CN1692075A - Particulate alumina, method for producing particulate alumina and composition containing particulate alumina - Google Patents
Particulate alumina, method for producing particulate alumina and composition containing particulate alumina Download PDFInfo
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- CN1692075A CN1692075A CNA028275500A CN02827550A CN1692075A CN 1692075 A CN1692075 A CN 1692075A CN A028275500 A CNA028275500 A CN A028275500A CN 02827550 A CN02827550 A CN 02827550A CN 1692075 A CN1692075 A CN 1692075A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
Particulate alumina has a mean particle size corresponding to a volume-cumulative 50% mean particle size (D50) falling within a range of 3 to 6 mum, has a ratio of D90 to D10 that is 2.5 or less, contains particles that have a particle size of at least 12 mum in an amount of 0.5 mass % or less, particles that have a particle size of 20 mum or more in an amount of 0.01 mass % or less and particles that have a particle size of 1.5 mum or less in an amount of 0.2 mass % or less, and contains an alpha-phase as a predominant phase. In addition, the particulate alumina has a ratio of longer diameter (DL) to shorter diameter (DS) that is 2 or less and a ratio of D50 to mean primary particle size (DP) that is 3 or less. With these features, the particulate alumina has a narrow particle size distribution profile, causes little wear and exhibits excellent flow characteristics.
Description
The cross reference of related application
The application is an application of submitting according to 35U.S.C. § 111 (a).According to 35U.S.C. § 119 (e) (1), the application enjoys the applying date of provisional application 60/345,654, and this provisional application is submitted on January 8th, 2002 according to 35U.S.C. § 111 (b).
Technical field
The present invention relates to the industry of particulate alumina and a kind of production particulate alumina and economic method, wherein particulate alumina is especially suitable for use as various materials, the for example body material of electronic component and sealing material, filler, finishing abrasive substance and the aggregate of sneaking into refractory materials, glass, pottery, or their matrix material; Has narrow size distribution (promptly containing seldom coarse particles and molecule); Cause very little abrasion; And the excellent flow characteristics of demonstration.The invention still further relates to particulate alumina of producing and the composition that contains particulate alumina by the inventive method.
Background technology
In recent years, the requirement of adaptation modularization with high speed, high frequency operation proposed the electronic component that is used for advanced information communication facility (for example by multimedia communication), so that realize this communication fully.Therefore, the improvement of characteristic electron (for example reducing specific inductivity) has become the key issue of this facility of exploitation.In addition, the power consumption that higher requirement integrated and more high-density electronic component has been improved each chip.The heat of effectively removing generation also is a key issue to suppress the rising of electronic component temperature.In view of the above, aluminum oxide, the particularly corundum (Alpha-alumina) that shows narrow size distribution and excellent heat conducting rate become the heat radiation dividing plate, be used for fixing the candidate filler of the body material etc. of semiconducting insulation sealing material and semiconductor components and devices, and in various fields aluminum oxide has been carried out modification.
In this corundum in granules, JP-A SHO 62-191420 discloses spherical corundum particle fissureless, median size 5-35 μ m, this particle prepares by following method: with aluminium hydroxide and the optional crushed products that adds aluminum oxide as other agent combination of crystallization promoter, for example fused alumina or sintered alumina, and this mixture that burns.
The prior art also discloses the corundum in granules that the crystal growing agent is added the summary circle that the known method of aluminium hydroxide can production median size≤5 μ m by comprising.
Especially, JP-A HEI 5-43224 discloses the ball-aluminium oxide particle can be by following method production: 700 ℃ or be lower than 700 ℃ down the heating aluminium hydroxides to being enough to cause dehydration and pyrolytic decomposition, the temperature that improves gained heating product with generation have 90% or higher α ratio burn till intermediate, then in the presence of fluorine-containing stiffening agent burning this burn till intermediate.
Understood method also have thermal spraying, in the method, the aluminum oxide that will produce by Bayer process sprays be sent in high-temperature plasma or the oxyhydrogen flame, with by fusing with quench rapidly and produce the slightly crystal grain of circle.But the defective of thermal spraying is to cause cost higher greatly because of the units of heat demand.In addition, though the aluminum oxide of Sheng Chaning mainly contains Alpha-alumina thus, also comprise some by products, for example δ-aluminum oxide.Because show lower thermal conductivity, these aluminum oxide by products are not preferred.
The crushed products of fused alumina or sintered alumina also is known corundum in granules.But the shape of these corundum in granules is uncertain, has sharp section, and rubber/plastics mixing period between cause significantly abrasion such as kneader, mould.Therefore, these corundum in granules are not preferred.
The electronic component that is used for portable phone or similar facilities need adapt with modularization and high speed, high frequency operation.Have in mind with combining of matrix from the conduction loss and the passive state element of for example lead, being used for the substrates multilayer of these facilities, particularly glass-ceramic substrate, to have low-k be particularly advantageous.But at for example aspect such as mechanical property and dielectric loss, glass-ceramic substrate ratio aluminum oxide ceramic matrix is poor.In order to guarantee the reinforcement feature of glass-ceramic substrate, must use the less particulate alumina of the summary circle that shows narrow size distribution and contain active chemical components and particle diameter as filler.Use traditional method not realize these characteristics.
But; because particle diameter is more little, high more from sticking power, so in the process of molecule being sneaked into glass, rubber or plastics mobile variation; and these molecules form aggregated particles in the glass that obtains, rubber or plastics composite, may reduce mechanical strength and thermal conductivity.Therefore, to the molecule particle diameter reduce also to be limited.
Disclosed particulate alumina has the shape that is suitable as rubber/plastics composite filler in JP-A HEI 6-191833.But, because above-mentioned particulate alumina is to produce by a kind of special methods that is known as original position CVD, therefore to compare with the particulate alumina of producing by other method, its production cost is significantly higher, thereby is disadvantageous at economic aspect.In addition, there is defective in above-mentioned particulate alumina aspect himself characteristic, i.e. the size distribution of broad.
The disclosed particulate alumina of JP-A SHO 62-191420 has thicker particle diameter and excessive maximum particle diameter, and the defective of the disclosed particulate alumina of JP-A HEI 5-43224 is strong gathering, thereby has widened the size distribution of its milling product.
The object of the present invention is to provide a kind of method of suitability for industrialized production particulate alumina of cheapness, the abrasion that wherein said particulate alumina has narrow size distribution, contain a small amount of coarse particles and molecule, cause are very little and show excellent flow characteristics; The particulate alumina of producing by this method is provided and a kind of composition that contains this particulate alumina is provided.
Disclosure of the Invention
The invention provides particulate alumina with following feature: with the corresponding median size of determining according to grain size distribution curve of 50% cumulative volume (being designated hereinafter simply as " 50% volume cumulative mean particle diameter (D50) ") be in the 3-6 mu m range, D90 is equal to or less than 2.5 with the ratio of D10, containing 0.5 quality % or particle diameter still less is that 20 μ m or bigger particle and 0.2 quality % or particle diameter still less are 1.5 μ m or littler particle for particle, 0.01 quality % or the particle diameter still less of at least 12 μ m, and contains α mutually as main phase.
Described particulate alumina comprise the ratio of longer diameter (DL) and shorter diameter (DS) be 2 or ratio littler and D50 and average primary particle diameter (DP) be 3 or littler particulate alumina.
Described particulate alumina comprises and contains 0.1% or Na still less
2O, B and the particulate alumina of the CaO of 500ppm at least of 80ppm at least.
The present invention further provides a kind of method of production particulate alumina, may further comprise the steps: boron compound, halogenide and calcium cpd are added in aluminium hydroxide or the aluminum oxide to form mixture and this mixture that burns.
In described method, halogenide is be selected from aluminum halide, ammonium halide, calcium halide, magnesium halide and hydrogen halide at least a.
In described method, boron compound is for being selected from boric acid, boron oxide and boratory at least a.
In described method, halogenide is be selected from aluminum fluoride, aluminum chloride, ammonium chloride, Neutral ammonium fluoride, Calcium Fluoride (Fluorspan), calcium chloride, magnesium chloride, magnesium fluoride, hydrogen fluoride and hydrogenchloride at least a.
In described method, calcium cpd is be selected from Calcium Fluoride (Fluorspan), calcium chloride, nitrocalcite and calcium sulfate at least a.
In described method, the addition of boron compound is counted 0.05-0.50 quality % based on aluminum oxide by boric acid; The addition of calcium cpd is counted 0.03-0.10 quality % based on aluminum oxide by Ca; Halid addition is the 0.20-0.70 quality % based on aluminum oxide.
In described method, combustion step is 1, and 200-1 carry out under 550 ℃, and the hold-time of top temperature is 10 minutes to 10 hours.
Described method further comprises by the air-flow pulverizer or by the ball mill or the vibrating mill that use alumina balls pulverizes the step that this burns till mixture, and wherein the nozzle ejection gauge pressure of air-flow pulverizer is 2 * 10
5To 6 * 10
5Pa; Be to use airflow separator to remove the step of molecule subsequently.
The present invention also provides a kind of composition that contains particulate alumina, and wherein the content of particulate alumina is at least 10 quality % but is no more than 90 quality %.
Described composition further comprises the polymkeric substance that is filled with particulate alumina, and this polymkeric substance is be selected from aliphatic resin, unsaturated polyester resin, acrylic resin, methacrylic resin, vinyl ester resin, Resins, epoxy and silicone resin at least a.
In described composition, polymkeric substance is oily mater and has 40-100 ℃ softening temperature or fusing point.
The present invention further provides a kind of electronic component or semiconducter device, wherein between thermal source and scatterer, contain the present composition.
Because 50% cumulative volume median size (D50) of particulate alumina of the present invention is in the 3-6 mu m range, so flowing property is improved.In addition, because the ratio of D90 and D10 is 2.5 or littler, it is narrower that size distribution becomes, thereby reduced the ratio of blended coarse particles and molecule.In addition, owing to contain α-phase as main phase, so this particulate alumina can be advantageously used for filler, for example body material of electronic component, sealing material or finishing abrasive substance, or the aggregate of refractory materials, glass, pottery, or the matrix material of these materials.
And because the inventive method only needs 1,550 ℃ or lower temperature of combustion to come the production particulate alumina, and soaking time needn't surpass 10 hours, so this method is economical and easy to implement.
Implement best mode of the present invention
Particulate alumina of the present invention has following feature: 50% cumulative volume median size (D50) is in the 3-6 mu m range, D90 is equal to or less than 2.5 with the ratio of D10, containing 0.5 quality % or particle diameter still less is 1.5 μ m or littler particle for particle, 0.01 quality % or the particle diameter still less of at least 12 μ m for the particle of at least 20 μ m and 0.2 quality % or particle diameter still less, and contains α mutually as main phase.
Term " contains α mutually as main phase " and refers to that the content of α phase is at least 95 quality %, preferably at least 98 quality %.Described α-phase content is determined in the following manner.
Under following condition, particulate alumina is carried out the X-ray diffraction analysis, target: Cu.K α; Slit: 0.3mm, scanning step: 2 °/minute, sweep limit: 2 θ=10-70 °.
α-phase content is derived by following equation: α-phase content=[(A-C)/{ (A-C)+(B-C) }] * 100, wherein A represents in 2 θ=68.2 ° peak height of locating (Alpha-alumina), the B representative is ° peak height of locating (κ-aluminum oxide) in 2 θ=63.1, and C represents the 2 θ=69.5 ° baseline height of locating.
Volume cumulative mean particle diameter of the present invention can be determined by any known size distribution metering facility.Preferably use for example laser diffraction size distribution metering facility mensuration particle diameter.Preferably, the particle of certain particle diameter (for example, 20 μ m) carries out water conservancy classification and definite by the amounts of particles of determining to be retained on the sieve by using the ultrafine particle sorter under ultra-sonic dispersion.
These particulate alumina are served as alumina particle and are especially suitable for use as the filler that adds in the glass ceramic composition.D50 must be in the 3-6 mu m range, and preferably in the 3.5-4.5 mu m range.The particle diameter of aluminum oxide preferably equates with particle diameter as the glass powder of main raw in the glass ceramic composition.When D50 surpasses 6 μ m or during less than 3 μ m, the mechanical strength of matrix is relatively poor, causes performance degradation.D90/D10 must control to 2.5 or littler, is preferably 2.2 or littler.When D90/D10 surpassed 2.5, size distribution broadened, thereby can not reach uniform distribution in the reaction of glass and alumina particle, and the result has reduced the mechanical strength of matrix.When the amounts of particles of particle diameter at least 12 μ m surpasses 0.5 quality % or particle diameter be the amounts of particles of at least 20 μ m during above 0.01 quality %, and the dielectric strength of matrix is relatively poor.When particle diameter is 1.5 μ m or littler amounts of particles when surpassing 0.2 quality %, the mobile variation of composition, and dielectric loss increases.
The ratio that particulate alumina of the present invention preferably has longer diameter (DL) and shorter diameter (DS) is 2 or littler, the ratio of D50 and average primary particle diameter (DP) is 3 or littler, because such particulate alumina is suitable as the filler that adds in the glass ceramic composition.
When the ratio of DL/DS surpassed 2, it is flat that particle shape becomes, and therefore makes the thermal conductivity variation of the mechanical strength and the composition of matrix.When the ratio of D50/DP surpassed 3, alumina particle was in accurate state of aggregation, therefore made the mobile variation of the mechanical strength and the composition of matrix.
In the present invention, the longer diameter of alumina particle and shorter diameter are determined by image analysis is carried out in the secondary electron imaging of observing down in scanning electronic microscope (SEM).Average primary particle diameter is calculated according to following equation by the BET specific surface area: the true density of primary particle diameter (μ m)=6/{ aluminum oxide * BET specific surface area (m
2/ g) }, wherein the true density of aluminum oxide is 3.987g/cm
3The BET specific surface area is determined by nitrogen adsorption method.
Particulate alumina of the present invention contains 0.1% or Na still less
2O, preferred 0.05% or still less.Work as Na
2The content of O surpasses 0.1%, the sintering characteristic deterioration, thus reduced the reliability of insulating material.The content of B is 80ppm at least, preferably 100ppm at least; CaO content is 500ppm at least, preferably 800ppm at least.B or Cao are as effective sintering aid of sintered glass stupalith.Particularly, B or CaO can promote the liquid phase sintering in the crystal boundary between glass matrix and particulate alumina, thereby strengthen the mechanical strength of matrix.
Particulate alumina of the present invention can be by comprising the method production of following step: will boron compound, halogenide and calcium cpd add in the raw material powder and form mixture, and this mixture then burns.Aluminium hydroxide or aluminum oxide are as raw material powder.But, also can use the mixed powder that contains aluminium hydroxide and aluminum oxide or the mixed powder of aluminium hydroxide and aluminum oxide.
If use as raw material powder, aluminum oxide preferably has 10-30m
2The BET specific surface area of/g.Usage ratio to aluminum oxide in the mixed powder and aluminium hydroxide is not particularly limited.The BET specific surface area is 10m
2/ g or littler, particularly less than 5m
2The aluminum oxide of/g is unfavorable to the α grain growth during burning.Therefore, the BET specific surface area preferably drops in the above-mentioned scope.
The preferred boron compound that uses comprises boric acid, boron oxide and borate.The preferred halogenide example that uses comprises and is selected from least a of aluminum halide, ammonium halide, calcium halide, magnesium halide and hydrogen halide.Wherein, more preferably use aluminum fluoride, aluminum chloride, ammonium chloride, Neutral ammonium fluoride, Calcium Fluoride (Fluorspan), calcium chloride, magnesium chloride, magnesium fluoride, hydrogen fluoride and hydrogenchloride.The example of the preferred calcium cpd that uses comprises Calcium Fluoride (Fluorspan), calcium chloride, nitrocalcite and calcium sulfate.
Boron compound, halogenide and calcium cpd can add separately.As selection, also can use the one matter that can serve as two or more compositions in these three kinds of compounds.For example, the halogenide of adding calcium just is equivalent to add halogenide of the present invention and calcium cpd.Add the halogenide that contains boron and calcium and just be equivalent to add boron compound of the present invention, halogenide and calcium cpd.
The method of particulate alumina produced according to the invention, the add-on of boron compound is preferably 0.05-0.5 quality % based on aluminum oxide, more preferably 0.1-0.4 quality % by boric acid.Halid add-on is preferably the 0.2-0.7 quality % based on aluminum oxide, more preferably 0.3-0.6 quality %.The add-on of calcium cpd is preferably 0.03-0.1 quality % based on aluminum oxide, more preferably 0.04-0.07 quality % by calcium.The addition of all cpds is lower than separately that the lower limit of respective range is not preferred, because slightly circular alumina particle can not be grown.The addition of all cpds is higher than separately, and the upper limit of respective range is not preferred, because effect of the present invention, promptly provide to be suitable as the particulate alumina that filler adds glass ceramic composition, no longer be enhanced, and thisly excessively say it is not preferred from economic angle.
When adding boron compound, halogenide and calcium cpd respectively, these compounds preferably add by the amount in the above-mentioned scope.When adding a kind of material of two or more compositions that can be used as these three kinds of compounds, preferably add by following mode.For example, when adding calcium halide, the amount of calcium cpd to be added is from the Ca cubage based on aluminum oxide, and halid amount to be added is to calculate from the amount of the calcium halide that adds.When adding contains the halogenide of boron and calcium, the amount of boron compound to be added is to calculate from the boric acid content based on aluminum oxide, the amount of calcium cpd to be added is from the Ca cubage based on aluminum oxide, and halid amount to be added is the halogenide calculating from boracic that adds and calcium.
In the present invention, carry out under the preferred temperature in 1200-1550 ℃ of scope of burning, and kept top temperature 10 minutes to 10 hours.More preferably be, temperature of combustion is controlled at 1350-1500 ℃, and the hold-time of top temperature is in 30 minutes to 8 hours scope.
When temperature of combustion was lower than 1200 ℃, α-phase can not form in particulate alumina, and this is not preferred; And if the hold-time of top temperature be less than 10 minutes, then the growth of alumina particle is suppressed, this also is not preferred.Even temperature of combustion surpasses 1550 ℃ or soaking time and surpasses 10 hours, effect of the present invention no longer further strengthens, so this is not preferred from the angle of economy.The type that is used for the incendiary process furnace is not specifically limited, can uses known instrument, for example single kiln (single kiln), tunnel furnace or rotary kiln.
Preferably, the method for production particulate alumina of the present invention comprises boron compound, halogenide and calcium cpd is added in the mixture of aluminium hydroxide, aluminum oxide or aluminium hydroxide and aluminum oxide to form mixture; Burn this mixture to generate alumina particle; The alumina particle that generates is 2 * 10 with the nozzle ejection gauge pressure
5Pa to 6 * 10
5Pa (2-6kgf/cm
2) the air-flow pulverizer or pulverize by the ball mill or the vibrating mill that use alumina balls, subsequently by using airflow separator to remove molecule.Preferably, described air-flow pulverizer uses 3 * 10
5Pa to 5 * 10
5The nozzle gauge pressure of Pa.When using described air-flow pulverizer, the rotating speed of air-flow, the material quantity of sending into and the separator that is used in combination with the air-flow pulverizer all should suitably be adjusted, and makes pulverized particulate alumina demonstrate predetermined maximum particle diameter.When nozzle injection pressure is lower than 2 * 10
5During Pa, crush efficiency descends; Be higher than 6 * 10 and work as nozzle injection pressure
5During Pa, degree of grinding too improves, and adds providing of alumina particle of the present invention in the glass ceramic composition thereby suppressed to be suitable as filler.The alumina balls that are used for ball mill or vibrating mill preferably have the diameter of 10-25mm.If the use ball mill, according to the scale and the performance of pulverizer, milling time was generally 180-420 minute.So the powder of pulverizing often contains overground ultrafine particle.These particles preferably use airflow separator to remove.
The particulate alumina that the inventive method is produced is sneaked into by borosilicate glass, MgO-Al
2O
3-SiO
2Glass, CaO-Al
2O
3-SiO
2In the glass powder that glass etc. are made, so that a kind of glass ceramic composition suitably to be provided.Preferably, described glass ceramic composition contains the described particulate alumina of 10-90 quality %.If the content of particulate alumina in said composition too improves, just must improve the temperature of combustion of glass-ceramic, thereby make the specific inductivity variation, otherwise, if the content of particulate alumina is too low, the mechanical properties decrease of matrix.Therefore, more preferably be that the content of particulate alumina is in 20-60 quality % scope.Because the mechanical property of the temperature of combustion of the content influence glass-ceramic of particulate alumina and the material that formed by this glass-ceramic is selected like this so its content is preferred, make the material that forms show the performance characteristics consistent with purpose.
The particulate alumina of producing by the inventive method is preferably sneaked into polymkeric substance for example in oil, rubber and the plastics, thereby high thermal conductivity fat or oil composition, high thermal conductivity rubber combination and high thermal conductivity plastics composite are provided.The content of particulate alumina is preferably at least 80 quality % especially.
Any known polymkeric substance can be as the component of polymer of resin combination of the present invention.Preferred examples of polymer comprises aliphatic resin, unsaturated polyester resin, acrylic resin, methacrylic resin, vinyl ester resin, Resins, epoxy and silicone resin.
These resins can have lower molecular weight or high molecular.The form of these resins can be determined arbitrarily according to application target and environment, and can be oily liquids, rubber-like material or hardening product.
The example of described resin comprises hydrocarbon resin { polyethylene for example, vinyl-vinyl acetate copolymer, ethylene-acrylate copolymer, ethylene-propylene copolymer, poly-(ethylene-propylene), polypropylene, polyisoprene, poly-(isoprene-butylene), polyhutadiene, poly-(styrene butadiene), poly-(butadiene-acrylonitrile), sovprene, Chlorinated Polypropylene III, polybutene, polyisobutene, olefin resin, petroleum resin, styrene resin, ABS resin, coumarone-indene resin, terpine resin, Gum Rosin and diene resin }; (methyl) acrylic resin { for example, homopolymer and multipolymer of producing by (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) 2-ethylhexyl acrylate, (methyl) vinylformic acid n-nonyl ester, (methyl) vinylformic acid and/or (methyl) glycidyl acrylate; Polyacrylonitrile and their multipolymer; Polybutylcyanoacrylate; Polyacrylamide; With poly-(methyl) acrylate }; Vinyl acetate resin and vinyl alcohol resin { for example, vinyl acetate resin, polyvinyl alcohol, polyvinyl acetal resin and polyvinyl ether }; Halogen-containing resin { for example vinyl chloride resin, vinylidene resin, fluoro-resin }; Nitrogenous Vinylite { for example, Polyvinyl carbazole, Polyvinylpyrolidone (PVP), polyvinylpyridine and polyvinyl imidazol }; Diene polymer { for example, butadienyl synthetic rubber, chloroprene base synthetic rubber and prenyl synthetic rubber }; Polyethers { for example, polyoxyethylene glycol, polypropylene glycol, hydrin rubber and oxetane resin }; Polyethylene imine resin; Phenol resins { for example, phenol-formaldehyde resin, cresol-formaldehyde resin, modified phenolic resin, phenol-furfural resin and resorcinol resin }; Aminoresin { for example, urea resin and modified urea resin, melamine resin, guanamine resin, aniline resin and sulfonamide resin }; Aromatic hydrocarbon resin { for example, xylene formal dehyde resin, toluene formaldehyde resin }; Ketone resin { for example, cyclohexanone resin and methylethylketone resin }; The saturated alcohol acid resin; Unsaturated polyester resin { for example, maleic anhydride-ethylene glycol polycondensate and maleic anhydride-phthalic anhydride-ethylene glycol polycondensate }; O-phthalic allyl propionate resin is for example, with the crosslinked unsaturated polyester resin of Phthalic acid, diallyl ester; Vinyl ester resin for example, by with the resin of crosslinked productions such as vinylbenzene, acrylate, have the primary polymer of dihydroxyphenyl propane ehter bond and highly active vinylformic acid terminal double link }; The allyl ester resin; Polycarbonate; The poly phosphate resin; Polyamide resin; Polyimide resin; Silicone resin { for example, silicone oil, silicon rubber and by polydimethylsiloxane deutero-silicone resin, and have in the molecule hydride siloxane, hydroxyl siloxanes, oxyalkylsiloxane or vinylsiloxane residue and by heating or in the presence of catalyzer sulfurized activated silica resin; Furane resin; Urethane resin; Urethanes; Resins, epoxy { for example, dihydroxyphenyl propane-Epicholorohydrin condenses, phenolic novolac-Epicholorohydrin condenses, polyglycol-Epicholorohydrin condenses }; Phenoxy resin; And their modified product.These resins can use in independent or multiple mixing.
These polymkeric substance can have lower molecular weight or high molecular.The form of these resins can be determined arbitrarily according to purpose of using and environment, and can be oily liquids, rubber-like material or hardening product.
Wherein, preferably use unsaturated polyester resin, acrylic resin, methacrylic resin, vinyl ester resin, Resins, epoxy and silicone resin.
More preferably be, described polymkeric substance is an oily mater, this is consistent because of the running surface shape of the running surface shape of grease that makes by blended particulate alumina and oil and thermal source and the scatterer in electron device, has reduced the distance between them, thereby has strengthened the dissipation of heat effect.
The type that is used for oil of the present invention is not specifically limited, and the oil of any kind of can use.Example comprises silicone oil, petroleum based oil, synthetic oil and contains fluorocarbon oil.
For the ease of the processing of thermally conductive composition, described oil is preferably a kind of like this polymkeric substance, it when room temperature in the form of sheets, with temperature raise softening or fusing after become grease-like.Such oil is not specifically limited, can uses those known oil.Example comprises thermoplastic resin, their lower molecular weight classification, and softening temperature or fusing point are through the thermoplastic resin composition of blend oil modification.Softening temperature or fusing point change with the temperature of thermal source, preferably in 40-100 ℃ of scope.
Above-mentioned thermally conductive resin is inserted between the thermal source and scatterer such as radiator element of electronic component or semiconducter device, thereby effectively evacuate the heat that produces, suppress electronic component or the thermal degradation when of semiconducter device or the deterioration of other type, reduce rate of breakdown, prolong their work-ing life.Electronic component and semiconducter device are not specifically limited, the example comprises that computer central processing unit (CPUs), plasma display (PDPs), secondary cell and relevant peripherals are (for example, be configured in the equipment of hybrid electric vehicle or the similar equipment by controlled temperature stable cell performance, wherein temperature control realizes by above-mentioned heat conductivity composition is provided between secondary cell and scatterer), motor radiating device, Peltier ' s device, phase inversion device and (height) power transistor.
Below, the present invention will describe in detail in the mode of embodiment and Comparative Examples, but these embodiment and Comparative Examples do not constitute any limitation the present invention.
Embodiment 1:
With (the BET value is 20m in boric acid (0.2 quality %), aluminum fluoride (0.03 quality %), Calcium Fluoride (Fluorspan) (0.1 quality %) and ammonium chloride (0.4 quality %) the adding aluminum oxide
2/ g), the mixture of formation burnt 4 hours down at 1450 ℃.
After burning was finished, will burning till product, to shift out and use the nozzle ejection gauge pressure be 5 * 10
5The air-flow pulverizer of Pa is pulverized.Confirm that through x-ray diffractometer the granulated product of pulverizing is the aluminum oxide that contains 95% α-phase.The BET specific surface area of the particulate alumina of Sheng Chaning is determined by nitrogen adsorption method thus.With the Sodium hexametaphosphate 99 is that dispersion agent utilizes laser diffraction size distribution survey meter (Microtrack HRA is made by Nikkiso) to measure the volume cumulative mean particle diameter and the size distribution of this particulate alumina.20 μ m particulate quantity are determined by following method: using supersound washing device (CH-30S-3A, ShimadaRika) under the ultra-sonic dispersion, the ultrafine particle separator (Shodex-Ps) that use has 20 μ m sieves carries out hydraulic classification, then the residuum on the sieve is transferred on the filter paper, used drying facility to make these residuum dehydrations and use platform balance measure dried residuum.The long and shorter particle diameter of particulate alumina utilizes the SEM photo to measure.Primary particle diameter is calculated by the BET specific surface area according to above-mentioned conversion formula.
Embodiment 2-6 and Comparative Examples 1-4:
Under the various situations, production particulate alumina under the listed condition of table 1.In embodiment 2 and Comparative Examples 1,2 and 4, use ball mill to pulverize.In embodiment 2, after the pulverizing, use airflow separator to remove molecule.Other condition that does not provide in the table 1 is identical with embodiment 1.Material behavior, combustion conditions and pulverization conditions are listed in table 1, and the assessment result of thus obtained particulate alumina product is listed in table 2.
Embodiment 7:
The particulate alumina (40 mass parts) that embodiment 1 obtains is mixed with borosilicate glass powder (60 mass parts), add solvent (ethanol/toluene) and acrylic acid binder, thereby form a kind of slurry.Make this slurry form biscuit by scraping the skill in using a kitchen knife in cookery.This biscuit forms ceramic plate at 1000 ℃ of following sintering.Measure the flexural strength of this ceramic plate by the method for JIS R1601 description.Assessment result is listed in table 3.
Embodiment 8:
Repeat the step of embodiment 7, but with the particulate alumina of the particulate alumina alternate embodiment 1 of embodiment 2 preparations, and so obtain ceramic plate.Measure the flexural strength of ceramic plate, and assessment result is listed in table 3.
Comparative Examples 5:
Repeat the step of embodiment 7, but with the particulate alumina of the particulate alumina alternate embodiment 1 of Comparative Examples 1 preparation, and so obtain ceramic plate.Measure the flexural strength of ceramic plate, and assessment result is listed in table 3.
Comparative Examples 6:
Repeat the step of embodiment 7, but with the particulate alumina of the particulate alumina alternate embodiment 1 of Comparative Examples 2 preparations, and so obtain ceramic plate.Measure the flexural strength of ceramic plate, and assessment result is listed in table 3.
Embodiment 9:
With silicone oil (KF96-100, by Shin-Etsu Chemical Co., Ltd. production) in the particulate alumina of (20 mass parts) adding embodiment 1 (80 mass parts), and with planetary stirring de-bubble facility (KK-100, produce by Kurabo Industries Ltd.) stir the mixture that forms, thus form grease.Use is measured this greasy thermotolerance according to U.S.'s test and the facility that materialogy meeting (ASTM) D5470 makes.Assessment result is listed in table 4.
Embodiment 10:
Repeat the step of embodiment 9, but silicone oil (KF96-100, by Shin-Etsu Chemical Co., Ltd. produces) (20 mass parts) is added in the particulate alumina (80 mass parts) of embodiment 2 productions, form grease.Measure this greasy thermotolerance, assessment result is listed in table 4.
Comparative Examples 7:
Repeat the step of embodiment 9, but, form grease in the particulate alumina of silicone oil (KF96-100, by Shin-Etsu Chemical Co., Ltd. produces) (20 mass parts) adding Comparative Examples 1 production (80 mass parts).Measure this greasy thermotolerance, assessment result is listed in table 4.
Comparative Examples 8:
Repeat the step of embodiment 9, but (KF96-100, by Shin-Etsu Chemical Co., Ltd. produces (20 mass parts) and adds in the particulate alumina (80 mass parts) of Comparative Examples 2 productions, forms grease with silicone oil.Measure this greasy thermotolerance, assessment result is listed in table 4.
Table 1
| Material behavior | Burning | Pulverize | ||||||
| BET value (m 2/g) | Compound addition (quality %) based on aluminum oxide | Pulverize | Pneumatic separation | |||||
| Boron compound | Halogenide | Calcium cpd | ||||||
| Boric acid | Aluminum fluoride | Aluminum chloride | Calcium Fluoride (Fluorspan) | |||||
| Embodiment 1 | Aluminum oxide | ??20 | ??0.2 | ??0.03 | ??0.4 | ??0.1 | The air-flow pulverizer | ??- |
| Embodiment 2 | Aluminum oxide | ??20 | ??0.2 | ??0.03 | ??0.4 | ??0.1 | Ball mill | Carry out |
| Embodiment 3 | Aluminum oxide | ??20 | ??0.2 | ??0.03 | ??0.4 | ??0.1 | The air-flow pulverizer | ??- |
| Embodiment 4 | Aluminum oxide | ??20 | ??0.3 | ??0.03 | ??0.4 | ??0.1 | The air-flow pulverizer | ??- |
| Embodiment 5 | Aluminium hydroxide | ??- | ??0.2 | ??0.03 | ??0.4 | ??0.1 | The air-flow pulverizer | ??- |
| Embodiment 6 | Mixture | ??- | ??0.2 | ??0.03 | ??0.4 | ??0.1 | The air-flow pulverizer | ??- |
| Comparative Examples 1 | Aluminum oxide | ??20 | ??0.3 | ??0.05 | ??0 | ??0 | Ball mill | Do not carry out |
| Comparative Examples 2 | Aluminum oxide | ??20 | ??0 | ??0.04 | ??0.6 | ??0 | Ball mill | Do not carry out |
| Comparative Examples 3 | Aluminum oxide | ??20 | ??0.3 | ??0.05 | ??0 | ??0 | The air-flow pulverizer | ??- |
| Comparative Examples 4 | Aluminum oxide | ??20 | ??0.2 | ??0.03 | ??0.4 | ??0.1 | Ball mill | Do not carry out |
Table 2
| Product performance | ||||||||||||
| BET value (m 2/g) | ??DP ??(μm) | ??D50 ??(μm) | ??D50/DP | ??D90/D10 | The granule content of 〉=20 μ m (quality %) | The granule content of 〉=12 μ m (quality %) | The granule content of≤1.5 μ m (quality %) | ??DL/DS | ??Na 2O ??(％) | ??B ??ppm | ??CaO ??ppm | |
| Embodiment 1 | ??0.7 | ??2.06 | ??4.5 | ??2.2 | ??2 | ??0.003 | ??0 | ??0 | ??1.6 | ??0.02 | ??150 | ??850 |
| Embodiment 2 | ??0.7 | ??2.18 | ??4.7 | ??2.15 | ??1.9 | ??0.002 | ??0.1 | ??0 | ??1.5 | ??0.02 | ??150 | ??850 |
| Embodiment 3 | ??0.7 | ??2.06 | ??4.1 | ??2 | ??2 | ??0.004 | ??0 | ??0 | ??1.7 | ??0.02 | ??150 | ??980 |
| Embodiment 4 | ??0.6 | ??2.35 | ??5.2 | ??2.19 | ??2.3 | ??0.006 | ??0.2 | ??0 | ??1.8 | ??0.02 | ??180 | ??850 |
| Embodiment 5 | ??0.8 | ??1.98 | ??3.8 | ??1.93 | ??2.1 | ??0.002 | ??0 | ??0.2 | ??1.6 | ??0.02 | ??150 | ??850 |
| Embodiment 6 | ??0.7 | ??2.12 | ??4.1 | ??1.91 | ??1.8 | ??0.002 | ??0 | ??0 | ??1.6 | ??0.02 | ??150 | ??850 |
| Comparative Examples 1 | ??1.8 | ??0.84 | ??1.5 | ??1.8 | ??0.8 | ??0.03 | ??0 | ??49.4 | ??2.3 | ??0.05 | ??180 | ??150 |
| Comparative Examples 2 | ??1.1 | ??1.33 | ??4.2 | ??3.15 | ??3.9 | ??0.1 | ??2.1 | ??4 | ??2.5 | ??0.03 | ??2 | ??150 |
| Comparative Examples 3 | ??1.1 | ??1.39 | ??2.9 | ??2.08 | ??2.1 | ??0.003 | ??0 | ??3.8 | ??2.2 | ??0.05 | ??180 | ??150 |
| Comparative Examples 4 | ??1.3 | ??1.18 | ??3.4 | ??2.87 | ??3.1 | ??0.04 | ??0 | ??8.4 | ??1.7 | ??0.02 | ??150 | ??850 |
Table 3
| Embodiment 7 | Embodiment 8 | Comparative Examples 5 | Comparative Examples 6 | |
| Flexural strength (MPa) | ??370 | ??360 | ??250 | ??251 |
Table 4
| Embodiment 9 | Embodiment 10 | Comparative Examples 7 | Comparative Examples 8 | |
| Thermotolerance (K.cm 2/W) | ??0.1 | ??0.11 | ??0.15 | ??0.16 |
Under 0.7MPa, measure in 35 ℃ (constant)
Industrial usability
According to the present invention, the compatibility between particulate alumina and the glass dust is enhanced, thereby a kind of glass ceramic composition with high strength is provided. In addition, the rubber-based, plastic base and the Silicon-oil-based resin combination that contain particulate alumina of the present invention demonstrate high thermal conductivity. When between the thermal source that the present composition is placed electronic component or semiconductor devices and the radiator, obtained the performance (for example anti-weight bearing power of the higher speed of service and Geng Gao) than conditional electronic element or semiconductor devices excellence.
Claims (17)
1. particulate alumina with following feature: with the 50% corresponding median size of volume cumulative mean particle diameter (D50) in the 3-6 mu m range, D90 is equal to or less than 2.5 with the ratio of D10, containing 0.5 quality % or particle diameter still less is that 20 μ m or bigger particle and 0.2 quality % or particle diameter still less are 1.5 μ m or littler particle for particle, 0.01 quality % or the particle diameter still less of at least 12 μ m, and contains α mutually as main phase.
2. particulate alumina according to claim 1, the ratio of wherein longer diameter (DL) and shorter diameter (DS) be 2 or ratio littler and D50 and average primary particle diameter (DP) be 3 or littler.
3. particulate alumina according to claim 1 and 2, wherein it contains 0.1% or Na still less
2O, B and the CaO of 500ppm at least of 80ppm at least.
4. a method of producing particulate alumina comprises and will form mixture in boron compound, halogenide and calcium cpd adding aluminium hydroxide or the aluminum oxide, and this mixture that burns.
5. method according to claim 4, wherein halogenide is be selected from aluminum halide, ammonium halide, calcium halide, magnesium halide and hydrogen halide at least a.
6. according to claim 4 or 5 described methods, wherein boron compound is for being selected from boric acid, boron oxide and boratory at least a.
7. according to each described method among the claim 4-6, wherein halogenide is be selected from aluminum fluoride, aluminum chloride, ammonium chloride, Neutral ammonium fluoride, Calcium Fluoride (Fluorspan), calcium chloride, magnesium chloride, magnesium fluoride, hydrogen fluoride and hydrogenchloride at least a.
8. according to each described method among the claim 4-7, wherein calcium cpd is be selected from Calcium Fluoride (Fluorspan), calcium chloride, nitrocalcite and calcium sulfate at least a.
9. according to each described method among the claim 4-8, wherein the addition of boron compound is counted 0.05-0.50 quality % based on aluminum oxide by boric acid; The addition of calcium cpd is counted 0.03-0.10 quality % based on aluminum oxide by Ca; Halid addition is the 0.20-0.70 quality % based on aluminum oxide.
10. according to each described method among the claim 4-9, wherein combustion step is 1, and 200-1 carry out under 550 ℃, and the hold-time of top temperature is 10 minutes to 10 hours.
11., comprise that further by the nozzle ejection gauge pressure be 2 * 10 according to each described method among the claim 4-10
5To 6 * 10
5The air-flow pulverizer of Pa is pulverized the step that this burns till mixture.
12. according to each described method among the claim 4-10, further comprise by the ball mill or the vibrating mill that use alumina balls and pulverize the step that this burns till mixture, be to use airflow separator to remove the step of molecule subsequently.
13. one kind contains the polymkeric substance and the composition of particulate alumina according to claim 1, wherein the content of particulate alumina is at least 10 quality % but is no more than 90 quality %.
14. composition according to claim 13, wherein polymkeric substance is be selected from aliphatic resin, unsaturated polyester resin, acrylic resin, methacrylic resin, vinyl ester resin, Resins, epoxy and silicone resin at least a.
15. composition according to claim 13, wherein polymkeric substance is an oily mater.
16. composition according to claim 13, wherein polymkeric substance has 40-100 ℃ softening temperature or fusing point.
17. electronic component or semiconducter device wherein contain the described composition of claim 13 between thermal source and radiator.
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| JP2001396221A JP2003192339A (en) | 2001-12-27 | 2001-12-27 | Alumina particle, manufacturing method for the same and composition containing the same |
| JP396221/2001 | 2001-12-27 | ||
| US60/345,654 | 2002-01-08 |
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| CN100343170C CN100343170C (en) | 2007-10-17 |
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| JP (1) | JP2003192339A (en) |
| KR (1) | KR20040071265A (en) |
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-
2001
- 2001-12-27 JP JP2001396221A patent/JP2003192339A/en active Pending
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2002
- 2002-12-23 TW TW091137044A patent/TW200301223A/en unknown
- 2002-12-27 CN CNB028275500A patent/CN100343170C/en not_active Expired - Lifetime
- 2002-12-27 KR KR10-2004-7010163A patent/KR20040071265A/en not_active Application Discontinuation
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Also Published As
| Publication number | Publication date |
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| JP2003192339A (en) | 2003-07-09 |
| KR20040071265A (en) | 2004-08-11 |
| TW200301223A (en) | 2003-07-01 |
| CN100343170C (en) | 2007-10-17 |
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