CN114654829A - Aluminum-based copper-clad plate with high breakdown voltage and production process thereof - Google Patents

Aluminum-based copper-clad plate with high breakdown voltage and production process thereof Download PDF

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Publication number
CN114654829A
CN114654829A CN202210370435.XA CN202210370435A CN114654829A CN 114654829 A CN114654829 A CN 114654829A CN 202210370435 A CN202210370435 A CN 202210370435A CN 114654829 A CN114654829 A CN 114654829A
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semi
production process
aluminum
micro powder
aluminum substrate
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CN114654829B (en
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邓飞
邓后胜
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Jiangxi Xinyuanji Electronic Technology Co ltd
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Jiangxi Xinyuanji Electronic Technology Co ltd
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    • 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
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/017—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of aluminium or an aluminium alloy, another layer being formed of an alloy based on a non ferrous metal other than aluminium
    • 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
    • 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
    • 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
    • B32B37/1018—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 using only vacuum
    • 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
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • 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
    • B32B38/0036—Heat treatment
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/06—Coating on the layer surface on metal 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention develops a high-breakdown-voltage aluminum-based copper-clad plate and a production process thereof, wherein the insulating adhesive layer has post-curing performance by adjusting the formula of the insulating adhesive layer and the pressing and forming process, so that the internal stress can be effectively released while the adhesive performance is ensured, the production efficiency is improved, and the breakdown voltage of the aluminum-based copper-clad plate can be greatly improved.

Description

Aluminum-based copper-clad plate with high breakdown voltage and production process thereof
Technical Field
The invention relates to a production process of an aluminum-based copper-clad plate, in particular to an aluminum-based copper-clad plate with high breakdown voltage and a production process thereof.
Background
The aluminum-based copper-clad plate is the most important raw material for preparing the PCB, and is a plate-shaped material which is prepared by using electronic glass fiber cloth or other reinforced materials, soaking resin or single resin and the like as an insulating bonding layer, coating copper foil on one surface or two surfaces of the electronic glass fiber cloth or other reinforced materials and performing hot pressing, wherein the structure of the plate-shaped material generally comprises three layers of copper foil, insulating bonding layers and aluminum plates. Because the aluminum-based copper-clad plate has good heat-conducting property, the aluminum-based copper-clad plate is more and more widely applied to PCB production.
The thickness of an aluminum base material of a common aluminum-based copper-clad plate is about 0.6-3.0mm, and the common aluminum-based copper-clad plate belongs to a rigid copper-clad plate. The aluminum-based copper-clad plate has the advantage of good heat dispersion, but also has the following defects: 1. because the aluminum base material is a rigid material, the difference of the thermal expansion coefficients of the three-layer structure is large in the process of laminating and forming the insulating bonding layer after copper is coated, so that the internal stress of the aluminum-based copper-clad plate is large, the aluminum-based copper-clad plate is warped, and an unqualified product is formed; 2. because the surface of the copper foil is not an ideal smooth plane but has burrs, when the aluminum-based copper-clad plate is used for breakdown voltage and voltage test, the burrs are easy to form point discharge, and the breakdown voltage of the aluminum-based copper-clad plate and the working stability of a PCB (printed circuit board) produced subsequently are influenced.
In the prior art, aiming at the 1 st defect, the internal stress is released slowly by a method of keeping the pressing pressure after pressing and forming and then slowly cooling so as to prevent the aluminum-based copper-clad plate from warping, but the influence on the production efficiency is large; aiming at the 2 nd defect, a plurality of process methods are adopted to solve the following problems: if an insulating bonding layer with better electrical insulation performance is adopted, insulating filler is added in the insulating bonding layer, and the like, because the aluminum-based copper-clad plate is not suitable to be too thick, a process method for increasing the thickness of the insulating bonding layer is rarely adopted.
Disclosure of Invention
The invention develops an aluminum-based copper-clad plate with high breakdown voltage and a production process thereof, which ensures that an insulating bonding layer has post-curing performance by adjusting the formula of the insulating bonding layer and the press-forming process, can effectively release internal stress while ensuring the bonding performance, improves the production efficiency, and greatly improves the breakdown voltage of the aluminum-based copper-clad plate.
A production process of an aluminum-based copper-clad plate with high breakdown voltage specifically comprises the following steps:
preparing insulating glue:
50-60 parts of epoxy resin, 10-15 parts of isocyanate modified epoxy resin, 15-20 parts of rubber modified epoxy resin, 5-10 parts of post-cured monomer, 0.1-0.3 part of curing agent and 0.01-0.03 part of inhibitor; preparing insulating glue according to the mass parts;
(II) preparing a semi-cured layer
Respectively coating the insulating glue on an aluminum substrate and a copper foil, and heating the aluminum substrate and the copper foil to 90-100 ℃ to semi-solidify the insulating glue to form a semi-solidified layer;
(III) Press Molding
Spreading and stacking the aluminum substrate and the copper foil with the semi-cured layer attached thereon, enabling the semi-cured layer on the aluminum substrate and the semi-cured layer on the copper foil to be opposite and contacted, then sending the aluminum substrate and the copper foil into a press for press-forming molding, wherein the press-forming molding is carried out in a vacuum atmosphere, the temperature is increased to 200-220 ℃ at the pressure of 0.8-1.0 MPa and the temperature-rising rate of 2.0-2.5 ℃/min, and the curing time is 10-15 min;
(IV) pressure cooling
Maintaining the pressure during press-forming, cooling to 120-130 ℃ at the cooling rate of 1.0-1.2 ℃/min, staying at the temperature for 1-2min, taking out, placing into a drying room with the same temperature for post-curing, and keeping for 2-3h to obtain the aluminum-based copper-clad plate.
The prepared aluminum-based copper-clad plate can be delivered through the working sections of plate shearing machine cutting, quality inspection, finished product packaging and the like.
Further, the post-curing monomer is one or more of isobornyl methacrylate, tert-butylcyclohexyl methacrylate and tetrahydrofuran methacrylate.
Further, the curing agent is a mixed curing agent of imidazole curing agent and Vicbase TC3635 in a mass ratio of 4-5: 1.
Further, the imidazole curing agent is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
Further, the inhibitor is methyl hydroquinone.
Furthermore, when the semi-cured layer is prepared in the second step, the insulating glue coated on the aluminum substrate is added with light insulating nano micro powder with the mass fraction of 0.2-0.5%.
Further, the light insulating nano micro powder is PE or PP micro powder with the particle size of 50nm-100 nm.
Further, the light insulating nano micro powder is modified, and the modification process is as follows:
(1) emulsifying 1-3 wt% of ethylene glycol dimethacrylate in pure water, adding 0.3-0.5 wt% of epichlorohydrin after uniform emulsification, and preparing modifying emulsion;
(2) hydrogen peroxide with the mass fraction of 3-5% is sprayed on the surface of the light insulating nano micro powder with the mass of 10-15 times that of the ethylene glycol dimethacrylate, and the mixture is fully stirred to activate the surface;
(3) and (2) adding the activated light insulating nano micro powder into the emulsion for modification prepared in the step (1), fully dispersing, heating to 50-60 ℃, simultaneously dropwise adding a small amount of hydrochloric acid, reacting for 1-2h, filtering out the light insulating nano micro powder, and drying to obtain the modified light insulating nano micro powder.
The invention has the advantages that:
1. the semi-cured layer for forming the insulating bonding layer is divided into two parts, one part is bonded on the aluminum substrate, and the other part is bonded on the copper foil; by heating the aluminum substrate and the copper foil, the semi-cured layers are more crosslinked on one surface close to the aluminum substrate and the copper foil, and less crosslinked on one surface far away from the aluminum substrate and the copper foil, so that the two semi-cured layers can be conveniently fused and cured subsequently while the semi-cured layers are fixed;
2. the post-curing monomer is added and post-cured in the drying room, so that the shrinkage stress in the insulating bonding layer can be effectively released, and the aluminum-based copper-clad plate can be effectively prevented from deforming and warping;
3. the light insulating nano micro powder is added to the semi-cured layer on the aluminum substrate, so that most of the light insulating nano micro powder is distributed in the middle of the insulating bonding layer after being cured, and the breakdown voltage of the aluminum-based copper-clad plate is effectively improved;
4. the light insulating nano micro powder is modified, so that the peeling strength of the aluminum-based copper-clad plate can be improved.
Detailed Description
Example 1
A production process of an aluminum-based copper-clad plate with high breakdown voltage specifically comprises the following steps:
preparing insulating glue:
50 parts of epoxy resin, 15 parts of isocyanate modified epoxy resin, 15 parts of rubber modified epoxy resin, 5 parts of isobornyl methacrylate, 0.1 part of curing agent and 0.01 part of methyl hydroquinone; the curing agent is a mixed curing agent with the mass ratio of 2-methylimidazole to Vicbase TC3635 being 5: 1; preparing insulating glue according to the mass parts;
(II) preparing a semi-cured layer
Coating insulating glue on a copper foil, and heating the copper foil to 90 ℃ to semi-solidify the insulating glue to form a semi-solidified layer;
meanwhile, adding 0.2 mass percent of modified light insulating nano micro powder into the insulating adhesive, then coating the insulating adhesive on an aluminum substrate, and heating the aluminum substrate to 90 ℃ to semi-cure the insulating adhesive to form a semi-cured layer;
the modified light insulating nano micro powder is modified as follows:
(1) emulsifying 1 percent by mass of ethylene glycol dimethacrylate in pure water, adding 0.3 percent of epoxy chloropropane after uniform emulsification, and preparing emulsion for modification;
(2) spraying hydrogen peroxide with the mass fraction of 5% on the surface of PE micro powder with the particle size of 50nm, wherein the mass of the PE micro powder is 15 times that of ethylene glycol dimethacrylate, and fully stirring to activate the surface;
(3) adding the activated PE micro powder into the emulsion for modification prepared in the step (1), fully dispersing, heating to 50 ℃, simultaneously dropwise adding a small amount of hydrochloric acid, reacting for 2 hours, filtering out the PE micro powder, and drying to obtain modified light insulating nano micro powder;
(III) Press Molding
Spreading and stacking the aluminum substrate and the copper foil with the semi-cured layer attached thereon, enabling the semi-cured layer on the aluminum substrate and the semi-cured layer on the copper foil to be opposite and contacted, then sending the aluminum substrate and the semi-cured layer on the copper foil into a press for press-forming, carrying out the press-forming in a vacuum atmosphere, raising the temperature to 200 ℃ at the pressure of 0.8MPa and the temperature raising rate of 2.0 ℃/min, and curing for 15 min;
(IV) pressure cooling
Maintaining the pressure during press-forming, cooling to 120 ℃ at the cooling rate of 1.0 ℃/min, staying at the temperature for 1min, taking out, placing into a drying room at 120 ℃ for post-curing, and keeping for 3h to obtain the aluminum-based copper-clad plate.
Example 2
A production process of an aluminum-based copper-clad plate with high breakdown voltage specifically comprises the following steps:
preparing insulating glue:
55 parts of epoxy resin, 12 parts of isocyanate modified epoxy resin, 18 parts of rubber modified epoxy resin, 9 parts of tert-butylcyclohexyl methacrylate, 0.2 part of curing agent and 0.02 part of methyl hydroquinone; the curing agent is a mixed curing agent with the mass ratio of 2-ethyl-4-methylimidazole to Vicbase TC3635 being 4: 1; preparing insulating glue according to the mass parts;
(II) preparing a semi-cured layer
Coating insulating glue on a copper foil, and heating the copper foil to 92 ℃ to semi-solidify the insulating glue to form a semi-solidified layer;
meanwhile, adding 0.3 mass percent of modified light insulating nano micro powder into the insulating adhesive, then coating the insulating adhesive on an aluminum substrate, and heating the aluminum substrate to 92 ℃ to semi-cure the insulating adhesive to form a semi-cured layer;
the modified light insulating nano micro powder is modified as follows:
(1) emulsifying 2 percent by mass of ethylene glycol dimethacrylate in pure water, adding 0.4 percent of epoxy chloropropane after uniform emulsification, and preparing emulsion for modification;
(2) spraying hydrogen peroxide with the mass fraction of 4% on the surface of PP micro powder with the particle size of 50nm, the mass of which is 12 times that of ethylene glycol dimethacrylate, and fully stirring to activate the surface;
(3) adding activated PP micro powder into the emulsion for modification prepared in the step (1), fully dispersing, heating to 60 ℃, simultaneously dropwise adding a small amount of hydrochloric acid, reacting for 2 hours, filtering out the PP micro powder, and drying to obtain modified light insulating nano micro powder;
(III) Press Molding
Spreading and stacking the aluminum substrate and the copper foil with the semi-cured layer attached thereon, enabling the semi-cured layer on the aluminum substrate and the semi-cured layer on the copper foil to be opposite and contacted, then sending the aluminum substrate and the semi-cured layer on the copper foil into a press for press-forming, carrying out the press-forming in a vacuum atmosphere, raising the temperature to 205 ℃ at the pressure of 1.0MPa and the temperature raising rate of 2.0 ℃/min, and curing for 12 min;
(IV) pressure cooling
Maintaining the pressure during press-forming, cooling to 120 ℃ at the cooling rate of 1.0 ℃/min, staying at the temperature for 2min, taking out, placing into a drying room at 120 ℃ for post-curing, and keeping for 3h to obtain the aluminum-based copper-clad plate.
Example 3
A production process of an aluminum-based copper-clad plate with high breakdown voltage specifically comprises the following steps:
preparing insulating glue:
60 parts of epoxy resin, 10 parts of isocyanate modified epoxy resin, 20 parts of rubber modified epoxy resin, 10 parts of tetrahydrofuran methacrylate, 0.3 part of curing agent and 0.03 part of methyl hydroquinone; the curing agent is a mixed curing agent with the mass ratio of 2-phenylimidazole to Vicbase TC3635 being 4: 1; preparing insulating glue according to the mass parts;
(II) preparing a semi-cured layer
Coating insulating glue on a copper foil, and heating the copper foil to 100 ℃ to semi-solidify the insulating glue to form a semi-solidified layer;
meanwhile, adding 0.5 mass percent of modified light insulating nano micro powder into the insulating adhesive, then coating the insulating adhesive on an aluminum substrate, and heating the aluminum substrate to 100 ℃ to semi-cure the insulating adhesive to form a semi-cured layer;
the modified light insulating nano micro powder is modified as follows:
(1) emulsifying 3 mass percent of ethylene glycol dimethacrylate in pure water, adding 0.5 percent of epoxy chloropropane after uniform emulsification, and preparing emulsion for modification;
(2) spraying hydrogen peroxide with the mass fraction of 3% on the surface of PP micro powder with the particle size of 100nm, the mass of which is 10 times that of ethylene glycol dimethacrylate, and fully stirring to activate the surface;
(3) adding the activated PP micro powder into the emulsion for modification prepared in the step (1), fully dispersing, heating to 60 ℃, simultaneously dropwise adding a small amount of hydrochloric acid, reacting for 1 hour, filtering out the PP micro powder, and drying to obtain modified light insulating nano micro powder;
(III) Press-bonding molding
Spreading and stacking the aluminum substrate and the copper foil with the semi-cured layer attached thereon, enabling the semi-cured layer on the aluminum substrate and the semi-cured layer on the copper foil to be opposite and contacted, then sending the aluminum substrate and the semi-cured layer on the copper foil into a press for press-forming, carrying out the press-forming in a vacuum atmosphere, raising the temperature to 220 ℃ at the pressure of 1.0MPa and the temperature raising rate of 2.5 ℃/min, and curing for 10 min;
(IV) pressure cooling
Maintaining the pressure during press-forming, cooling to 130 ℃ at the cooling rate of 1.2 ℃/min, staying at the temperature for 2min, taking out, placing into a drying room at 130 ℃ for post-curing, and keeping for 2h to obtain the aluminum-based copper-clad plate.
Example 4
In the second step of the production process, the semi-cured layer is prepared, and the modified light insulating nano micro powder is not added into the insulating adhesive coated on the aluminum substrate, and the other processes are the same as the example 2.
Example 5
In the second step of the production process, in the process of preparing the semi-cured layer, the unmodified PP micro powder with the particle size of 50nm is added into the insulating glue coated on the aluminum substrate, and the rest processes are the same as the example 2.
Comparative example 1
In the process for preparing the semi-cured layer in the second step in the production process, insulating glue is coated on copper foil to prepare the semi-cured layer with the thickness 2 times that of the semi-cured layer in the embodiment 2; the aluminum substrate was not coated, and then the copper foil having the semi-cured layer was laminated with the aluminum substrate, and the other process was the same as in example 2.
Comparative example 2
In the process for preparing the semi-cured layer in the second step in the production process, after the copper foil and the aluminum substrate are coated, the semi-cured layer is prepared by curing in a drying room at the temperature of 92 ℃, and the other processes are the same as the process in the example 2.
Comparative example 3
In the process for preparing the semi-cured layer in the second step in the production process, the PP micro powder is not activated by hydrogen peroxide in the modification process of the PP micro powder, and the rest processes are the same as in the example 2.
Comparative example 4
In the process for preparing the semi-cured layer in the second step in the production process, trimethylolpropane dimethacrylate is used for replacing ethylene glycol dimethacrylate in the modification process of the PP micro powder, and the other processes are the same as in the example 2.
Comparative example 5
In the process of pressure cooling in the fourth step, the aluminum-based copper-clad plate is directly placed into a drying room at the temperature of 120 ℃ and is solidified for 3 hours without staying after being cooled to 120 ℃, and other processes are the same as the process in the embodiment 2.
Comparative example 6
A production process of an aluminum-based copper-clad plate is characterized in that tert-butylcyclohexyl methacrylate and Vicbase TC3635 are not added into insulating glue, the process for preparing a semi-cured layer in the second step is the same as that in example 2, the third step of press-forming is carried out in a vacuum atmosphere, the temperature is raised to 205 ℃ at the pressure of 1.0MPa and the temperature raising rate of 2.0 ℃/min, and the curing time is 30 min; and the fourth step of pressure cooling is to maintain the pressure during the press-molding, to reduce the temperature to 60 ℃ at a cooling rate of 0.5 ℃/min, and to stay at the temperature for 10min, and the rest of the processes are the same as those in example 2.
Comparative example 7
The production process of the aluminum-based copper-clad plate is the same as that of the embodiment 2 except that tert-butylcyclohexyl methacrylate is not added into insulating glue.
Comparative example 8
A production process of an aluminum-based copper-clad plate is characterized in that Vicbase TC3635 is not added into insulating glue, and the rest processes are the same as those in embodiment 2.
Comparative example 9
The third step of pressing and forming is carried out in a vacuum atmosphere, the temperature is raised to 205 ℃ at the pressure of 1.0MPa and the heating rate of 2.0 ℃/min, and the curing time is 30 min; and the fourth step of pressure cooling is to maintain the pressure during the press-molding, to reduce the temperature to 60 ℃ at a cooling rate of 0.5 ℃/min, and to stay at the temperature for 10min, and the rest of the processes are the same as those in example 2.
Using the same batch of raw materials and production lines, trial-manufacturing 200 aluminum-based copper-clad plates with dielectric layers of 120 +/-10 microns according to the production processes of the embodiment and the comparative example, measuring the thickness of the insulating bonding layer, selecting 10 aluminum-based copper-clad plates produced by the embodiment and the comparative example for performance detection with the thickness deviation within 1 micron, and taking the average value of the test results:
1. the warpage (. 10) was measured according to GB/T4677.5-1984 printed Board warpage test method-2mm/mm)；
2. The peel strength (N/mm) was tested according to the method 4010 peeling strength in GJB 1651-1993 test method for metal-clad laminate for printed Circuit;
3. the breakdown voltage (kV) was tested according to method 5040 dielectric breakdown Strength (perpendicular to the plane of the board) in GJB 1651-.
Figure BDA0003588341910000091
And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.

Claims (8)

1. A production process of an aluminum-based copper-clad plate with high breakdown voltage is characterized by comprising the following steps: the production process specifically comprises the following steps:
preparing insulating glue:
50-60 parts of epoxy resin, 10-15 parts of isocyanate modified epoxy resin, 15-20 parts of rubber modified epoxy resin, 5-10 parts of post-cured monomer, 0.1-0.3 part of curing agent and 0.01-0.03 part of inhibitor; preparing insulating glue according to the mass parts;
(II) preparing a semi-cured layer
Respectively coating the insulating glue on an aluminum substrate and a copper foil, and heating the aluminum substrate and the copper foil to 90-100 ℃ to semi-solidify the insulating glue to form a semi-solidified layer;
(III) Press Molding
Spreading and stacking the aluminum substrate and the copper foil with the semi-cured layer attached thereon, enabling the semi-cured layer on the aluminum substrate and the semi-cured layer on the copper foil to be opposite and contacted, then sending the aluminum substrate and the copper foil into a press for press-forming molding, wherein the press-forming molding is carried out in a vacuum atmosphere, the temperature is increased to 200-220 ℃ at the pressure of 0.8-1.0 MPa and the temperature-rising rate of 2.0-2.5 ℃/min, and the curing time is 10-15 min;
(IV) pressure cooling
Maintaining the pressure during press-forming, cooling to 120-130 ℃ at the cooling rate of 1.0-1.2 ℃/min, staying at the temperature for 1-2min, taking out, placing into a drying room with the same temperature for post-curing, and keeping for 2-3h to obtain the aluminum-based copper-clad plate.
2. The production process according to claim 1, characterized in that: the post-curing monomer is one or more of isobornyl methacrylate, tert-butylcyclohexyl methacrylate and tetrahydrofuran methacrylate.
3. The production process according to claim 1, characterized in that: the curing agent is a mixed curing agent of imidazole curing agent and Vicbase TC3635 in a mass ratio of 4-5: 1.
4. The production process according to claim 3, characterized in that: the imidazole curing agent is one or more of 2-methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole.
5. The production process according to claim 1, characterized in that: the inhibitor is methyl hydroquinone.
6. The production process according to claim 1, characterized in that: when the semi-cured layer is prepared in the second step, the insulating glue coated on the aluminum substrate is added with the light insulating nano micro powder with the mass fraction of 0.2-0.5%.
7. The production process according to claim 6, characterized in that: the light insulating nano micro powder is PE or PP micro powder with the particle size of 50nm-100 nm.
8. The production process according to claim 6, characterized in that: the light insulating nano micro powder is modified, and the modification process comprises the following steps:
(1) emulsifying 1-3 wt% of ethylene glycol dimethacrylate in pure water, adding 0.3-0.5 wt% of epichlorohydrin after uniform emulsification, and preparing modifying emulsion;
(2) hydrogen peroxide with the mass fraction of 3-5% is sprayed on the surface of the light insulating nano micro powder with the mass of 10-15 times that of the ethylene glycol dimethacrylate, and the mixture is fully stirred to activate the surface;
(3) and (2) adding the activated light insulating nano micro powder into the emulsion for modification prepared in the step (1), fully dispersing, heating to 50-60 ℃, simultaneously dropwise adding a small amount of hydrochloric acid, reacting for 1-2h, filtering out the light insulating nano micro powder, and drying to obtain the modified light insulating nano micro powder.
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