent;
the epoxy resin consists of an epoxy resin A and an epoxy resin B, wherein the epoxy resin A is o-cresol type epoxy resin; the epoxy resin B is cardanol-based epoxy resin;
the curing agent is multifunctional phenolic resin;
the preparation method of the cardanol-based epoxy resin comprises the following steps:
s1, mixing 100-150 parts by weight of cardanol and 1-3 parts by weight of oxalic acid under the protection of inert gas, heating to 90-100 ℃, adding 20-25 parts of 30-40 wt% formaldehyde aqueous solution, reacting for 2-3 hours, heating to 110-120 ℃, adding 550 parts of epichlorohydrin and 1-3 parts of alkyl dimethyl ammonium chloride, reacting for 3-5 hours, cooling to 50-70 ℃, adding 20-30 parts of solid sodium hydroxide, continuing to react for 1-3 hours, washing twice with water at 50-70 ℃, and combining organic phases to obtain an intermediate A;
s2, mixing 65-75 parts of the intermediate A, 65-75 parts of alkyl siloxane and 0.001-0.005 part of Karstedt catalyst in parts by weight, heating to 100-120 ℃, reacting for 5-8 hours, cooling to 70-80 ℃, adding 2-5 parts of activated carbon, reacting for 1-3 hours, naturally cooling to room temperature, and filtering to remove solids.
2. The high heat-resistant middle Tg copper-clad plate according to claim 1, wherein the filler is any one or more of micro silica powder, nano carbon spheres and foamed graphite powder.
3. The high heat-resistant middle Tg copper-clad plate according to claim 2, wherein the preparation method of the carbon nanospheres comprises the following steps:
s1, adding 3-8 parts by weight of 0.1-0.3g/mL ethyl orthosilicate ethanol solution into a solution consisting of 5-12 parts by weight of ethanol, 0.1-1 part by weight of water and 1-3 parts by weight of ammonia water, stirring for 1-3 hours, centrifuging, and taking a solid to obtain crude silicon dioxide;
s2, dissolving 1-3 parts by weight of crude silicon dioxide in 60-80 parts by weight of ethanol, heating to 60-80 ℃, adding 1-3 parts by weight of silane coupling agent, stirring for 24-36 hours, centrifuging to obtain solid, and drying at the temperature of 100 ℃ and 120 ℃ for 4-8 hours to obtain a silicon dioxide template;
s3, dispersing 1-3 parts by weight of silicon dioxide template in 3-8 parts of 0.2-0.8mol/L sucrose aqueous solution, transferring the solution to a high-pressure reaction kettle, heating to 180 ℃ and keeping the temperature for 2-3 hours, centrifuging, taking solid, drying, and carbonizing at 850 ℃ and 900 ℃ for 1-3 hours under the atmosphere of inert gas to obtain carbonized polysaccharide-silicon dioxide spheres;
s4, soaking 1-3 parts by weight of carbonized polysaccharide-silicon dioxide balls in 2-5 parts by weight of 5-20 wt% hydrofluoric acid aqueous solution for 1-3 hours, centrifuging to obtain a solid, and drying to obtain the silicon dioxide/silicon dioxide/silicon.
4. The high heat-resistant middle Tg copper-clad plate according to claim 2, wherein the preparation method of the graphite foam powder comprises the following steps:
s1, dissolving 0.2-0.8 part by weight of PAN-based carbon fiber in 10-30 parts by weight of DMF, heating to 70-90 ℃, adding 2-5 parts by weight of magnesium powder, removing liquid by rotary evaporation, grinding the obtained solid, sieving with a 100-fold and 500-mesh sieve, placing the obtained solid in a chemical vapor deposition device, heating to 900-fold and 1000 ℃ at a heating rate of 5-10 ℃/min in an argon/hydrogen atmosphere, keeping at 900-fold and 1000 ℃ for 20-60 minutes, cooling to room temperature along with a furnace, and taking out to obtain an intermediate;
s2, soaking 1-3 parts of the intermediate in parts by weight in 3-5 parts of 1mol/L ferric chloride aqueous solution for 24-72 hours, filtering, taking the solid, washing with water for 1-3 times, and drying to obtain the product.
5. The high heat resistant middle Tg copper clad laminate of claim 1 wherein the catalyst is selected from any one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole.
6. The high heat-resistant middle Tg copper-clad plate according to claim 1, wherein the preparation method of the glue comprises the following steps:
s1, filler dispersion: adding the epoxy resin A and the solvent into a stirrer, stirring at a rotating speed of more than 1000rpm, adding the filler while stirring, and after the filler is added, continuously stirring at a rotating speed of more than 1000rpm for 4-5 hours to obtain an intermediate product A;
s2, adding the epoxy resin A and the epoxy resin B into a batching tank, adding the intermediate product A, and stirring to obtain an intermediate product B;
s3, adding the intermediate product B into a batching vat, adding a curing agent and a catalyst, sampling and detecting the curing time of the glue solution after stirring for at least 5 hours, and stopping stirring when the curing time of the glue solution is 280-320S to obtain the glue solution.
7. The preparation method of the high heat-resistant middle Tg copper-clad plate according to any one of claims 1 to 6, characterized by comprising the following steps:
and stacking 1-10 layers of semi-solidified plates, covering copper foil on one side or two sides, adding a mould, and pressing by using a hot press to obtain the composite material.
CN201910509041.6A 2019-06-13 2019-06-13 High-heat-resistance middle-Tg copper-clad plate and preparation method thereof Active CN110239164B (en)

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