CN104371274B - Modified alumina composite material, copper-coated substrate and preparation method of copper-coated substrate - Google Patents
Modified alumina composite material, copper-coated substrate and preparation method of copper-coated substrate Download PDFInfo
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- CN104371274B CN104371274B CN201410660339.4A CN201410660339A CN104371274B CN 104371274 B CN104371274 B CN 104371274B CN 201410660339 A CN201410660339 A CN 201410660339A CN 104371274 B CN104371274 B CN 104371274B
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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
- B32B15/04—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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
Abstract
The invention discloses a modified alumina composite material, comprising the following raw materials in parts by mass: 35-55 parts of modified alumina particles, 25-35 parts of reinforced fibers, 15-35 parts of liquid crystal epoxy resin, 10-21 parts of a curing agent and 0.1-1 part of an accelerant, wherein the modified alumina particles are prepared by modifying alumina particles with a silane coupling agent. The modified alumina composite material comprises modified alumina particles, reinforced fibers and liquid crystal epoxy resin; active chemical groups of amino, hydroxyl and the like are formed on the surfaces after the alumina particles are modified by the silane coupling agent; the alumina particles are connected with liquid crystal epoxy resin through the active groups of amino, hydroxyl and the like formed on the surfaces by virtue of chemical bonds; the interaction between interfaces is improved; the heat resistance of the interfaces is reduced; and the cluster phenomenon is reduced. The invention also discloses a copper-coated substrate adopting the modified alumina composite material, and a preparation method of the copper-coated substrate.
Description
Technical field
The present invention relates to the preparation field of copper-clad base plate, more particularly to a kind of modified oxidized aluminium composite material, employing should
Copper-clad base plate of modified oxidized aluminium composite material and preparation method thereof.
Background technology
Copper-clad base plate is with resin, simultaneously or two faces are coated with Copper Foil and Jing is warm by electronic glass-fiber cloth or the leaching of other reinforcing materials
Pressure and made by a kind of board-like material.Copper-clad base plate mainly provides heat conduction, insulation and supports the function of three aspects for chip,
It is the key raw material for manufacturing printed substrate (PCB).In recent years, electronic product just towards portable, miniaturization, lightweight and
Multifunctional direction develops, and this market demand is put forward higher requirement to copper-clad base plate.
Up to the present, aluminium oxide is baseplate material the most frequently used in microelectronics industry, because in machinery, heat, electrical property
Above it is better than the ceramic particle silicon dioxide being usually used in baseplate material.Alumina raw material enriches, cheap, heat stability
Height, aluminium oxide up to 1925 DEG C oxidation and reducing atmosphere in be all stable.The preferable heat conductivity of aluminium oxide reaches
30W/mK, alumina particle is equably added in copper-clad base plate, can be greatly enhanced the mechanical performance of baseplate material
And hot property.
However, alumina particle specific surface area is larger, surface energy is higher, so that alumina particle is easy to be gathered into
Group, and because aluminium oxide is relatively low with the intermolecular forces of polymer, aluminium oxide is more difficult to be uniformly distributed in polymeric matrix,
Easily there is Cluster Phenomenon in the traditional copper-clad base plate containing alumina particle.
The content of the invention
Based on this, it is necessary to provide a kind of copper-clad base plate for being not easy Cluster Phenomenon occur and preparation method, Yi Jike
For the modified oxidized aluminium composite material of the copper-clad base plate.
A kind of modified oxidized aluminium composite material, according to mass fraction include 35 parts～55 parts modified alumina particles, 25
Part～35 parts of reinforcing fiber, 15 parts～35 parts of epoxy resin by using liquid crystal, 10 parts～21 parts of firming agent and 0.1 part～1 part
Accelerator；
The modified alumina particles are obtained for silane coupler modified alumina particle, the modified alumina particles
Particle diameter is 100nm～1000nm.
In one embodiment, the process of the silane coupler modified alumina particle is as follows：By the oxidation
Alumina particles are added to ultrasonic disperse in solvent, and after being warming up to 50 DEG C～60 DEG C the silane coupler is added, and are followed by stirring for heating up
To 70 DEG C of reaction 4h～5h, cooled and filtered simultaneously retains filtering residue, and the modified alumina particles are after the filter residue and drying, its
In, the silane coupler is 3 with the mass ratio of the alumina particle：100.
In one embodiment, the silane coupler is gamma-aminopropyl-triethoxy-silane, γ-(2,3- epoxies third
Oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
In one embodiment, the reinforcing fiber is according to the rule cross arrangement of X-Y direction of principal axis.
In one embodiment, the reinforcing fiber is silicon carbide fibre.
In one embodiment, the silicon carbide fibre is made up of 80～120 monofilament, per the diameter of monofilament described in root
For 12 μm～13 μm.
In one embodiment, the epoxy resin by using liquid crystal is 3,3 ', 5,5 '-tetramethyl biphenyl diglycidyl ether, double
In phenol A diglycidyl ethers, 4,4 '-dihydroxybiphenyl diglycidyl ether and 4,4 '-Dihydroxy binaphthyl base diglycidyl ether
At least one.
In one embodiment, the firming agent is 4,4 '-dihydroxybiphenyl, 4,4 '-benzidine and 4,4 '-diamino
At least one in base diphenyl sulphone (DPS).
In one embodiment, the epoxy resin by using liquid crystal and the firming agent for etc. stoichiometric proportion.
In one embodiment, the accelerator is at least one in triphenylphosphine, imidazoles and chromium acetylacetonate.
A kind of copper-clad base plate, including the first electrode layer, dielectric layer and the second electrode lay that stack gradually；Its feature exists
In the material of the dielectric layer is above-mentioned modified oxidized aluminium composite material.
In one embodiment, the material of the first electrode layer is at least one in copper, pyrite, al and ni, described
The second electrode lay is at least one in copper, pyrite, al and ni.
A kind of preparation method of copper-clad base plate, comprises the steps：
According to mass fraction by 35 parts～55 parts of modified alumina particles, 15 parts～35 parts of epoxy resin by using liquid crystal, 10
Part～21 parts of firming agent and 0.1 part～1 part of accelerator dissolves in organic solvent, mixed after ultrasonic 0.5h～2h
Solution；
25 parts～35 parts of reinforcing fiber is arranged on centrifugation film according to mass fraction, then applies the mixed solution
10min～90min is overlayed in the reinforcing fiber and toasted at 60 DEG C～150 DEG C, prepreg is obtained；And
The prepreg is placed between first electrode layer and the second electrode lay, then in 120 DEG C～200 DEG C, 5kgf/
cm2～30kgf/cm2Pressure under hot pressing 4h～10h, final curing obtains the copper-clad base plate.
In one embodiment, the preparation process of the modified alumina particles is as follows：The alumina particle is added
The ultrasonic disperse in solvent, after being warming up to 50 DEG C～60 DEG C the silane coupler is added, and is followed by stirring for being warming up to 70 DEG C of reactions
4h～5h, cooled and filtered simultaneously retains filtering residue, and the modified alumina particles are after the filter residue and drying, wherein, the silicon
Alkane coupling agent is 3 with the mass ratio of the alumina particle：100.
In one embodiment, the silane coupler is gamma-aminopropyl-triethoxy-silane, γ-(2,3- epoxies third
Oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane, the silane coupler and the oxygen
The mass ratio for changing alumina particles is 3：100.
In one embodiment, it is by the operation that 25 parts～35 parts of reinforcing fiber is arranged on centrifugation film：By 25 parts～
According to the rule cross arrangement of X-Y direction of principal axis on the centrifugation film, the reinforcing fiber is carbonization to 35 parts of the reinforcing fiber
Silica fibre.
In one embodiment, the silicon carbide fibre is made up of 80～120 monofilament, per the diameter of monofilament described in root
For 12 μm～13 μm.
In one embodiment, the epoxy resin by using liquid crystal is 3,3 ', 5,5 '-tetramethyl biphenyl diglycidyl ether, double
In phenol A diglycidyl ethers, 4,4 '-dihydroxybiphenyl diglycidyl ether and 4,4 '-Dihydroxy binaphthyl base diglycidyl ether
At least one；
The firming agent be 4,4 '-dihydroxybiphenyl, 4,4 '-benzidine and 4,4 '-DADPS in extremely
Few one kind；
The epoxy resin by using liquid crystal and the firming agent for etc. stoichiometric proportion.
In one embodiment, the material that the centrifugation film is is polyethylene terephthalate.
This modified oxidized aluminium composite material, including modified alumina particles, reinforcing fiber and epoxy resin by using liquid crystal, are modified
Alumina particle is obtained for silane coupler modified alumina particle.Alumina particle surface shape after silane coupler modified
Into amino, hydroxyl isoreactivity chemical group, amino, hydroxyl isoreactivity group and liquid crystal ring that alumina particle is formed by surface
It is bonded by chemistry between oxygen tree fat, the interaction at interface is improve, interface resistance is reduced, reduce Cluster Phenomenon.
Relative to traditional composite, this modified oxidized aluminium composite material is not easy Cluster Phenomenon occur.
Description of the drawings
Fig. 1 is the flow chart of the manufacture method of the copper-clad base plate of an embodiment；
Fig. 2 is the alumina particle scattered SEM photograph in organic solvent in embodiment 1；
Fig. 3 is that the alumina particle that gamma-aminopropyl-triethoxy-silane obtained in embodiment 1 is modified divides in organic solvent
Scattered SEM photograph；
Fig. 4 is the section electron microscope of prepreg obtained in embodiment 1；
Fig. 5 is the section electron microscope of prepreg obtained in embodiment 1.
Specific embodiment
Below the manufacture method of ferrite powder is described in further detail mainly in combination with drawings and the specific embodiments.
The modified oxidized aluminium composite material of one embodiment, according to mass fraction 35 parts～55 parts of modified aluminas are included
Granule, 25 parts～35 parts of reinforcing fiber, 15 parts～35 parts of epoxy resin by using liquid crystal, 10 parts～21 parts of firming agent and 0.1
Part～1 part of accelerator.
Modified alumina particles are obtained for silane coupler modified alumina particle.The particle diameter of modified alumina particles can be with
For 100nm～1000nm.
In one preferably embodiment, the particle diameter of modified alumina particles is 700nm.
Silane coupler be gamma-aminopropyl-triethoxy-silane, γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane or
γ-methacryloxypropyl trimethoxy silane.
The process of silane coupler modified alumina particle can be：Alumina particle is added to into ultrasound point in solvent
Dissipate, after being warming up to 50 DEG C～60 DEG C silane coupler is added, be followed by stirring for being warming up to 70 DEG C of reaction 4h～5h, cooled and filtered is simultaneously
Retain filtering residue, modified alumina particles are after filter residue and drying.Wherein, silane coupler and the mass ratio of alumina particle are 3：
100.Solvent can be dehydrated alcohol or dimethylbenzene.The temperature of filter residue and drying can be 120 DEG C, and the dry time can be 24h.
Alumina particle surface after silane coupler modified forms amino, hydroxyl isoreactivity chemical group, aluminium oxide
It is amino that granule is formed by surface, bonded by chemistry between hydroxyl isoreactivity group and epoxy resin by using liquid crystal, improve
The interaction at interface, reduces interface resistance, reduces Cluster Phenomenon.
According to the rule cross arrangement of X-Y direction of principal axis, with good heat conductivility and mechanical property, raising changes reinforcing fiber
The overall performance of property alumina composite material.
Reinforcing fiber can be silicon carbide fibre.Silicon carbide fibre is made up of 80～120 monofilament, every monofilament it is straight
Footpath is 12 μm～13 μm.
Silicon carbide fibre serves as the effect of heat-conductive bridges in modified oxidized aluminium composite material, enhances modified alumina particles
Interconnection function and modified alumina particles and modified alumina particles and silicon carbide fibre between, forms to a great extent
Heat conduction network structure or heat conduction chain.
In present embodiment, the tensile strength of every monofilament of silicon carbide fibre is 2GPa, and modulus is 150GPa.
Epoxy resin by using liquid crystal is selected with the big rigid biphenyl structural of more draw ratio or naphthalene structure, more common asphalt mixtures modified by epoxy resin
Fat or BT resins are greatly improved in terms of hot property, mechanical property and dielectric properties；The big rigidity knot of such as draw ratio
Structure can effectively suppress the scattering of phonon, increase the mean free path of phonon, so that its heat conductivility is significantly improved.
Specifically, epoxy resin by using liquid crystal is selected from 3,3 ', 5, and 5 '-tetramethyl biphenyl diglycidyl ether, bisphenol-A two shrink sweet
At least one in oily ether, 4,4 '-dihydroxybiphenyl diglycidyl ether and 4,4 '-Dihydroxy binaphthyl base diglycidyl ether.
Firming agent can in 4,4 '-dihydroxybiphenyl, 4,4 '-benzidine and 4,4 '-DADPS extremely
Few one kind.
In present embodiment, epoxy resin by using liquid crystal and firming agent for etc. stoichiometric proportion, i.e. epoxy resin by using liquid crystal and solidification
Both agent are reacted completely just.
In present embodiment, the quality sum of modified aluminas and liquid crystalline epoxy tree is total with modified oxidized aluminium composite material
The ratio of quality is 7：10.
Accelerator is at least one in triphenylphosphine, imidazoles and chromium acetylacetonate.
This modified oxidized aluminium composite material, including modified alumina particles, reinforcing fiber and epoxy resin by using liquid crystal, are modified
Alumina particle is obtained for silane coupler modified alumina particle.Alumina particle surface shape after silane coupler modified
Into amino, hydroxyl isoreactivity chemical group, amino, hydroxyl isoreactivity group and liquid crystal ring that alumina particle is formed by surface
It is bonded by chemistry between oxygen tree fat, the interaction at interface is improve, interface resistance is reduced, reduce Cluster Phenomenon.
Relative to traditional composite, this modified oxidized aluminium composite material is not easy Cluster Phenomenon occur.
The copper-clad base plate of one embodiment, including the first electrode layer, dielectric layer and the second electrode lay that stack gradually.
The material of dielectric layer is above-mentioned modified oxidized aluminium composite material.
The material of first electrode layer is at least one in copper, pyrite, al and ni.The material of the second electrode lay is copper, Huang
At least one in copper, al and ni.
The thickness of first electrode layer is 10 μm～35 μm, and the thickness of the second electrode lay is 10 μm～35 μm.
The preparation method of above-mentioned copper-clad base plate as shown in Figure 1, comprises the steps：
S10, according to mass fraction by 35 parts～55 parts of modified alumina particles, 15 parts～35 parts of liquid crystalline epoxy tree
Fat, 10 parts～21 parts of firming agent and 0.1 part～1 part of accelerator are dissolved in organic solvent, after ultrasonic 0.5h～2h
To mixed solution.
Organic solvent can be 2-butanone or acetone.
Modified alumina particles are obtained for silane coupler modified alumina particle.The particle diameter of modified alumina particles can be with
For 100nm～1000nm.
In one preferably embodiment, the particle diameter of modified alumina particles is 700nm.
Silane coupler be gamma-aminopropyl-triethoxy-silane, γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane or
γ-methacryloxypropyl trimethoxy silane.
The process of silane coupler modified alumina particle can be：Alumina particle is added to into ultrasound point in solvent
Dissipate, after being warming up to 50 DEG C～60 DEG C silane coupler is added, be followed by stirring for being warming up to 70 DEG C of reaction 4h～5h, cooled and filtered is simultaneously
Retain filtering residue, modified alumina particles are after filter residue and drying.Wherein, silane coupler and the mass ratio of alumina particle are 3：
100.Solvent can be dehydrated alcohol or dimethylbenzene.The temperature of filter residue and drying can be 120 DEG C, and the dry time can be 24h.
Alumina particle surface after silane coupler modified forms amino, hydroxyl isoreactivity chemical group, aluminium oxide
It is amino that granule is formed by surface, bonded by chemistry between hydroxyl isoreactivity group and epoxy resin by using liquid crystal, improve
The interaction at interface, reduces interface resistance, reduces Cluster Phenomenon.
Epoxy resin by using liquid crystal is selected with the big rigid biphenyl structural of more draw ratio or naphthalene structure, more common asphalt mixtures modified by epoxy resin
Fat or BT resins are greatly improved in terms of hot property, mechanical property and dielectric properties；The big rigidity knot of such as draw ratio
Structure can effectively suppress the scattering of phonon, increase the mean free path of phonon, so that its heat conductivility is significantly improved.
Specifically, epoxy resin by using liquid crystal is selected from 3,3 ', 5, and 5 '-tetramethyl biphenyl diglycidyl ether, bisphenol-A two shrink sweet
At least one in oily ether, 4,4 '-dihydroxybiphenyl diglycidyl ether and 4,4 '-Dihydroxy binaphthyl base diglycidyl ether.
Firming agent can in 4,4 '-dihydroxybiphenyl, 4,4 '-benzidine and 4,4 '-DADPS extremely
Few one kind.
In present embodiment, epoxy resin by using liquid crystal and firming agent for etc. stoichiometric proportion, i.e. epoxy resin by using liquid crystal and solidification
Both agent are reacted completely just.
Accelerator is at least one of triphenylphosphine, imidazoles and chromium acetylacetonate.
S20, according to mass fraction by 25 parts～35 parts of reinforcing fiber be arranged in centrifugation film on, then S10 is obtained
Mixed solution is coated in reinforcing fiber and toasts at 60 DEG C～150 DEG C 10min～90min, and being cooled to after room temperature will be from
Heart film is peeled off and obtains prepreg.
The material that centrifugation film is can be polyethylene terephthalate.Pet material from
Heart film is less due to its surface tension, easily peelable when prepreg is obtained.
Specifically, in S20, by 25 parts～35 parts of reinforcing fiber according to the rule cross arrangement of X-Y direction of principal axis in centrifugation film
On.
Reinforcing fiber can be silicon carbide fibre.Silicon carbide fibre is made up of 80～120 monofilament, every monofilament it is straight
Footpath is 12 μm～13 μm.
Silicon carbide fibre serves as the effect of heat-conductive bridges in modified oxidized aluminium composite material, enhances modified alumina particles
Interconnection function and modified alumina particles and modified alumina particles and silicon carbide fibre between, forms to a great extent
Heat conduction network structure or heat conduction chain.
In present embodiment, the tensile strength of every monofilament of silicon carbide fibre is 2GPa, and modulus is 150GPa.
S30, the prepreg that S20 is obtained is placed between first electrode layer and the second electrode lay, then 120 DEG C～
200℃、5kgf/cm2～30kgf/cm2Pressure under hot pressing 4h～10h, final curing obtains copper-clad base plate.
The material of first electrode layer is at least one in copper, pyrite, al and ni.The material of the second electrode lay is copper, Huang
At least one in copper, al and ni.
The thickness of first electrode layer is 10 μm～35 μm, and the thickness of the second electrode lay is 10 μm～35 μm.
The operation of solidification can be：Solidify 2h at 150 DEG C, 180 DEG C, 220 DEG C respectively.
Through test, the radial direction heat conductivity of the dielectric layer of copper-clad base plate obtained in the preparation method of this copper-clad base plate
For 0.701～1.004W/mK, axial thermal conductivity coefficient is 1.325～1.526W/mK, glass transition temperature is 170～
180℃。
The material of the dielectric layer of copper-clad base plate obtained in the preparation method of this copper-clad base plate is compound for modified aluminas
Material, modified oxidized aluminium composite material includes modified alumina particles, reinforcing fiber and epoxy resin by using liquid crystal, modified aluminas
Grain is obtained for silane coupler modified alumina particle.Alumina particle after silane coupler modified surface formed amino,
Hydroxyl isoreactivity chemical group, amino, hydroxyl isoreactivity group and epoxy resin by using liquid crystal that alumina particle is formed by surface
Between by chemistry it is bonded, improve the interaction at interface, reduce interface resistance, reduce Cluster Phenomenon.
It is below specific embodiment.In embodiment, ball milling selects the ball mill 50kg level ball mill of the rich making of Meizhou China, swashs
Light Particle Size Analyzer is Malvern MS3000 laser particle analyzers, and specific surface area analysis instrument is ASAP2020 specific-surface area detection instruments,
Heat conduction coefficient tester is Hot Disk TPS2500s thermal analyzers, and glass transition temperature tester is swept for TA Q20 differentials
Calorimetric tester is retouched, scanning electron microscope is the Nova Nano SEM 450 of FEI Co..
Embodiment 1
(1) the modified aluminium oxide of gamma-aminopropyl-triethoxy-silane is prepared.
First alumina particle is dried into 4h at 110 DEG C, is cooled to after room temperature weigh 15.0g particle diameters for 700nm's
Alumina particle, 50mL dimethylbenzene are added in there-necked flask after ultrasonic disperse 10min and are put into oil bath pan, and magnetic agitation solution is simultaneously
It is warming up to 90 DEG C.1.0g surface modifier gamma-aminopropyl-triethoxy-silanes are added dropwise over dropper, 115 are warming up to after Deca
DEG C, magnetic agitation is kept, react 6h.
Mixed solution is cooled down, suction funnel is poured into while hot, the sample dehydrated alcohol that sucking filtration is obtained repeatedly is washed, and is put into
110 DEG C of vacuum drying oven is dried 12h, obtains the modified aluminium oxide in gamma-aminopropyl-triethoxy-silane surface.
Fig. 2 and Fig. 3 are respectively the alumina particle in embodiment 1 and gamma-aminopropyl-triethoxy silicon obtained in embodiment 1
The modified alumina particle of alkane scattered SEM photograph in organic solvent.
As seen from Figure 2, alumina particle before modified easily forms in organic solvent cluster, and dispersibility is poor.It is main
Less because of alumina particle specific surface area, surface energy is very big, and in bulk is easily combined between alumina particle.
As seen from Figure 3, the modified alumina particle of gamma-aminopropyl-triethoxy-silane is presented single dispersing substantially, very
Rare reunion.Modified Membranes On Alumina Particles Surface is primarily due to electric charge, because the interaction of electric charge is γ-aminopropyl
The modified alumina particle dispersibility of triethoxysilane is preferable.
(2) prepreg is prepared.
By 2.60g 3,3 ', 5,5 '-tetramethyl biphenyl diglycidyl ethers, 1.40g 4,4 '-DADPS and
20.00mg triphenylphosphines are uniformly mixed at 180 DEG C, maintain 180 DEG C of reaction 30min of temperature, obtain amber thick transparent
Epoxy resin composite.
By the modified oxygen in obtained 4.00g epoxy resin composites, 4.00g Jing gamma-aminopropyl-triethoxy-silanes surface
Change aluminum to be added in the 2-butanone solvent of 4.50g, 2h is stirred by ultrasonic wave concussion method, mix homogeneously obtains mixed solution.
The mixed solution of above-mentioned preparation is coated in X-Y plane in regular shape cross arrangement using bar type coating method
Silicon carbide fibre on.It is put in convection oven 130 DEG C to toast 120 minutes, makes solvent volatilize, obtains prepreg.Semi-solid preparation
In piece, the gross mass percent of aluminium oxide and epoxy resin by using liquid crystal composite is 70%.
Fig. 4 and Fig. 5 are respectively the section electron microscope of prepreg obtained in embodiment 1.
Fig. 4 is the electron microscope of the silicon carbide fibre that epoxy resin by using liquid crystal coats longitudinal direction arrangement, and as seen from Figure 4, be modified oxygen
Change alumina particles to be dispersed in epoxy resin by using liquid crystal, while modified alumina particles are closely attached to the table of silicon carbide fibre
Face.
Fig. 5 is the electron microscope that epoxy resin by using liquid crystal coats the radially silicon carbide fibre of arrangement, as seen from Figure 5, liquid crystal ring
Preferably, existing defects are less, and silicon carbide fibre sufficiently act as the effect of heat-conductive bridges, enhance for oxygen tree fat integral coating effect
Connection between modified alumina particles and modified alumina particles and between modified alumina particles and silicon carbide fibre is made
With forming heat conduction network structure or heat conduction chain to a great extent.
(3) copper-clad base plate is prepared.
The copper foil that two thickness is 40 microns is cleaned with the hydrochloric acid solution that concentration is 15wt% first, then again by two
Copper foil is placed in acetone to be cleaned by ultrasonic to be placed in dehydrated alcohol after 10min and is cleaned by ultrasonic 10min, and 60 DEG C of drying, obtain in baking oven
To first electrode layer that is clean, being dried and the second electrode lay.
Two prepregs are overlapped into the silicon carbide fibre of the latter two to be adjacent to, first electrode layer and second electrode is placed on
Between layer, in vacuum press, in 150 DEG C, 5kgf/cm2Pressure under hot pressing 3 hours, finally in convection oven, exist respectively
150 DEG C, 180 DEG C, solidify 2h at 220 DEG C, copper-clad base plate is obtained.
Obtained copper-clad base plate includes first electrode layer, dielectric layer and the second electrode lay for stacking gradually, wherein first
Electrode layer and the second electrode lay are the copper foil that thickness is 40 microns, and dielectric layer is made up of two panels prepreg, and half is solid
It is 500 microns to change piece thickness.
Find after test, the radial direction heat conductivity of the copper-clad base plate that embodiment 1 is prepared is 0.701W/mK, axially
Heat conductivity is 1.325W/mK, and glass transition temperature is 175 DEG C.
Embodiment 2
Preparation method is substantially the same manner as Example 1, differs only in：The firming agent that step (2) is used is 4,4 '-dihydroxy
Biphenyl, 130 DEG C are uniformly mixed, and maintain 130 DEG C of reaction 30min of temperature, obtain amber thick transparent epoxy resin and answer
Compound.
The copper-clad base plate for preparing includes first electrode layer, dielectric layer and the second electrode lay for stacking gradually, wherein
First electrode layer and the second electrode lay are the copper foil that thickness is 40 microns, and dielectric layer is made up of 2 prepregs, thickness
For 500 microns.
Find after test, baseplate material radial direction heat conductivity 0.876W/mK, axial thermal conductivity coefficient is 1.358W/mK,
Glass transition temperature is 130 DEG C.
Embodiment 3
Preparation method is substantially the same manner as Example 1, differs only in：Step (2) is by 5.60g (55 parts) Jing γ-aminopropyl
The aluminium oxide and 2.40g epoxy-resin systems of triethoxysilane is added in the 2-butanone solvent of 4.50g, is shaken by ultrasound wave
Oscillation method stirs 2h, and mix homogeneously obtains alumina composite material.
The copper-clad base plate for preparing includes first electrode layer, dielectric layer and the second electrode lay for stacking gradually, wherein
First electrode layer and the second electrode lay are the copper foil that thickness is 40 microns, and dielectric layer is made up of 2 prepregs, thickness
For 500 microns.
Find after test, baseplate material radial direction heat conductivity is 1.004W/mK, and axial thermal conductivity coefficient is 1.526W/m
K, glass transition temperature is 180 DEG C.
Comparative example 1
Preparation method is same as Example 1, differs only in：Step is coated on glass fabric in (2).
The copper-clad base plate for preparing includes first electrode layer, electrolyte and the second electrode lay for stacking gradually, wherein the
One electrode layer and the second electrode lay are the copper foil that thickness is 40 microns, and dielectric layer is made up of 2 prepregs, and thickness is
100 microns.
Find after test, baseplate material radial direction heat conductivity is 0.777W/mK, and axial thermal conductivity coefficient is 0.803W/m
K, glass transition temperature is 175 DEG C.
Comparative example 2
Preparation method is same as Example 2, differs only in：The same amount of unmodified aluminium oxide of addition in step (2).
The copper-clad base plate for preparing includes first electrode layer, dielectric layer and the second electrode lay for stacking gradually, wherein
First electrode layer and the second electrode lay are the copper foil that thickness is 40 microns, and dielectric layer is made up of 2 prepregs, thickness
For 500 microns.Baseplate material radial direction heat conductivity 0.592W/mK, axial thermal conductivity coefficient is 0.888W/mK, and vitrification turns
Temperature is 175 DEG C.
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art
For, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the guarantor of the present invention
Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.
Claims (4)
1. a kind of modified oxidized aluminium composite material, it is characterised in that according to mass fraction by 5.6 parts of the ethoxy of γ-aminopropyl three
The modified alumina particle of base silane, 3.429 parts of silicon carbide fibre, 1.56 parts of 3,3 ', 5,5 '-tetramethyl biphenyl two shrink
Glycerin ether, 0.84 part of 4,4 '-DADPS and 0.012 part of triphenylphosphine composition；
The modified alumina particle of gamma-aminopropyl-triethoxy-silane is obtained by following operation：Alumina particle is existed first
4h is dried at 110 DEG C, it is that the alumina particle of 700nm, 50mL dimethylbenzene are added to three to be cooled to after room temperature to weigh 15g particle diameters
It is put into oil bath pan in mouthful flask after ultrasonic disperse 10min, magnetic agitation solution is simultaneously warming up to 90 DEG C；1g tables are added dropwise over dropper
Face modifying agent gamma-aminopropyl-triethoxy-silane, is warming up to 115 DEG C after Deca, keep magnetic agitation, reacts 6h；To mix molten
Liquid is cooled down, and pours suction funnel into while hot, and the sample dehydrated alcohol that sucking filtration is obtained repeatedly is washed, and is put into 110 DEG C of vacuum drying oven
12h is dried, the modified aluminium oxide in gamma-aminopropyl-triethoxy-silane surface is obtained；
Silicon carbide fibre is in X-Y plane in regular shape cross arrangement.
2. a kind of copper-clad base plate, including the first electrode layer, dielectric layer and the second electrode lay that stack gradually；Characterized in that,
The material of the dielectric layer is modified oxidized aluminium composite material as claimed in claim 1.
3. copper-clad base plate as claimed in claim 2, it is characterised in that the material of the first electrode layer be copper, pyrite, aluminum and
At least one in nickel, the second electrode lay is at least one in copper, pyrite, al and ni.
4. a kind of preparation method of copper-clad base plate, it is characterised in that comprise the steps：
First alumina particle is dried into 4h at 110 DEG C, is cooled to after room temperature weigh the oxidation that 15.0g particle diameters are 700nm
Alumina particles, 50mL dimethylbenzene are added in there-necked flask after ultrasonic disperse 10min and are put into oil bath pan, and magnetic agitation solution simultaneously heats up
To 90 DEG C；1.0g surface modifier gamma-aminopropyl-triethoxy-silanes are added dropwise over dropper, 115 DEG C are warming up to after Deca, protected
Magnetic agitation is held, 6h is reacted；Mixed solution is cooled down, suction funnel is poured into while hot, the sample dehydrated alcohol that sucking filtration is obtained is more
Secondary washing, is put into 110 DEG C of vacuum drying oven and is dried 12h, obtains the modified aluminium oxide in gamma-aminopropyl-triethoxy-silane surface；
By 2.60g 3,3 ', 5,5 '-tetramethyl biphenyl diglycidyl ethers, 1.40g 4,4 '-DADPS and
20.00mg triphenylphosphines are uniformly mixed at 180 DEG C, maintain 180 DEG C of reaction 30min of temperature, obtain amber thick transparent
Epoxy resin composite；
The modified aluminium oxide in obtained 2.4g epoxy resin composites, 5.6g Jing gamma-aminopropyl-triethoxy-silanes surface is added
Enter in the 2-butanone solvent of 4.50g, 2h is stirred by ultrasonic wave concussion method, mix homogeneously obtains mixed solution；
The mixed solution of above-mentioned preparation is coated on in X-Y plane the carbon in regular shape cross arrangement using bar type coating method
On SiClx fiber；It is put in convection oven 130 DEG C to toast 120 minutes, makes solvent volatilize, obtains prepreg；In prepreg,
The gross mass percent of aluminium oxide and epoxy resin composite is 70%；
The copper foil that two thickness is 40 microns is cleaned with the hydrochloric acid solution that concentration is 15wt% first, then again by two Copper Foils
Piece is placed in acetone to be cleaned by ultrasonic to be placed in dehydrated alcohol after 10min and is cleaned by ultrasonic 10min, and 60 DEG C of drying, obtain clean in baking oven
Only the first electrode layer, being dried and the second electrode lay；
Two prepregs are overlapped into the silicon carbide fibre of the latter two to be adjacent to, be placed on first electrode layer and the second electrode lay it
Between, in vacuum press, in 150 DEG C, 5kgf/cm2Pressure under hot pressing 3 hours, finally in convection oven, respectively 150
DEG C, 180 DEG C, solidify 2h at 220 DEG C, copper-clad base plate is obtained；
Obtained copper-clad base plate includes first electrode layer, dielectric layer and the second electrode lay for stacking gradually, wherein first electrode
Layer and the second electrode lay are the copper foil that thickness is 40 microns, and dielectric layer is made up of two panels prepreg, prepreg
Thickness is 500 microns.
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| PCT/CN2015/084011 WO2016078432A1 (en) | 2014-11-18 | 2015-07-14 | Modified aluminium oxide composite material, copper-coated substrate and preparation method thereof |
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| CN104371274B (en) * | 2014-11-18 | 2017-04-12 | 中国科学院深圳先进技术研究院 | Modified alumina composite material, copper-coated substrate and preparation method of copper-coated substrate |
| CN105694109B (en) * | 2016-01-29 | 2018-07-10 | 合肥工业大学 | It is a kind of that there is toughening and the nucleocapsid structure conduction powder of chain extension and preparation method thereof |
| CN106009525A (en) * | 2016-07-14 | 2016-10-12 | 强新正品（苏州）环保材料科技有限公司 | Silica gel gasket |
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