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WO2024071431A1 - Particules d'alumine sphériques, leur méthode de production et composition composite de résine les comprenant - Google Patents

Particules d'alumine sphériques, leur méthode de production et composition composite de résine les comprenant Download PDF

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Publication number
WO2024071431A1
WO2024071431A1 PCT/JP2023/035864 JP2023035864W WO2024071431A1 WO 2024071431 A1 WO2024071431 A1 WO 2024071431A1 JP 2023035864 W JP2023035864 W JP 2023035864W WO 2024071431 A1 WO2024071431 A1 WO 2024071431A1
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WIPO (PCT)
Prior art keywords
particles
spherical alumina
alumina
spherical
alumina particles
Prior art date
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PCT/JP2023/035864
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English (en)
Japanese (ja)
Inventor
竜太郎 沼尾
孝広 和田
睦人 田中
克昌 矢木
正徳 阿江
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Nippon Steel Chemical and Materials Co Ltd
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Nippon Steel Chemical and Materials Co Ltd
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Priority to JP2024550532A priority Critical patent/JPWO2024071431A1/ja
Priority to CN202380068477.0A priority patent/CN119923371A/zh
Priority to KR1020257009359A priority patent/KR20250052437A/ko
Publication of WO2024071431A1 publication Critical patent/WO2024071431A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C01F7/021—After-treatment of oxides or hydroxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area

Definitions

  • the present invention relates to spherical alumina particles, in particular spherical alumina particles with a reduced surface residual Na concentration and low degree of aggregation, a method for producing the same, and a resin composite composition containing the same.
  • thermally conductive inorganic fillers are made from inexpensive aluminum hydroxide and aluminum oxide (hereafter referred to as alumina), as well as materials such as silicon carbide, boron nitride, and aluminum nitride, which are expected to have high thermal conductivity.
  • alumina in particular is often used as a thermally conductive inorganic filler because it is inexpensive and chemically stable.
  • the Bayer process is a widely known method for producing alumina.
  • bauxite is treated with caustic soda (sodium hydroxide) to dissolve aluminum as sodium aluminate, and impurities such as iron, titanium, and silicon are precipitated as red mud.
  • caustic soda sodium hydroxide
  • impurities such as iron, titanium, and silicon are precipitated as red mud.
  • This is filtered, and seeds of hydrous alumina Al 2 O 3.3H 2 O are added to the filtrate (sodium aluminate solution) and stirred for several days to precipitate hydrous alumina in the liquid, which is then recovered.
  • the recovered hydrous alumina is calcined to obtain high-purity alumina Al 2 O 3 .
  • the alumina is treated with caustic soda (sodium hydroxide), so sodium may remain in the finished product. If a large amount of sodium is present on the filler surface, it reacts with the resin or moisture in the air and releases hydroxide ions. These hydroxide ions react with the epoxy groups present in the epoxy resin, inhibiting the polymerization reaction between the resins and causing poor curing. Furthermore, if sodium or potassium ions are present in the resin composition created by kneading with the epoxy groups, the voltage resistance will be impaired. For these reasons, it is preferable for the amount of sodium to be small. In order to remove or reduce the sodium, the alumina is washed with water and then dried.
  • caustic soda sodium hydroxide
  • Patent Document 1 discloses an apparatus that can efficiently wash, filter, and dry powders such as alumina in the same container. More specifically, it proposes that by introducing compressed gas into the container, it is possible to wash, filter, and dry powders in the same container without the need for stirring blades inside the container. It also discloses the use of electrical or steam heating and microwave irradiation to improve the drying speed.
  • Patent Document 2 discloses fine spherical aluminum oxide powder using fine low-soda aluminum oxide as the raw material, with a maximum particle size of 7 ⁇ m or less and an average particle size in the range of 0.2 to 0.9 ⁇ m. It discloses that this powder is produced by subjecting the raw material powder to a strong crushing process before being introduced into the flame, and by continuously introducing the powder into the flame immediately after the agglomerated particles have been sufficiently crushed and dispersed, a spherical inorganic oxide powder free of coarse particles and with an average particle size of less than 1 ⁇ m can be stably obtained.
  • Patent Document 1 there is a risk that foreign matter from the crusher may be mixed (contaminated) into the alumina powder product as a result of the crushing process. There is no disclosure of the concentration of the sodium component in this powder.
  • the present invention was made in consideration of the above situation, and its purpose is to provide spherical alumina particles with a low surface residual Na concentration and low degree of aggregation, a method for producing the same, and a resin composite composition containing the same.
  • the inventors discovered that by drying the alumina slurry that has been washed with water using a specified method, it is possible to directly dry and powder the slurry without having to disintegrate it.
  • the gist of the present invention is as follows.
  • Spherical alumina particles having an average particle size of 0.4 to 1.9 ⁇ m, a specific surface area of 1.0 to 5.0 m 2 /g, a surface residual Na content of 20 ppm or less, a Na 2 O content of 1000 ppm or less, a degree of aggregation of 1.0% or less, and a circularity of 0.9 or more.
  • the method for producing spherical alumina particles comprising the steps of: [4] a raw material spherical alumina washing step of washing the raw material spherical alumina with water before the water slurry preparation step;
  • a resin composite composition comprising the spherical alumina particles according to [1] or [2].
  • the resin composite composition according to [5] further comprising at least one inorganic filler selected from amorphous spherical silica particles, crystalline spherical silica particles, titania particles, magnesia particles, aluminum nitride particles, boron nitride particles, barium titanate particles, calcium titanate particles, and carbon fibers.
  • the present invention provides spherical alumina particles with a low surface residual Na concentration and a small degree of agglomeration, and a resin composite composition containing the same. Because the spherical alumina particles have a low surface residual Na concentration, when used as a filler, poor curing and loss of voltage resistance can be avoided. In addition, because the degree of agglomeration is small, crushing is not necessary, and the introduction of foreign matter (contamination) due to crushing can be avoided. Furthermore, the spherical alumina particles can be easily manufactured by the manufacturing method that is one aspect of the present invention.
  • FIG. 1 is a schematic diagram showing the state of alumina particles in the case of conventional heat drying and in the case of freeze drying according to the present embodiment.
  • the spherical alumina particles according to one embodiment of the present invention have an average particle size of 0.4 to 1.9 ⁇ m. If the average particle size is less than 0.4 ⁇ m, the particles will tend to aggregate, and the fluidity of the resin composition will be significantly reduced when used as a filler, which is not preferable. If the average particle size exceeds 1.9 ⁇ m, the particles may get caught in the narrow space between the mounting substrate and the chip in semiconductor packages that are becoming smaller and thinner, which may cause the fluidity of the liquid encapsulant to decrease, resulting in a decrease in moldability.
  • the average particle size refers to the average particle size (D50), and means the median diameter D50 at 50% cumulative volume in the volume-based particle size distribution measured by the laser diffraction/scattering particle size distribution measurement method.
  • the laser diffraction/scattering particle size distribution measurement method is a method in which a dispersion liquid in which spherical alumina particles are dispersed is irradiated with laser light, and the particle size distribution is determined from the intensity distribution pattern of the diffracted/scattered light emitted from the dispersion liquid.
  • a laser diffraction/scattering particle size distribution measurement device "Mastersizer 3000" manufactured by Malvern
  • the average particle size of the raw material for spherical alumina particles can also be determined in a similar manner.
  • the spherical alumina particles have a specific surface area measured by the BET method of 1.0 m 2 /g or more and 5.0 m 2 /g or less.
  • the specific surface area of the spherical particles is less than 1.0 m2 /g, the particles are unlikely to form a close-packed structure, and the fluidity of the liquid encapsulant containing the particles may decrease.
  • the specific surface area of the spherical particles is more than 5.0 m2 /g, the particles may tend to aggregate more easily, and the fluidity of the liquid encapsulant may decrease.
  • the specific surface area is measured by the BET method. Typically, the specific surface area is measured by the following procedure. Approximately 5 g of a sample was weighed out and vacuum dried for 5 minutes at 250° C. Next, the sample was set in an automatic specific surface area measuring device (Macsorb, manufactured by Mountec Co., Ltd.), and the nitrogen gas adsorption amount was measured at a relative pressure P/P0 value of 0.291 at a measurement temperature of 77 K using pure nitrogen and a nitrogen-helium mixed gas (mixture ratio: nitrogen 30%, He 70%), and the BET specific surface area was calculated by the one-point method.
  • Macsorb manufactured by Mountec Co., Ltd.
  • the spherical alumina particles have a surface residual Na content of 20 ppm or less.
  • the surface residual Na referred to here means Na remaining attached to the alumina surface, and is measured by ion chromatography. If sodium is present in a large amount on the filler surface, i.e., on the alumina surface, it reacts with the resin or moisture in the air and releases hydroxide ions. These hydroxide ions react with the epoxy groups present in the epoxy resin, inhibiting the polymerization reaction between the resins and causing poor curing. Furthermore, if sodium ions or potassium ions are present in the resin composition prepared by kneading with the epoxy groups, the voltage resistance is impaired.
  • the amount of sodium remaining on the surface is measured by ion chromatography. Typically, the measurement is performed according to the following procedure. Add 4 g of sample and 40 ml of distilled water to a centrifuge tube, close the lid, and shake thoroughly to mix. After mixing, use a centrifuge to separate the sample and the sample solution. Separate the sample solution and use an ion chromatograph to analyze sodium ions. The ion chromatograph was made by Toa Medical Electronics.
  • the spherical alumina particles contain 1000 ppm or less of Na 2 O.
  • the contained Na 2 O referred to here is the total amount of Na present on the surface and inside of the alumina, and is quantified as the oxide Na 2 O using an atomic absorption spectrometer. If a large amount of Na 2 O is present in alumina, sodium is present not only on the surface of alumina but also inside, and when the alumina is heat-treated, the sodium component is liberated on the particle surface, which may increase the residual Na on the surface. If the Na 2 O content is 1000 ppm or less, the sodium content is low and liberation on the particle surface can be reduced.
  • the amount of Na 2 O contained in the alumina particles may be measured by elemental analysis known to those skilled in the art, for example, by using an atomic absorption spectrometer and converting the amount into oxide.
  • the spherical alumina particles have an agglomeration degree of 1.0% or less.
  • the degree of aggregation referred to here is an index showing whether particles are aggregated, and was measured by a sieving method.
  • the aggregation requires disintegration to separate the particles. Disintegration causes equipment wear and costs due to contact with the disintegration device.
  • the particles aggregate to each other, resulting in insufficient dispersion in the resin, which may deteriorate the fluidity and viscosity of the resin composition.
  • the degree of aggregation is 1.0% or less, it means that there are few lumps, which means that a disintegration operation is not necessary. From the above perspective, the lower the degree of aggregation, the more desirable it is, but since it is difficult to completely prevent aggregation, the lower limit may be 0.0001% or more.
  • the method for measuring the degree of cohesion is as follows. Two types of standard sieves with mesh sizes of 4.75 mm and 212 ⁇ m are stacked in order. The sieve with 212 ⁇ m mesh is placed at the bottom, and the sieves with gradually larger mesh sizes are stacked on top of it. 50 g of sample is placed on the top sieve with 4.75 mm mesh and set in a sieve shaker.
  • the sieve shaker used was an OCTAGON 200 manufactured by Endecotts. After setting the sieves, the vibration sieve was set to an amplitude of 5 and a shaking time of 3 minutes. After shaking was completed, the particle weights of the particles remaining on each sieve mesh and the particles that passed through the 212 ⁇ m mesh were measured. If the amount of particles on the 4.75 mm mesh is Ag, the amount of particles on the 212 um mesh is Bg, and the amount of particles that passed through the 212 um mesh is Cg, then the degree of agglomeration is calculated as A/(B+C) ⁇ 100(%).
  • the spherical alumina particles have a circularity of 0.90 or more.
  • the circularity may be 0.91 or more, 0.92 or more, or 0.93 or more.
  • the upper limit of the circularity is theoretically 1.0, but may be 0.98 or less, or 0.95 or less from the viewpoint of production management.
  • Circularity can be measured using an electron microscope or optical microscope and an image analyzer.
  • Sysmex FPIA These devices are used to measure the circularity of particles (perimeter of equivalent circle/perimeter of projected image of particle). The circularity of 100 or more particles is measured, and the average value is taken as the circularity of the powder.
  • the spherical alumina particles may have a gelatinization rate of 10.0% or less.
  • the alpha-alumina ratio refers to the ratio of alpha-alumina crystals in the crystalline phase.
  • Alumina is known to be crystalline, and alpha-alumina, ⁇ -alumina, and ⁇ -alumina are known as typical crystalline forms.
  • the spherical alumina particles which are one embodiment of the present invention, can be manufactured based on a thermal spraying method in which a raw material is put into a flame, melted, and then quenched, as described in detail below.
  • the obtained alumina can have a high amorphous ratio, and spherical alumina particles with an alpha-alumina ratio of 10.0% or less can be easily obtained.
  • the upper limit of the alpha-alumina ratio may be 5.0%, 3.0%, or 1.0%.
  • the lower limit of the alpha-alumina ratio is not particularly limited and may be 0.0%, but may be 0.1% or 0.4% from the viewpoint of the burden of manufacturing management and the thermal conductivity characteristics as a resin composite composition.
  • the alpha-conversion rate is measured using a powder X-ray diffractometer.
  • the integrated area of the obtained diffraction peaks is calculated, and the ratio of the diffraction peak area derived from alpha-alumina to the total is analyzed using the Rietveld method.
  • an X-ray diffraction pattern is obtained using a Bruker D2PHASER with 2 ⁇ in the range of 10° to 90°.
  • the alpha-conversion rate is calculated from the obtained pattern using a Bruker DIFFRAC. TOPAS by the Rietveld method.
  • the analysis is performed assuming that only three types of crystal phases, alpha-alumina, delta-alumina, and theta-alumina, are present, and the alpha-alumina content is calculated.
  • the purity of the aluminum oxide in the alumina particles is preferably 99.99% or more and 100.00% or less. If the purity of the aluminum oxide is less than 99.99%, the alumina particles tend to have an irregular shape.
  • ICP emission spectrometry ICP emission spectrometry
  • AES AES
  • SIMS SIMS
  • the amount of impurities in the alumina particles in this embodiment was measured by ICP emission spectrometry and atomic absorption spectrometry. The measurements were performed for each metal oxide according to the following JIS standard measurement method.
  • the purity of the alumina particles was calculated from the following formula: where the value is rounded off to two decimal places.
  • a method for producing spherical alumina particles which is a method for suitably producing the above-mentioned alumina particles and includes the following steps: (1) Manufacturing process of raw alumina. (2) A step of spheroidizing the raw alumina to produce raw spherical alumina. (3) a water slurry preparation step of mixing the raw material spherical alumina with water to prepare a water slurry containing the raw material spherical alumina; and (4) a drying step of drying the water slurry.
  • the raw material alumina can be produced by, for example, thermal decomposition of ammonium aluminum carbonate, vapor phase oxidation, deflagration, Bayer process, or hydrolysis of aluminum alkoxide.
  • the raw material alumina can be spheroidized by a flame fusion method to obtain raw material spherical alumina.
  • the flame fusion method is a type of known thermal spraying method in which particles are sprayed into a flame to make the particles spherical.
  • the average sphericity can be adjusted by the amount of fuel gas fed into the flame per unit time and the type of fuel gas.
  • the particle size of the spherical alumina powder can be adjusted by adjusting the particle size of the particles used.
  • the refrigerant is not particularly limited, but from the viewpoint of not reducing the purity of the spherical particles, a gas with few impurities and low activity such as air, nitrogen, or argon is preferable.
  • raw material spherical alumina may be produced by a deflagration method in which a chemical flame is formed by a burner in an atmosphere containing oxygen, and metallic aluminum powder is introduced into the chemical flame in an amount sufficient to form a dust cloud, causing a deflagration to produce spherical alumina particles.
  • the raw material spherical alumina is mixed with water to prepare a water slurry containing the raw material spherical alumina.
  • the water to be mixed is preferably distilled water or ion-exchanged water that does not contain sodium ions or chlorine ions as impurities.
  • the amount of the mixture can be appropriately adjusted taking into account the viscosity of the slurry, etc.
  • a raw material spherical alumina washing step may be performed in which the raw material spherical alumina is washed with water.
  • the washing water may be distilled water or ion-exchanged water that does not contain sodium ions or chlorine ions as impurities.
  • washing may be performed using a cleaning agent, a surfactant, or the like, depending on the target to be removed by washing.
  • the conditions such as the temperature, number of times, and time of washing can be appropriately adjusted to bring the alumina particles into a desired washing state.
  • the desired surface residual Na concentration and contained Na 2 O concentration can be obtained.
  • dehydration may be performed using a filter or the like until the desired particle concentration is reached.
  • the Na content and cleaning agent dissolved in the water can be washed away, thereby preventing re-adhesion after drying.
  • water may be further added to the raw material spherical alumina after washing to dissolve the remaining impurity components in the water.
  • dehydration can be performed again to wash away the impurity components attached to the alumina particle surface.
  • the efficiency of drying in the subsequent step can be increased by controlling the particle concentration to an arbitrary concentration.
  • FIG. 1 is a diagram showing the state of alumina particles in the case of conventional heat drying and in the case of freeze-drying of this embodiment.
  • the freeze-drying of this embodiment when the freeze-drying of this embodiment is performed, the alumina particles obtained are suppressed in aggregation, and there is no need to break up the agglomerates of alumina particles.
  • a breaker such as a mill is used to break up the agglomerates, and there is a risk of contamination from the breaker.
  • the heating temperature is low (10 to 90° C., more preferably 80° C.), the seepage of sodium from inside the particles is minimized, and therefore the amount of free sodium reattached to the powder surface after drying is reduced.
  • the slurry is sprayed into a high-temperature airflow of 100 to 300°C, and only the water content is evaporated, thereby extracting spherical alumina powder from the slurry.
  • the slurry is sprayed into a high-temperature airflow using a nozzle such as a two-fluid nozzle.
  • the sprayed slurry becomes fine droplets due to the dispersion effect in the airflow.
  • the airflow heat drying method has a very large surface area because the slurry is made into droplets using a nozzle.
  • the amount of heat received by the slurry is proportional to the surface area where the heat source and the slurry are in contact, so the water content of the droplets evaporates and dries in an instant. Since the drying time is shorter (about 0.01 to 10 seconds) than conventional heat drying methods, the seepage of sodium from inside the particles is minimized, and the amount of sodium that reattaches to the powder after drying is reduced. Furthermore, since the spherical alumina powder is sprayed into the airflow, the aggregation of the spherical alumina powder particles is suppressed, and there is no need to break up the agglomerates of alumina particles.
  • the composite composition of the finally obtained spherical alumina particles and resin can be produced.
  • the composition of the resin composite composition will be described in more detail below.
  • a slurry composition containing spherical alumina particles and a resin By using a slurry composition containing spherical alumina particles and a resin, it is possible to obtain resin composite compositions such as semiconductor encapsulants (particularly solid encapsulants) and interlayer insulating films. Furthermore, by curing these resin composite compositions, it is possible to obtain resin composites such as encapsulants (cured bodies) and substrates for semiconductor packages.
  • the resin composite composition for example, in addition to the spherical alumina particles and resin, a curing agent, a curing accelerator, a flame retardant, a silane coupling agent, etc. are mixed as necessary, and the mixture is compounded by a known method such as kneading. The mixture is then molded into pellets, films, etc., depending on the application.
  • inorganic fillers When producing the resin composite composition, other inorganic fillers may be blended in addition to the spherical alumina particles and resin.
  • the inorganic fillers include amorphous spherical silica particles, crystalline spherical silica particles, titania particles, magnesia particles, aluminum nitride particles, boron nitride particles, barium titanate particles, calcium titanate particles, and carbon fibers.
  • the blending ratio of the inorganic fillers can be adjusted appropriately depending on the application of the resin composite composition.
  • the resin composite composition when the resin composite composition is cured to produce a resin composite, for example, the resin composite composition is heated to melt it, processed into a shape according to the intended use, and then heated to a temperature higher than that at the time of melting to completely cure it.
  • a known method such as a transfer molding method can be used.
  • epoxy resin is not particularly limited, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, phenoxy type epoxy resin, etc. can be used.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin
  • biphenyl type epoxy resin phenol novolac type epoxy resin
  • cresol novolac type epoxy resin cresol novolac type epoxy resin
  • naphthalene type epoxy resin phenoxy type epoxy resin, etc.
  • epoxy resins having two or more epoxy groups in one molecule are preferred from the viewpoints of curability, heat resistance, etc.
  • biphenyl type epoxy resins phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, epoxidized novolac resins of phenols and aldehydes, glycidyl ethers of bisphenol A, bisphenol F, bisphenol S, etc.
  • glycidyl ester acid epoxy resins obtained by reacting polybasic acids such as phthalic acid and dimer acid with epochlorohydrin, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, alkyl-modified polyfunctional epoxy resins, ⁇ -naphthol novolac type epoxy resins, 1,6-dihydroxynaphthalene type epoxy resins, 2,7-dihydroxynaphthalene type epoxy resins, bishydroxybiphenyl type epoxy resins, and epoxy resins into which halogens such as bromine have been introduced to impart flame retardancy.
  • these epoxy resins having two or more epoxy groups in one molecule
  • resins other than epoxy resins can be used in applications other than composite materials for semiconductor encapsulation, such as prepregs for printed circuit boards and various engineering plastics, as resin composite compositions.
  • resins that can be used other than epoxy resins include silicone resins, phenolic resins, melamine resins, urea resins, unsaturated polyesters, fluororesins, polyamides such as polyimide, polyamideimide, and polyetherimide; polyesters such as polybutylene terephthalate and polyethylene terephthalate; polyphenylene sulfide, aromatic polyesters, polysulfones, liquid crystal polymers, polyethersulfones, polycarbonates, maleimide-modified resins, ABS resins, AAS (acrylonitrile-acrylic rubber-styrene) resins, and AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resins.
  • the curing agent used in the resin composite composition may be any known curing agent for curing the resin, for example, a phenol-based curing agent.
  • a phenol-based curing agent phenol novolac resin, alkylphenol novolac resin, polyvinylphenols, etc.
  • phenol novolac resin phenol novolac resin, alkylphenol novolac resin, polyvinylphenols, etc.
  • phenol novolac resin alkylphenol novolac resin
  • polyvinylphenols, etc. may be used alone or in combination of two or more kinds.
  • the amount of the phenolic hardener to be blended is preferably such that the equivalent ratio to the epoxy resin (phenolic hydroxyl group equivalent/epoxy group equivalent) is 0.1 or more and less than 1.0. This eliminates the residue of unreacted phenolic hardener and improves moisture absorption and heat resistance.
  • the amount of the spherical alumina particles of the present invention added to the resin composite composition is preferably large from the viewpoint of heat resistance and thermal expansion coefficient, but is usually appropriate to be 70% by mass or more and 95% by mass or less, preferably 80% by mass or more and 95% by mass or less, and more preferably 85% by mass or more and 95% by mass or less.
  • additives such as silane coupling agents, hardeners, colorants, hardening retarders, and other known additives can be used.
  • any known coupling agent may be used, but it is preferable to use one that has an epoxy-based functional group.
  • a slurry composition containing spherical alumina particles and resin can be used to produce heat dissipation sheets, heat dissipation grease, etc.
  • the spherical alumina particles, resin, and additives are appropriately mixed and compounded using a known method such as kneading.
  • the resulting composite is molded into a sheet using a known method.
  • known resins can be used as the resin for the resin composite composition, and specific examples include silicone resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyamide such as polyimide, polyamideimide, polyetherimide, polyester such as polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide modified resin, ABS resin, AAS (acrylonitrile-acrylic rubber-styrene) resin, AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resin.
  • silicone resin there are no particular limitations on the silicone resin, but for example, peroxide curing type, addition curing type, condensation curing type, ultraviolet curing type, etc. can be used.
  • additives such as silane coupling agents, hardeners, colorants, hardening retarders, and other known additives can be used.
  • the spherical alumina particles, resin, and additives are appropriately mixed and compounded using a known method such as kneading.
  • the resin used in the heat dissipating grease is also called the base oil.
  • known resins can be used in the resin composite composition, specifically silicone resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyamides such as polyimide, polyamideimide, and polyetherimide; polyesters such as polybutylene terephthalate and polyethylene terephthalate; polyphenylene sulfide, aromatic polyester, polysulfone, liquid crystal polymer, polyethersulfone, polycarbonate, maleimide-modified resin, ABS resin, AAS (acrylonitrile-acrylic rubber-styrene) resin, AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resin, mineral oil, synthetic hydrocarbon oil, ester oil, polyglycol oil, silicone oil, and fluorine oil.
  • silicone resin phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin
  • polyamides such as polyimide, polyamideimide, and polyetherimide
  • polyesters such
  • additives such as silane coupling agents, colorants, thickeners, and other known additives can be used.
  • the thickeners that can be used include known ones such as calcium soap, lithium soap, aluminum soap, calcium complex, aluminum complex, lithium complex, barium complex, bentonite, urea, PTFE, sodium terephthalamate, silica gel, and organic bentonite.
  • the raw spherical alumina particles (Materials 1 to 4) listed in Table 1 were prepared and mixed with water to make a water slurry.
  • the mixing ratio of ion-exchanged water and particles to make the water slurry was 200 kg of particle powder per 1000 L of water.
  • 300 kg of particle powder per 1000 L of ion-exchanged water was used.
  • 200 kg of particle powder per 1000 L of ion-exchanged water was used.
  • the water slurry was mixed and stirred for 20 minutes to 1 hour, and then filtered using an appropriate filter until the moisture content was about 60 to 80 wt%.
  • Examples 1 to 3 The prepared slurry was once pre-frozen at ⁇ 40° C., and then freeze-dried at 80° C. for 24 hours while the inside of the apparatus was degassed under vacuum.
  • Example 4 The prepared slurry was air-dried at 200° C. using a jet turbo dryer manufactured by Hiraiwa Iron Works.
  • the kneading conditions were 15 seconds of pre-kneading and 90 seconds of vacuum kneading. After kneading, the plastic container containing the kneaded product was placed in a water bath adjusted to 25 ° C. and cooled for 1 hour. 10 g of this resin composite composition was placed on a smooth-surfaced iron plate and tilted 60 ° to the horizontal direction to check the flow rate of the resin composite composition. As a result, after 5 hours of tilting, the resin composite composition flowed 15 cm or more, showing good fluidity.
  • the kneading conditions were 15 seconds of pre-kneading and 90 seconds of vacuum kneading. After kneading, the plastic container containing the kneaded product was placed in a water bath adjusted to 25 ° C. and cooled for 1 hour. 10 g of this resin composite composition was placed on a smooth-surfaced iron plate and tilted 60 ° to the horizontal direction to check the flow rate of the resin composite composition. As a result, after 5 hours of tilting, the resin composite composition flowed 15 cm or more, showing good fluidity.
  • the laser diffraction/scattering particle size distribution measurement method is a method in which a dispersion liquid in which spherical alumina particles are dispersed is irradiated with laser light, and the particle size distribution is obtained from the intensity distribution pattern of the diffracted/scattered light emitted from the dispersion liquid.
  • a laser diffraction/scattering particle size distribution measurement device "Mastersizer 3000" (manufactured by Malvern) was used.
  • the specific surface area was determined by applying the BET theory to the adsorption isotherm measured by the gas adsorption method (BET method). The specific surface area was measured using a specific surface area measuring device manufactured by Mountech Co., Ltd. under the trade name "Maxsorb Model HM-1208".
  • the amount of ionic impurities adhering to the surface can be measured using ion chromatography. 4 g of sample and 40 ml of distilled water are added to a centrifuge tube, the tube is covered and shaken thoroughly to mix. After mixing, the sample and sample solution are separated using a centrifuge. The sample solution is separated and analyzed for sodium ions using ion chromatography. The ion chromatography was performed using an ion chromatograph manufactured by Toa Medical Electronics.
  • the degree of agglomeration is calculated as A/(B+C) ⁇ 100(%).
  • the spherical alumina particles of the present invention have a low surface residual Na concentration, so when used as a filler, poor curing and loss of voltage resistance can be avoided. In addition, because the degree of aggregation is small, crushing is not necessary, and contamination due to crushing can be avoided. Therefore, as a filler, it can be suitably used in miniaturized and thinned semiconductor packages, etc. Furthermore, the spherical alumina particles can be easily manufactured by the manufacturing method which is one aspect of the present invention. A resin composite composition containing the spherical alumina particles exhibits good quality and can be used for other purposes as well as semiconductor encapsulation materials. Specifically, it can be used as a prepreg for printed circuit boards, various engineering plastics, etc.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Geology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'objectif est de fournir des particules d'alumine sphériques ayant un faible niveau de Na résiduel de surface et un faible degré d'agglomération, leur méthode de production et une composition composite de résine les comprenant.　Les particules d'alumine sphériques ont un diamètre moyen de 0,4 à 1,9 µm, une surface spécifique de 1,0 à 5,0 m2/g, un Na résiduel de surface inférieur ou égal à 200 ppm, une teneur en Na2O inférieure ou égale à 1 000 ppm, un degré d'agglomération inférieur ou égal à 1,0 % et un degré de circularité supérieur ou égal à 0,9. L'invention concerne une méthode de production de celles-ci et une composition composite de résine les comprenant.
PCT/JP2023/035864 2022-09-30 2023-10-02 Particules d'alumine sphériques, leur méthode de production et composition composite de résine les comprenant Ceased WO2024071431A1 (fr)

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CN202380068477.0A CN119923371A (zh) 2022-09-30 2023-10-02 球状氧化铝颗粒、其制造方法、以及含有其的树脂复合组合物
KR1020257009359A KR20250052437A (ko) 2022-09-30 2023-10-02 구상 알루미나 입자, 그 제조 방법 및 그것을 함유하는 수지 복합 조성물

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WO2025229851A1 (fr) * 2024-04-30 2025-11-06 デンカ株式会社 Poudre d'alumine, poudre inorganique et composition de résine

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JP2006199579A (ja) * 2004-12-24 2006-08-03 Micron:Kk 球状アルミナ粉末およびその製造方法
JP2007008730A (ja) * 2005-06-28 2007-01-18 Denki Kagaku Kogyo Kk 球状アルミナ粉末、その製造方法および用途
JP2009062244A (ja) * 2007-09-07 2009-03-26 Nissan Motor Co Ltd 粒子分散溶液およびその樹脂組成物ならびにそれらの製造方法
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JP2008120673A (ja) 2006-10-19 2008-05-29 Showa Denko Kk 球状無機酸化物粉体とその製造方法およびその用途
JP2012021710A (ja) 2010-07-15 2012-02-02 Nippon Steel Materials Co Ltd 粉体の水洗処理方法および水洗処理装置

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WO2006041170A1 (fr) * 2004-10-15 2006-04-20 Ngk Insulators, Ltd. Méthode de fabrication d’un matériau poreux
JP2006199579A (ja) * 2004-12-24 2006-08-03 Micron:Kk 球状アルミナ粉末およびその製造方法
JP2007008730A (ja) * 2005-06-28 2007-01-18 Denki Kagaku Kogyo Kk 球状アルミナ粉末、その製造方法および用途
JP2009062244A (ja) * 2007-09-07 2009-03-26 Nissan Motor Co Ltd 粒子分散溶液およびその樹脂組成物ならびにそれらの製造方法
JP2009090272A (ja) * 2007-09-20 2009-04-30 Nissan Motor Co Ltd 粒子分散ゾルと粒子分散樹脂組成物の製造方法
JP2012020900A (ja) * 2010-07-14 2012-02-02 Denki Kagaku Kogyo Kk 球状アルミナ粉末、その製造方法及び用途

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Publication number Priority date Publication date Assignee Title
WO2025229851A1 (fr) * 2024-04-30 2025-11-06 デンカ株式会社 Poudre d'alumine, poudre inorganique et composition de résine

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