CN104371274A - 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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- CN104371274A CN104371274A CN201410660339.4A CN201410660339A CN104371274A CN 104371274 A CN104371274 A CN 104371274A CN 201410660339 A CN201410660339 A CN 201410660339A CN 104371274 A CN104371274 A CN 104371274A
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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
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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
- 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
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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
- 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
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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
- 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
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- 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, particularly relate to a kind of modified oxidized aluminum composite, the copper-clad base plate adopting this modified oxidized aluminum composite and preparation method thereof.
Background technology
Copper-clad base plate soaks electronic glass-fiber cloth or other strongtheners with resin, one side or two a kind of board-like materials made coated with Copper Foil and through hot pressing.Copper-clad base plate mainly provides the function of heat conduction, insulation and support three aspects for chip, is the key raw material manufacturing printed-wiring board (PWB) (PCB).In recent years, electronic product is just towards portable, miniaturization, lightweight and multifunctional direction development, and this market requirement is had higher requirement to copper-clad base plate.
Up to the present, aluminum oxide is baseplate material the most frequently used in microelectronics industry, because it is better than the ceramic particle silicon-dioxide be usually used in baseplate material on machinery, heat, electrical property.Alumina raw material enriches, and cheap, thermostability is high, and aluminum oxide is all stable in the oxidation up to 1925 DEG C and reducing atmosphere.The desirable thermal conductivity of aluminum oxide reaches 30W/mK, is added to equably in copper-clad base plate by alumina particle, greatly can improve mechanical property and the thermal characteristics of baseplate material.
But, alumina particle specific surface area is comparatively large, surface energy is higher, thus it is agglomerating to make alumina particle be easy to gathering, and due to the intermolecular forces of aluminum oxide and polymkeric substance lower, aluminum oxide is more difficult to be uniformly distributed in polymeric matrix, traditional copper-clad base plate containing alumina particle easily there is Cluster Phenomenon.
Summary of the invention
Based on this, be necessary to provide a kind of copper-clad base plate and the preparation method that are not easy to occur Cluster Phenomenon, and may be used for the modified oxidized aluminum composite of this copper-clad base plate.
A kind of modified oxidized aluminum composite, comprises the promotor of the modified alumina particles of 35 parts ~ 55 parts, the fortifying fibre of 25 parts ~ 35 parts, the epoxy resin by using liquid crystal of 15 parts ~ 35 parts, the solidifying agent of 10 parts ~ 21 parts and 0.1 part ~ 1 part according to massfraction;
Described modified alumina particles is that silane coupler modified alumina particle obtains, and the particle diameter of described modified alumina particles is 100nm ~ 1000nm.
In one embodiment, the process of described silane coupler modified described alumina particle is as follows: described alumina particle is joined ultrasonic disperse in solvent, described silane coupling agent is added after being warming up to 50 DEG C ~ 60 DEG C, then stir and be warming up to 70 DEG C of reaction 4h ~ 5h, cooled and filtered also retains filter residue, be described modified alumina particles after described filter residue and drying, wherein, the mass ratio of described silane coupling agent and described alumina particle is 3:100.
In one embodiment, described silane coupling agent is γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
In one embodiment, described fortifying fibre is according to the cross arrangement of X-Y direction of principal axis rule.
In one embodiment, described fortifying fibre is silicon carbide fiber.
In one embodiment, described silicon carbide fiber is made up of 80 ~ 120 monofilament, and the diameter of monofilament described in every root is 12 μm ~ 13 μm.
In one embodiment, described epoxy resin by using liquid crystal is 3,3 ', 5,5 '-tetramethyl biphenyl diglycidylether, bisphenol A diglycidyl ether, 4,4 '-dihydroxybiphenyl diglycidylether and 4, at least one in 4 '-Dihydroxy binaphthyl base diglycidylether.
In one embodiment, described solidifying agent is 4,4 '-dihydroxybiphenyl, 4, at least one in 4 '-benzidine and DDS.
In one embodiment, described epoxy resin by using liquid crystal and described solidifying agent such as are at the stoichiometric ratio.
In one embodiment, described promotor is at least one in triphenylphosphine, imidazoles and chromium acetylacetonate.
A kind of copper-clad base plate, comprises the first electrode layer, dielectric layer and the second electrode lay that stack gradually; It is characterized in that, the material of described dielectric layer is above-mentioned modified oxidized aluminum composite.
In one embodiment, the material of described first electrode layer is at least one in copper, brass, al and ni, and described the second electrode lay is at least one in copper, brass, al and ni.
A preparation method for copper-clad base plate, comprises the steps:
According to massfraction, the promotor of the modified alumina particles of 35 parts ~ 55 parts, the epoxy resin by using liquid crystal of 15 parts ~ 35 parts, the solidifying agent of 10 parts ~ 21 parts and 0.1 part ~ 1 part is dissolved in organic solvent, after ultrasonic 0.5h ~ 2h, obtain mixing solutions;
According to massfraction, the fortifying fibre of 25 parts ~ 35 parts is arranged on centrifugal film, then described mixing solutions is coated on described fortifying fibre and toasts 10min ~ 90min at 60 DEG C ~ 150 DEG C, obtaining prepreg; And
Described prepreg is placed between the first electrode layer and the second electrode lay, then at 120 DEG C ~ 200 DEG C, 5kgf/cm
2~ 30kgf/cm
2pressure under hot pressing 4h ~ 10h, final curing, obtains described copper-clad base plate.
In one embodiment, the preparation process of described modified alumina particles is as follows: described alumina particle is joined ultrasonic disperse in solvent, described silane coupling agent is added after being warming up to 50 DEG C ~ 60 DEG C, then stir and be warming up to 70 DEG C of reaction 4h ~ 5h, cooled and filtered also retains filter residue, be described modified alumina particles after described filter residue and drying, wherein, the mass ratio of described silane coupling agent and described alumina particle is 3:100.
In one embodiment, described silane coupling agent is γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane, the mass ratio of described silane coupling agent and described alumina particle is 3:100.
In one embodiment, the fortifying fibre of 25 parts ~ 35 parts is arranged in being operating as on centrifugal film: by the described fortifying fibre of 25 parts ~ 35 parts according to X-Y direction of principal axis rule cross arrangement on described centrifugal film, described fortifying fibre is silicon carbide fiber.
In one embodiment, described silicon carbide fiber is made up of 80 ~ 120 monofilament, and the diameter of monofilament described in every root is 12 μm ~ 13 μm.
In one embodiment, described epoxy resin by using liquid crystal is 3,3 ', 5,5 '-tetramethyl biphenyl diglycidylether, bisphenol A diglycidyl ether, 4,4 '-dihydroxybiphenyl diglycidylether and 4, at least one in 4 '-Dihydroxy binaphthyl base diglycidylether;
Described solidifying agent is 4,4 '-dihydroxybiphenyl, 4, at least one in 4 '-benzidine and DDS;
The stoichiometric ratios such as described epoxy resin by using liquid crystal and described solidifying agent are.
In one embodiment, the material that described centrifugal film is is polyethylene terephthalate.
This modified oxidized aluminum composite, comprises modified alumina particles, fortifying fibre and epoxy resin by using liquid crystal, and modified alumina particles is that silane coupler modified alumina particle obtains.Alumina particle forms amino, hydroxyl isoreactivity chemical group through silane coupler modified rear surface, the amino that alumina particle is formed by surface, hydroxyl isoreactivity group are connected by chemical bond with between epoxy resin by using liquid crystal, improve the interaction at interface, reduce interface resistance, decrease Cluster Phenomenon.Relative to traditional matrix material, this modified oxidized aluminum composite is not easy to occur Cluster Phenomenon.
Accompanying drawing explanation
Fig. 1 is the schema of the manufacture method of the copper-clad base plate of an embodiment;
Fig. 2 is the SEM photo that the alumina particle in embodiment 1 disperses in organic solvent;
Fig. 3 is the SEM photo that the alumina particle of the γ-aminopropyl triethoxysilane modification that embodiment 1 obtains disperses in organic solvent;
Fig. 4 is the cross section Electronic Speculum figure of the prepreg that embodiment 1 obtains;
Fig. 5 is the cross section Electronic Speculum figure of the prepreg that embodiment 1 obtains.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments the manufacture method of ferrite powder is described in further detail below.
The modified oxidized aluminum composite of one embodiment, comprises the promotor of the modified alumina particles of 35 parts ~ 55 parts, the fortifying fibre of 25 parts ~ 35 parts, the epoxy resin by using liquid crystal of 15 parts ~ 35 parts, the solidifying agent of 10 parts ~ 21 parts and 0.1 part ~ 1 part according to massfraction.
Modified alumina particles is that silane coupler modified alumina particle obtains.The particle diameter of modified alumina particles can be 100nm ~ 1000nm.
In one preferably embodiment, the particle diameter of modified alumina particles is 700nm.
Silane coupling agent is γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
The process of silane coupler modified alumina particle can be: alumina particle is joined ultrasonic disperse in solvent, silane coupling agent is added after being warming up to 50 DEG C ~ 60 DEG C, then stir and be warming up to 70 DEG C of reaction 4h ~ 5h, cooled and filtered also retains filter residue, is modified alumina particles after filter residue and drying.Wherein, the mass ratio of silane coupling agent and alumina particle is 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 forms amino, hydroxyl isoreactivity chemical group through silane coupler modified rear surface, the amino that alumina particle is formed by surface, hydroxyl isoreactivity group are connected by chemical bond with between epoxy resin by using liquid crystal, improve the interaction at interface, reduce interface resistance, decrease Cluster Phenomenon.
Fortifying fibre, according to the cross arrangement of X-Y direction of principal axis rule, has good heat conductivility and mechanical property, improves the overall performance of modified oxidized aluminum composite.
Fortifying fibre can be silicon carbide fiber.Silicon carbide fiber is made up of 80 ~ 120 monofilament, and the diameter of every root monofilament is 12 μm ~ 13 μm.
Silicon carbide fiber serves as the effect of heat-conductive bridges in modified oxidized aluminum composite, enhance modified alumina particles and modified alumina particles and the ligation between modified alumina particles and silicon carbide fiber, form heat conduction network structure or heat conduction chain to a great extent.
In present embodiment, the tensile strength of every root monofilament of silicon carbide fiber is 2GPa, and modulus is 150GPa.
Epoxy resin by using liquid crystal selects to have the large rigidity biphenyl structural of more length-to-diameter ratio or naphthalene structure, and comparatively ordinary epoxy resin or BT resin are greatly improved in thermal characteristics, mechanical property and dielectric properties; The rigid structure that such as length-to-diameter ratio is large effectively can suppress the scattering of phonon, increases the mean free path of phonon, thus its heat conductivility is significantly improved.
Concrete, epoxy resin by using liquid crystal is selected from 3, and 3 ', 5,5 '-tetramethyl biphenyl diglycidylether, bisphenol A diglycidyl ether, 4,4 '-dihydroxybiphenyl diglycidylether and 4, at least one in 4 '-Dihydroxy binaphthyl base diglycidylether.
Solidifying agent can be 4,4 '-dihydroxybiphenyl, 4, at least one in 4 '-benzidine and DDS.
In present embodiment, epoxy resin by using liquid crystal and solidifying agent such as are at the stoichiometric ratio, that is, complete reaction all just both epoxy resin by using liquid crystal and solidifying agent.
In present embodiment, the ratio of the quality sum of modified aluminas and liquid crystalline epoxy tree and the total mass of modified oxidized aluminum composite is 7:10.
Promotor is at least one in triphenylphosphine, imidazoles and chromium acetylacetonate.
This modified oxidized aluminum composite, comprises modified alumina particles, fortifying fibre and epoxy resin by using liquid crystal, and modified alumina particles is that silane coupler modified alumina particle obtains.Alumina particle forms amino, hydroxyl isoreactivity chemical group through silane coupler modified rear surface, the amino that alumina particle is formed by surface, hydroxyl isoreactivity group are connected by chemical bond with between epoxy resin by using liquid crystal, improve the interaction at interface, reduce interface resistance, decrease Cluster Phenomenon.Relative to traditional matrix material, this modified oxidized aluminum composite is not easy to occur Cluster Phenomenon.
The copper-clad base plate of one embodiment, comprises the first electrode layer, dielectric layer and the second electrode lay that stack gradually.
The material of dielectric layer is above-mentioned modified oxidized aluminum composite.
The material of the first electrode layer is at least one in copper, brass, al and ni.The material of the second electrode lay is at least one in copper, brass, al and ni.
The thickness of the 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 massfraction, the promotor of the modified alumina particles of 35 parts ~ 55 parts, the epoxy resin by using liquid crystal of 15 parts ~ 35 parts, the solidifying agent of 10 parts ~ 21 parts and 0.1 part ~ 1 part to be dissolved in organic solvent, after ultrasonic 0.5h ~ 2h, obtain mixing solutions.
Organic solvent can be 2-butanone or acetone.
Modified alumina particles is that silane coupler modified alumina particle obtains.The particle diameter of modified alumina particles can be 100nm ~ 1000nm.
In one preferably embodiment, the particle diameter of modified alumina particles is 700nm.
Silane coupling agent is γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
The process of silane coupler modified alumina particle can be: alumina particle is joined ultrasonic disperse in solvent, silane coupling agent is added after being warming up to 50 DEG C ~ 60 DEG C, then stir and be warming up to 70 DEG C of reaction 4h ~ 5h, cooled and filtered also retains filter residue, is modified alumina particles after filter residue and drying.Wherein, the mass ratio of silane coupling agent and alumina particle is 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 forms amino, hydroxyl isoreactivity chemical group through silane coupler modified rear surface, the amino that alumina particle is formed by surface, hydroxyl isoreactivity group are connected by chemical bond with between epoxy resin by using liquid crystal, improve the interaction at interface, reduce interface resistance, decrease Cluster Phenomenon.
Epoxy resin by using liquid crystal selects to have the large rigidity biphenyl structural of more length-to-diameter ratio or naphthalene structure, and comparatively ordinary epoxy resin or BT resin are greatly improved in thermal characteristics, mechanical property and dielectric properties; The rigid structure that such as length-to-diameter ratio is large effectively can suppress the scattering of phonon, increases the mean free path of phonon, thus its heat conductivility is significantly improved.
Concrete, epoxy resin by using liquid crystal is selected from 3, and 3 ', 5,5 '-tetramethyl biphenyl diglycidylether, bisphenol A diglycidyl ether, 4,4 '-dihydroxybiphenyl diglycidylether and 4, at least one in 4 '-Dihydroxy binaphthyl base diglycidylether.
Solidifying agent can be 4,4 '-dihydroxybiphenyl, 4, at least one in 4 '-benzidine and DDS.
In present embodiment, epoxy resin by using liquid crystal and solidifying agent such as are at the stoichiometric ratio, that is, complete reaction all just both epoxy resin by using liquid crystal and solidifying agent.
Promotor is at least one of triphenylphosphine, imidazoles and chromium acetylacetonate.
S20, according to massfraction, the fortifying fibre of 25 parts ~ 35 parts is arranged on centrifugal film, then being coated in by the mixing solutions that S10 obtains on fortifying fibre and toasting 10min ~ 90min at 60 DEG C ~ 150 DEG C, to be cooled stripping by centrifugal film to room temperature obtains prepreg.
The material that centrifugal film is can be polyethylene terephthalate.The centrifugal film of pet material is less due to its surface tension, easily peels off when obtaining prepreg.
Concrete, in S20, by the fortifying fibre of 25 parts ~ 35 parts according to the cross arrangement of X-Y direction of principal axis rule on centrifugal film.
Fortifying fibre can be silicon carbide fiber.Silicon carbide fiber is made up of 80 ~ 120 monofilament, and the diameter of every root monofilament is 12 μm ~ 13 μm.
Silicon carbide fiber serves as the effect of heat-conductive bridges in modified oxidized aluminum composite, enhance modified alumina particles and modified alumina particles and the ligation between modified alumina particles and silicon carbide fiber, form heat conduction network structure or heat conduction chain to a great extent.
In present embodiment, the tensile strength of every root monofilament of silicon carbide fiber is 2GPa, and modulus is 150GPa.
S30, the prepreg obtained by S20 are placed between the first electrode layer and the second electrode lay, then at 120 DEG C ~ 200 DEG C, 5kgf/cm
2~ 30kgf/cm
2pressure under hot pressing 4h ~ 10h, final curing, obtains copper-clad base plate.
The material of the first electrode layer is at least one in copper, brass, al and ni.The material of the second electrode lay is at least one in copper, brass, al and ni.
The thickness of the 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: at 150 DEG C, 180 DEG C, 220 DEG C, solidify 2h respectively.
Through test, the radial thermal conductivity of the dielectric layer of the copper-clad base plate that the preparation method of this copper-clad base plate obtains is 0.701 ~ 1.004W/mK, and axial thermal conductivity coefficient is 1.325 ~ 1.526W/mK, and second-order transition temperature is 170 ~ 180 DEG C.
The material of the dielectric layer of the copper-clad base plate that the preparation method of this copper-clad base plate obtains is modified oxidized aluminum composite, modified oxidized aluminum composite comprises modified alumina particles, fortifying fibre and epoxy resin by using liquid crystal, and modified alumina particles is that silane coupler modified alumina particle obtains.Alumina particle forms amino, hydroxyl isoreactivity chemical group through silane coupler modified rear surface, the amino that alumina particle is formed by surface, hydroxyl isoreactivity group are connected by chemical bond with between epoxy resin by using liquid crystal, improve the interaction at interface, reduce interface resistance, decrease Cluster Phenomenon.
Be specific embodiment below.In embodiment, ball milling selects the ball mill 50kg level ball mill of the rich making of Meizhou China, laser particle size analyzer is Malvern MS3000 laser particle analyzer, specific surface area analysis instrument is ASAP2020 specific-surface area detection instrument, heat conduction coefficient tester is Hot Disk TPS2500s thermal analyzer, second-order transition temperature tester is TA Q20 means of differential scanning calorimetry tester, and scanning electron microscope is the Nova Nano SEM 450 of FEI Co..
Embodiment 1
(1) aluminum oxide of γ-aminopropyl triethoxysilane modification is prepared.
First by alumina particle dry 4h at 110 DEG C, to be cooledly to room temperature, take alumina particle that 15.0g particle diameter is 700nm, 50mL dimethylbenzene joins in there-necked flask and put into oil bath pan after ultrasonic disperse 10min, magnetic agitation solution is also warming up to 90 DEG C.Dropwise add 1.0g surface-modifying agent γ-aminopropyl triethoxysilane with dropper, after dropping, be warming up to 115 DEG C, keep magnetic agitation, reaction 6h.
Cooled by mixing solutions, pour suction funnel into while hot, the sample dehydrated alcohol that suction filtration obtains repeatedly washs, and puts into vacuum drying oven 110 DEG C of dry 12h, obtains the aluminum oxide of γ-aminopropyl triethoxysilane surface modification.
The SEM photo that the alumina particle that Fig. 2 and Fig. 3 is respectively alumina particle in embodiment 1 and the obtained γ-aminopropyl triethoxysilane modification of embodiment 1 disperses in organic solvent.
As seen from Figure 2, alumina particle before modified easily forms cluster in organic solvent, dispersed poor.Main because alumina particle specific surface area is less, surface energy is very large, is easily combined into block between alumina particle.
As seen from Figure 3, the alumina particle of γ-aminopropyl triethoxysilane modification presents single dispersing substantially, seldom has reunion.Main because modified Membranes On Alumina Particles Surface is with electric charge, the interaction due to electric charge is that the alumina particle of γ-aminopropyl triethoxysilane modification is better dispersed.
(2) prepreg is prepared.
By 2.60g 3,3 ', 5,5 '-tetramethyl biphenyl diglycidylether, 1.40g 4,4 '-diaminodiphenylsulfone(DDS) and 20.00mg triphenylphosphine are uniformly mixed at 180 DEG C, and holding temperature 180 DEG C reaction 30min, obtains amber thick transparent epoxy resin composite.
Obtained 4.00g epoxy resin composite, 4.00g are joined in the 2-butanone solvent of 4.50g through the aluminum oxide of γ-aminopropyl triethoxysilane surface modification, stirs 2h by ultrasonic oscillation method, mix, obtain mixing solutions.
On the silicon carbide fiber adopting bar type coating method to be coated in regular shape cross arrangement in X-Y plane the mixing solutions of above-mentioned preparation.Put into convection oven 130 DEG C baking 120 minutes, make solvent evaporates, obtain prepreg.In prepreg, the total mass percentage ratio of aluminum oxide and epoxy resin by using liquid crystal matrix material is 70%.
Fig. 4 and Fig. 5 is respectively the cross section Electronic Speculum figure of the obtained prepreg of embodiment 1.
Fig. 4 is the Electronic Speculum figure of the coated longitudinally silicon carbide fiber of arrangement of epoxy resin by using liquid crystal, and as seen from Figure 4, modified alumina particles is dispersed in epoxy resin by using liquid crystal, and modified alumina particles is attached to the surface of silicon carbide fiber closely simultaneously.
Fig. 5 is the Electronic Speculum figure of the silicon carbide fiber of the coated radial direction arrangement of epoxy resin by using liquid crystal, as seen from Figure 5, epoxy resin by using liquid crystal integral coating effect is better, existing defects is less, silicon carbide fiber act as the effect of heat-conductive bridges fully, enhance the ligation between modified alumina particles and modified alumina particles and between modified alumina particles and silicon carbide fiber, form heat conduction network structure or heat conduction chain to a great extent.
(3) copper-clad base plate is prepared.
First clean with the hydrochloric acid soln that concentration is 15wt% the copper foil that two thickness are 40 microns, and then two copper foils are placed in acetone ultrasonic cleaning 10min are placed on dehydrated alcohol ultrasonic cleaning 10min, 60 DEG C of oven dry in baking oven, obtain cleaning, the first dry electrode layer and the second electrode lay.
The latter two silicon carbide fiber overlapping for two prepregs is adjacent to, is placed between the first electrode layer and the second electrode lay, in vacuum press, at 150 DEG C, 5kgf/cm
2pressure under hot pressing 3 hours, finally in convection oven, at 150 DEG C, 180 DEG C, 220 DEG C, solidify 2h respectively, obtained copper-clad base plate.
Obtained copper-clad base plate comprises the first electrode layer, dielectric layer and the second electrode lay that stack gradually, wherein the first electrode layer and the second electrode lay are the copper foil that thickness is 40 microns, dielectric layer is formed by two panels prepreg, and prepreg thickness is 500 microns.
Find after test, the radial thermal conductivity of the copper-clad base plate that embodiment 1 prepares is 0.701W/mK, and axial thermal conductivity coefficient is 1.325W/mK, and second-order transition temperature is 175 DEG C.
Embodiment 2
Preparation method is substantially the same manner as Example 1, difference is only: the solidifying agent that step (2) uses is 4,4 '-dihydroxybiphenyl, and 130 DEG C are uniformly mixed, holding temperature 130 DEG C reaction 30min, obtains amber thick transparent epoxy resin composite.
The copper-clad base plate prepared comprises the first electrode layer, dielectric layer and the second electrode lay that stack gradually, and wherein the 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, and thickness is 500 microns.
Find after test, the radial thermal conductivity 0.876W/mK of baseplate material, axial thermal conductivity coefficient is 1.358W/mK, and second-order transition temperature is 130 DEG C.
Embodiment 3
Preparation method is substantially the same manner as Example 1, difference is only: 5.60g (55 parts) joins in the 2-butanone solvent of 4.50g through the aluminum oxide of γ-aminopropyl triethoxysilane and 2.40g epoxy-resin systems by step (2), 2h is stirred by ultrasonic oscillation method, mix, obtain alumina composite material.
The copper-clad base plate prepared comprises the first electrode layer, dielectric layer and the second electrode lay that stack gradually, and wherein the 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, and thickness is 500 microns.
Find after test, the radial thermal conductivity of baseplate material is 1.004W/mK, and axial thermal conductivity coefficient is 1.526W/mK, and second-order transition temperature is 180 DEG C.
Comparative example 1
Preparation method is identical with embodiment 1, and difference is only: step is coated on glasscloth in (2).
The copper-clad base plate prepared comprises the first electrode layer, dielectric medium and the second electrode lay that stack gradually, and wherein the 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, and thickness is 100 microns.
Find after test, the radial thermal conductivity of baseplate material is 0.777W/mK, and axial thermal conductivity coefficient is 0.803W/mK, and second-order transition temperature is 175 DEG C.
Comparative example 2
Preparation method is identical with embodiment 2, and difference is only: the unmodified aluminum oxide adding identical amount in step (2).
The copper-clad base plate prepared comprises the first electrode layer, dielectric layer and the second electrode lay that stack gradually, and wherein the 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, and thickness is 500 microns.The radial thermal conductivity 0.592W/mK of baseplate material, axial thermal conductivity coefficient is 0.888W/mK, and second-order transition temperature is 175 DEG C.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (19)
1. a modified oxidized aluminum composite, it is characterized in that, comprise the promotor of the modified alumina particles of 35 parts ~ 55 parts, the fortifying fibre of 25 parts ~ 35 parts, the epoxy resin by using liquid crystal of 15 parts ~ 35 parts, the solidifying agent of 10 parts ~ 21 parts and 0.1 part ~ 1 part according to massfraction;
Described modified alumina particles is that silane coupler modified alumina particle obtains, and the particle diameter of described modified alumina particles is 100nm ~ 1000nm.
2. modified oxidized aluminum composite as claimed in claim 1, it is characterized in that, the process of described silane coupler modified described alumina particle is as follows: described alumina particle is joined ultrasonic disperse in solvent, described silane coupling agent is added after being warming up to 50 DEG C ~ 60 DEG C, then stir and be warming up to 70 DEG C of reaction 4h ~ 5h, cooled and filtered also retains filter residue, described modified alumina particles is after described filter residue and drying, wherein, the mass ratio of described silane coupling agent and described alumina particle is 3:100.
3. modified oxidized aluminum composite as claimed in claim 1 or 2, it is characterized in that, described silane coupling agent is γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane.
4. modified oxidized aluminum composite as claimed in claim 1, is characterized in that, described fortifying fibre is according to the cross arrangement of X-Y direction of principal axis rule.
5. the modified oxidized aluminum composite as described in claim 1 or 4, is characterized in that, described fortifying fibre is silicon carbide fiber.
6. modified oxidized aluminum composite as claimed in claim 5, is characterized in that, described silicon carbide fiber is made up of 80 ~ 120 monofilament, and the diameter of monofilament described in every root is 12 μm ~ 13 μm.
7. modified oxidized aluminum composite as claimed in claim 1, it is characterized in that, described epoxy resin by using liquid crystal is 3,3 ', 5,5 '-tetramethyl biphenyl diglycidylether, bisphenol A diglycidyl ether, 4,4 '-dihydroxybiphenyl diglycidylether and 4, at least one in 4 '-Dihydroxy binaphthyl base diglycidylether.
8. modified oxidized aluminum composite as claimed in claim 1, is characterized in that, described solidifying agent is 4,4 '-dihydroxybiphenyl, 4, at least one in 4 '-benzidine and DDS.
9. the modified oxidized aluminum composite as described in claim 1,7 or 8, is characterized in that, described epoxy resin by using liquid crystal and described solidifying agent such as are at the stoichiometric ratio.
10. modified oxidized aluminum composite as claimed in claim 1, is characterized in that, described promotor is at least one in triphenylphosphine, imidazoles and chromium acetylacetonate.
11. 1 kinds of copper-clad base plates, comprise the first electrode layer, dielectric layer and the second electrode lay that stack gradually; It is characterized in that, the material of described dielectric layer is the modified oxidized aluminum composite such as according to any one of claim 1 ~ 10.
12. copper-clad base plates as claimed in claim 11, it is characterized in that, the material of described first electrode layer is at least one in copper, brass, al and ni, described the second electrode lay is at least one in copper, brass, al and ni.
The preparation method of 13. 1 kinds of copper-clad base plates, is characterized in that, comprises the steps:
According to massfraction, the promotor of the modified alumina particles of 35 parts ~ 55 parts, the epoxy resin by using liquid crystal of 15 parts ~ 35 parts, the solidifying agent of 10 parts ~ 21 parts and 0.1 part ~ 1 part is dissolved in organic solvent, after ultrasonic 0.5h ~ 2h, obtain mixing solutions;
According to massfraction, the fortifying fibre of 25 parts ~ 35 parts is arranged on centrifugal film, then being coated in by described mixing solutions on described fortifying fibre and toasting 10min ~ 90min at 60 DEG C ~ 150 DEG C, to be cooled stripping by described centrifugal film to room temperature obtains prepreg;
Described prepreg is placed between the first electrode layer and the second electrode lay, then at 120 DEG C ~ 200 DEG C, 5kgf/cm
2~ 30kgf/cm
2pressure under hot pressing 4h ~ 10h, final curing, obtains described copper-clad base plate.
The preparation method of 14. copper-clad base plates as claimed in claim 13, it is characterized in that, the preparation process of described modified alumina particles is as follows: described alumina particle is joined ultrasonic disperse in solvent, described silane coupling agent is added after being warming up to 50 DEG C ~ 60 DEG C, then stir and be warming up to 70 DEG C of reaction 4h ~ 5h, cooled and filtered also retains filter residue, is described modified alumina particles after described filter residue and drying, wherein, the mass ratio of described silane coupling agent and described alumina particle is 3:100.
The preparation method of 15. copper-clad base plates as claimed in claim 14, it is characterized in that, described silane coupling agent is γ-aminopropyl triethoxysilane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-methacryloxypropyl trimethoxy silane, the mass ratio of described silane coupling agent and described alumina particle is 3:100.
The preparation method of 16. copper-clad base plates as claimed in claim 13, it is characterized in that, the fortifying fibre of 25 parts ~ 35 parts is arranged in being operating as on centrifugal film: by the described fortifying fibre of 25 parts ~ 35 parts according to X-Y direction of principal axis rule cross arrangement on described centrifugal film, described fortifying fibre is silicon carbide fiber.
The preparation method of 17. copper-clad base plates as claimed in claim 16, it is characterized in that, described silicon carbide fiber is made up of 80 ~ 120 monofilament, the diameter of monofilament described in every root is 12 μm ~ 13 μm.
The preparation method of 18. copper-clad base plates as claimed in claim 13, it is characterized in that, described epoxy resin by using liquid crystal is 3,3 ', 5,5 '-tetramethyl biphenyl diglycidylether, bisphenol A diglycidyl ether, 4,4 '-dihydroxybiphenyl diglycidylether and 4, at least one in 4 '-Dihydroxy binaphthyl base diglycidylether;
Described solidifying agent is 4,4 '-dihydroxybiphenyl, 4, at least one in 4 '-benzidine and DDS;
The stoichiometric ratios such as described epoxy resin by using liquid crystal and described solidifying agent are.
The preparation method of 19. copper-clad base plates as claimed in claim 13, it is characterized in that, the material that described centrifugal film is is polyethylene terephthalate.
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| CN201410660339.4A CN104371274B (en) | 2014-11-18 | 2014-11-18 | Modified alumina composite material, copper-coated substrate and preparation method of copper-coated substrate |
| 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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