WO2022202584A1 - Poudre d'oxyde inorganique, composition de résine et article moulé par compression - Google Patents

Poudre d'oxyde inorganique, composition de résine et article moulé par compression Download PDF

Info

Publication number
WO2022202584A1
WO2022202584A1 PCT/JP2022/012147 JP2022012147W WO2022202584A1 WO 2022202584 A1 WO2022202584 A1 WO 2022202584A1 JP 2022012147 W JP2022012147 W JP 2022012147W WO 2022202584 A1 WO2022202584 A1 WO 2022202584A1
Authority
WO
WIPO (PCT)
Prior art keywords
cumulative frequency
particle size
inorganic oxide
region
oxide powder
Prior art date
Application number
PCT/JP2022/012147
Other languages
English (en)
Japanese (ja)
Inventor
輝洋 相京
朋浩 川畑
純 山口
敦司 山下
Original Assignee
デンカ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to JP2023509090A priority Critical patent/JPWO2022202584A1/ja
Publication of WO2022202584A1 publication Critical patent/WO2022202584A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • 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
    • 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
    • C01F7/022—Classification
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • C01F7/027—Treatment involving fusion or vaporisation

Definitions

  • the present invention relates to inorganic oxide powders, resin compositions and compression molded articles.
  • Patent Document 1 a spherical alumina powder having a predetermined average particle size and having at least two or more maximum frequency peaks within a predetermined range in the particle size distribution and a spherical silica powder having a predetermined average particle size and specific surface area are combined into a predetermined A highly thermally conductive inorganic powder containing a proportion of According to this highly thermally conductive inorganic powder, it is possible to prepare a highly thermally conductive resin composition that does not easily become highly viscous even when highly filled in a resin, and has high fluidity and low burr characteristics.
  • Transfer molding and compression molding are known as molding methods for resin encapsulation of electronic components.
  • the transfer molding method is a molding method in which tablet-shaped resin is put into a pot of a mold that has been kept warm in advance, and the melted resin is filled into the cavity using a plunger.
  • the compression molding method is a method in which a powder or granular resin composition is supplied into a cavity, and a workpiece is pressed against the melted resin composition to perform compression molding. From the viewpoint of cost reduction, the compression molding method is desirable.
  • the resin composition to be used is required to have not only excellent fluidity under high shear but also excellent fluidity under low shear. That is, there is a demand for an inorganic oxide powder that can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity.
  • the present invention provides an inorganic oxide powder, a resin composition containing an inorganic oxide powder, and a resin composition that can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity.
  • An object of the present invention is to provide a compression-molded product that is
  • the present invention has the following aspects.
  • An inorganic oxide powder having a particle size of 0.001 ⁇ m or more and 20 ⁇ m or less with respect to the cumulative frequency of the first region located in the range of 0.001 ⁇ m or more and 10 ⁇ m or less in the volume-based frequency particle size distribution.
  • the value of the ratio of the cumulative frequency of the second region located in the range of (cumulative frequency of the second region / cumulative frequency of the first region) is 1.2 to 1.4
  • the grain size is 20 ⁇ m or more and 46 ⁇ m or less
  • An inorganic oxide powder having a viscosity of 45 to 70 Pa ⁇ s measured at a temperature of 30° C. and a rotation speed of 1 rpm using a type viscometer.
  • [2] The inorganic oxide powder according to [1], wherein the cumulative frequency of the first region is 35 to 60% by volume.
  • [3] The inorganic oxide powder according to [1] or [2], which has a BET specific surface area of 0.5 to 2.0 m 2 /g.
  • [4] A resin composition comprising the inorganic oxide powder according to any one of [1] to [3] and a resin.
  • [5] The resin composition according to [4], which is used for producing a compression-molded product.
  • [6] A compression-molded article containing the resin composition according to [4] or [5].
  • an inorganic oxide powder, a resin composition containing an inorganic oxide powder, and a resin composition that can provide a resin composition having a low ratio of viscosity at low shear to viscosity at high shear are molded.
  • a compression-molded product can be provided.
  • the inorganic oxide powder according to the present embodiment is In the volume-based frequency particle size distribution, - The value of the ratio of the cumulative frequency of the second region located in the range of 0.001 ⁇ m or more and 20 ⁇ m or less to the cumulative frequency of the first region located in the range of 0.001 ⁇ m or more and 10 ⁇ m or less of the grain size (second The cumulative frequency of the regions/the cumulative frequency of the first regions) is 1.2 to 1.4; Also, a resin composition comprising 20% by mass of a bisphenol F type epoxy resin (epoxy equivalent: 170, viscosity: 4 Pa s) and 80% by mass of inorganic oxide powder was measured using an E-type viscometer at a temperature of 30°C and 1 rpm.
  • the viscosity measured by the number of revolutions is 45 to 70 Pa ⁇ s.
  • An inorganic oxide powder designed in this way can provide a resin composition having a low ratio of low-shear viscosity to high-shear viscosity.
  • a resin composition with a small ratio of low-shear viscosity to high-shear viscosity is excellent in moldability because the viscosity is kept low from the beginning to the end when the workpiece is pressed against the resin in the compression molding method. ing.
  • the inorganic oxide powder designed in this way can provide a resin composition with excellent fluidity when melted. As a result, the moldability can be further improved in the compression molding method.
  • volume-based frequency particle size distribution is measured by a laser diffraction light scattering method (refractive index: 1.68), with a distribution curve in which the horizontal axis is the particle size ( ⁇ m) and the vertical axis is the volume-based frequency (%). is represented by "Particle size” is a numerical value represented on the horizontal axis of the volume-based frequency particle size distribution.
  • Peak means a distribution curve having one maximum in the volume-based frequency particle size distribution.
  • Shader is an incomplete peak that is not completely separated from the peak (i.e., a stepped portion in which a bulge is formed in the middle of the slope of the distribution curve that constitutes the peak) and has one maximum value. does not mean a distribution curve.
  • Maximum means the boundary where the slope of the curve changes from positive to negative in the volume-based frequency particle size distribution.
  • a “region” here means a distribution curve located in a range having a given particle size in the volume-based frequency particle size distribution, regardless of the presence or absence and number of local maxima.
  • the “first region” means one region of the distribution curve in which the particle size is located in the range of 0.001 to 10 ⁇ m in the volume-based frequency particle size distribution.
  • “Second region” means a region of the distribution curve in which the particle size is located in the range of 0.001 to 20 ⁇ m in the volume-based frequency particle size distribution. Note that the second area includes the first area.
  • Cumulative frequency means the cumulative value of frequency (%) in a predetermined particle size range of the volume-based frequency particle size distribution.
  • the "viscosity at low shear” is measured using an E-type viscometer for a resin composition consisting of 20% by mass of a bisphenol F type epoxy resin (epoxy equivalent: 170, viscosity: 4 Pa s) and 80% by mass of inorganic oxide powder. viscosities measured at a temperature of 30° C. and a rotation speed of 1 rpm.
  • "Viscosity at high shear” is measured using an E-type viscometer for a resin composition consisting of 20% by mass of a bisphenol F type epoxy resin (epoxy equivalent: 170, viscosity: 4 Pa s) and 80% by mass of inorganic oxide powder. viscosities measured at a temperature of 30° C. and a rotation speed of 10 rpm. The manufacturer's nominal value is used for the viscosity of the bisphenol F type epoxy resin.
  • the inorganic oxide powder has a particle size in the range of 0.001 to 20 ⁇ m with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 ⁇ m.
  • the value of the ratio of the cumulative frequencies of the regions is 1.2 to 1.4.
  • the inorganic oxide powder according to the present embodiment not only has excellent fluidity, but can also provide a resin composition with low viscosity under low shear.
  • the value of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region is 1.2 to 1.3, or 1.3 to 1.4 can also be
  • the inorganic oxide powder preferably has a cumulative frequency in the first region of 35 to 60%, more preferably 40 to 60%, even more preferably 45 to 55%.
  • the cumulative frequency of the first region can be 42-58%.
  • the inorganic oxide powder preferably has a cumulative frequency of the second region of 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable.
  • the cumulative frequency of the second region can be 54-75%.
  • the inorganic oxide powder has a particle size in the range of 0.01 to 20 ⁇ m with respect to the cumulative frequency of region 1a in which the particle size is in the range of 0.01 to 10 ⁇ m in the volume-based frequency particle size distribution.
  • the value of the ratio of the cumulative frequency of a certain 2a region (cumulative frequency of the 2a region/cumulative frequency of the 1a region) is 1.2 to 1.4.
  • the ratio of the cumulative frequency of the 2a region to the cumulative frequency of the 1a region (cumulative frequency of the 2a region/cumulative frequency of the 1a region) is 1.2 to 1.3 or 1.3 to 1.4.
  • the inorganic oxide powder preferably has a cumulative frequency in the 1a region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable.
  • the cumulative frequency of region 1a can be 42-58%.
  • the cumulative frequency of the 2a region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable.
  • the cumulative frequency of region 2a can be 54-75%.
  • the inorganic oxide powder has a particle size in the range of 0.1 to 20 ⁇ m with respect to the cumulative frequency of region 1b in which the particle size is in the range of 0.1 to 10 ⁇ m in the volume-based frequency particle size distribution.
  • the value of the ratio of the cumulative frequency of a certain 2b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.4.
  • the ratio of the cumulative frequency of the 2b region to the cumulative frequency of the 1b region (cumulative frequency of the 2b region/cumulative frequency of the 1b region) is 1.2 to 1.3 or 1.3 to 1.4.
  • the inorganic oxide powder preferably has a cumulative frequency in the 1b region of 30 to 70%, more preferably 35 to 70%, and further preferably 40 to 65%. preferable.
  • the cumulative frequency of region 1b can be 42-58%.
  • the cumulative frequency of the 2b region is preferably 40 to 80%, more preferably 45 to 75%, and further preferably 50 to 70%. preferable.
  • the cumulative frequency of region 2b can be 54-75%.
  • the cumulative frequency of the first and second regions is adjusted to the preferred range described above, and if necessary, has a first peak, a second peak, and a third peak described later, and the maximum frequency is a preferred range described later and the like.
  • the cumulative frequency can be adjusted by adjusting the blending amount of the raw material powder whose particle size is adjusted, or by sieving, classifying, or the like.
  • the inorganic oxide powder has a cumulative frequency of 15 to 45% by volume in the range of particle diameters from 20 ⁇ m to 46 ⁇ m.
  • the cumulative frequency of particles having a particle size in the range of 20 ⁇ m to 46 ⁇ m is preferably 17 to 45% by volume, more preferably 18 to 43% by volume.
  • the cumulative frequency of particle sizes ranging from 20 ⁇ m to 46 ⁇ m can be 19-41% by volume.
  • the cumulative frequency can be adjusted by adjusting the blending amount of the raw material powder whose particle size is adjusted, or by sieving, classifying, or the like.
  • the inorganic oxide powder is a resin composition composed of 20% by mass of a bisphenol F type epoxy resin (epoxy equivalent: 170, viscosity: 4 Pa s) and 80% by mass of inorganic oxide powder.
  • the viscosity (viscosity at low shear) measured at 30° C. and 1 rpm is 45 to 70 Pa ⁇ s. Since the viscosity at low shear is 45 to 70 Pa s, in the compression molding (compression molding) method, the viscosity is kept low at the stage of starting to press the work against the resin composition, so the influence on wire deformation is reduced. It is less and has excellent moldability.
  • the viscosity at low shear is 45 to 70 Pa ⁇ s.
  • the viscosity at low shear can be from 49 to 69 Pa ⁇ s.
  • the viscosity at low shear is adjusted by setting the ratio of the cumulative frequency of the second region / the cumulative frequency of the first region, the cumulative frequency in the range of 20 ⁇ m to 46 ⁇ m, and the cumulative frequency of the first region to the predetermined value
  • a predetermined range can be obtained by adjusting within the range. For example, in order to increase the viscosity at low shear, the value of the ratio of the cumulative frequency of the second region / the cumulative frequency of the first region is made smaller within the above-described predetermined range (that is, the range where the particle size is smaller and to make the cumulative frequency in the range of 20 ⁇ m to 46 ⁇ m smaller within the predetermined range described above.
  • inorganic oxide powders examples include metal oxide powders.
  • metal oxide powders include inorganic powders such as silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), magnesia (MgO) and calcia (CaO).
  • the inorganic powder preferably contains one or more metal oxide powders selected from these, more preferably alumina, and still more preferably alumina. From the viewpoint of high filling of the resin, it is preferable to contain spherical alumina. "Spherical" means that when observed with a scanning electron microscope at a magnification of 100, the particles are observed to have a circular or rounded grain shape.
  • the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of alumina. In one embodiment, the inorganic oxide powder contains 90% by mass or more, or 92% by mass or more of spherical amorphous alumina.
  • the inorganic oxide powder preferably has a BET specific surface area of 0.5 to 2.0 m 2 /g, more preferably 0.8 to 1.8 m 2 /g, and more preferably 1.0 to 1.0 m 2 /g. It is more preferably 1.5 m 2 /g, particularly preferably 1.1 to 1.5 m 2 /g.
  • the specific surface area by the BET method can be measured using a specific surface area measuring instrument such as "Macsorb HM model-1208" (manufactured by MACSORB).
  • the specific surface area can be adjusted by changing the particle size and ratio of the inorganic oxide powder to be blended.
  • the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 ⁇ m or more and 70 ⁇ m or less. , more preferably 98% or more.
  • the inorganic oxide powder may have a cumulative frequency of 100% with a particle size in the range of 0.01 ⁇ m to 70 ⁇ m.
  • the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 0.01 ⁇ m or more and 60 ⁇ m or less. , more preferably 98% or more.
  • the inorganic oxide powder may have a cumulative frequency of 100% with a particle size in the range of 0.01 ⁇ m to 60 ⁇ m.
  • the inorganic oxide powder preferably has a cumulative frequency of 90% or more, more preferably 95% or more, in a particle size range of 1 ⁇ m or more and 50 ⁇ m or less. % or more is more preferable.
  • the inorganic oxide powder may have a cumulative frequency of 100% in the particle size range of 1-50 ⁇ m.
  • the inorganic oxide powder preferably has a volume-based cumulative 50 % diameter D50 of 5 to 20 ⁇ m, more preferably 5 to 15 ⁇ m, from the viewpoint of fluidity and viscosity of the resin composition.
  • the volume-based cumulative 50% diameter D50 is a particle size corresponding to a cumulative value of 50% in a volume-based cumulative particle size distribution measured by a laser diffraction light scattering method (refractive index: 1.68).
  • the inorganic oxide powder facilitates adjustment of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region (cumulative frequency of the second region/cumulative frequency of the first region), and/or In order to facilitate adjustment of the cumulative frequency in the range of 20 ⁇ m or more and 46 ⁇ m or less, one or more peaks having a maximum value may be present in a predetermined particle size range.
  • the inorganic oxide powder has at least a particle size (particle size) in the range of 1 ⁇ m or more and 7 ⁇ m or less, preferably in the range of 2 ⁇ m or more and 7 ⁇ m or less, more preferably in the range of 2 ⁇ m or more and 6 ⁇ m or less. / Or it may have a shoulder maxima (more preferably a peak maxima).
  • the peak and/or shoulder having the maximum value in the range of 1 ⁇ m or more and 7 ⁇ m or less in particle size is also referred to as “first peak”.
  • Inorganic oxide powders having a peak and/or shoulder maximum value in the particle size range of 1 ⁇ m or more and 7 ⁇ m or less have a value of the ratio of the cumulative frequency of the second region to the cumulative frequency of the first region within a predetermined range. can be easily designed, and a resin composition having a low ratio of viscosity under low shear to viscosity under high shear can be obtained more easily.
  • a powder having a peak and/or shoulder in the range of 1 ⁇ m or more and 7 ⁇ m or less in particle size is also called fine powder. It is possible to provide a resin composition with
  • the maximum frequency (frequency at the maximum value) of the first peak is preferably 1-7%, more preferably 1-6%, and even more preferably 2-6%.
  • the maximum frequency of each peak can be adjusted by adjusting the blending amount of the raw material powder whose particle size has been adjusted, or by sieving, classification, or the like.
  • the inorganic oxide powder preferably has a particle size of more than 7 ⁇ m and 15 ⁇ m or less, more preferably a particle size of 8 to 14 ⁇ m, and still more preferably a particle size of 9 to 12 ⁇ m. may have peaks and/or shoulder maxima at .
  • the peak and/or the shoulder having the maximum value in the range of the particle size exceeding 7 ⁇ m and not more than 15 ⁇ m are also referred to herein as the “second peak”.
  • the second peak is a shoulder that is not completely separated from the first peak. In other embodiments, the second peak is a completely separate peak from the first peak.
  • the second peak is the cumulative frequency ( Hereinafter, also referred to as “second peak cumulative frequency”) is preferably 40 to 80%, more preferably 45 to 75%, and even more preferably 50 to 70%.
  • second peak cumulative frequency is preferably 40 to 80%, more preferably 45 to 75%, and even more preferably 50 to 70%.
  • the value of the ratio of the cumulative frequency of the second peak to the sum of the cumulative frequency of the first peak and the cumulative frequency of the second peak [cumulative frequency of the second peak/(cumulative frequency of the first peak + 2 peak cumulative frequency)] is 1.2 to 1.4.
  • "Peak cumulative frequency” refers to the cumulative frequency from the point where the curve forming each peak rises to the point where the curve converges (the frequency becomes zero or becomes a minimum value).
  • the value of the ratio of the cumulative frequencies of the two regions can be 1.2 to 1.4.
  • the maximum frequency (frequency at the maximum value) of the second peak is preferably 1-4%, more preferably 2-4%, and even more preferably 2-3%. By setting the maximum frequency of the second peak to 1 to 4%, it is possible to impart easiness of movement of the particles at the time of low shear.
  • the inorganic oxide powder preferably has a volume-based frequency particle size distribution in a range of more than 15 ⁇ m and 30 ⁇ m or less, more preferably in a particle size range of 20 to 30 ⁇ m, still more preferably in a particle size range of 20 to 25 ⁇ m. / Or it may have a shoulder maxima (more preferably a peak maxima).
  • the peak and/or shoulder having the maximum value in the range of the particle size exceeding 15 ⁇ m and 30 ⁇ m or less is also referred to herein as the “third peak”.
  • the inorganic oxide powder has a volume-based frequency particle size distribution with a peak maximum in the range of 18-29 ⁇ m.
  • the third peak is from the starting point where the curve rises (minimum point between the second peak) to the minimum point between the fourth peak (if there is no fourth peak, the frequency becomes zero) Or the point where the distribution curve converges) (hereinafter also referred to as "cumulative frequency of the third peak") is preferably 65 to 95%, more preferably 70 to 95%, 75 More preferably ⁇ 95%.
  • the maximum frequency of the third peak (frequency at the maximum value) is preferably 2-8%, more preferably 3-7%, and even more preferably 4-6%. By setting the maximum frequency of the third peak to 2 to 8%, high fluidity can be imparted to the resin composition.
  • the inorganic oxide powder preferably has a volume-based frequency particle size distribution in a range of more than 30 ⁇ m and 50 ⁇ m or less, more preferably in a particle size range of 35 to 50 ⁇ m, still more preferably in a particle size range of 40 to 46 ⁇ m. / Or it may have a shoulder maxima (more preferably a peak maxima).
  • the peak and/or the shoulder having the maximum value in the range of the particle size exceeding 30 ⁇ m and not more than 50 ⁇ m are also referred to as “fourth peak”. By having the fourth peak, high fluidity can be imparted to the resin composition.
  • the maximum frequency (frequency at the maximum value) of the fourth peak is preferably 2-8%, more preferably 3-7%, and even more preferably 4-6%. By setting the maximum frequency of the fourth peak to 2 to 8%, high fluidity can be imparted to the resin composition.
  • the inorganic oxide powder has a particle size in the range of 0.001 to 35 ⁇ m with respect to the cumulative frequency in the first region in which the particle size is in the range of 0.001 to 10 ⁇ m.
  • the value of the ratio of the cumulative frequencies of the regions is preferably 1.4 to 2.2, more preferably 1.5 to 2.0. preferable.
  • the “third region” means a region of the distribution curve in which the particle size is located in the range of 0.001 to 35 ⁇ m in the volume-based frequency particle size distribution.
  • the "first area” is as described above. Note that the third area includes the first area and the second area.
  • the inorganic oxide powder has a cumulative frequency in the third region of 70 to 95%, preferably 75 to 95%, more preferably 75 to 90%. preferable.
  • the cumulative frequency of the first area is as described above.
  • the cumulative frequency of the third region can be 77-94%.
  • the ratio of the cumulative frequency of the third region (particle size: 0.001 to 35 ⁇ m) to the cumulative frequency of the first region (particle size: 0.001 to 10 ⁇ m) to 1.4 to 2.2 has, for example, the cumulative frequency of the first to third regions and / or the maximum frequency of the first peak adjusted to the preferred range described above, and optionally the second peak, the third peak and the fourth peak, A method of adjusting the maximum frequency to the above-mentioned preferable range, and the like can be mentioned.
  • the cumulative frequency and the maximum frequency can be adjusted by adjusting the blending amount of the raw material powder whose particle size is adjusted, sieving, classification, or the like.
  • the inorganic oxide powder may be produced by mixing commercially available inorganic oxide powders having a predetermined particle size distribution, or may be produced by existing thermal spraying techniques. From the viewpoint of productivity and production cost, thermal spraying technology is preferred.
  • the existing thermal spraying technology is based on, for example, "About thermal spraying collection technology for steel kiln furnace" Tetsusei Kenkyu 1982 No. 310, and is formed with fuel gas such as hydrogen, natural gas, acetylene gas, propane gas, butane.
  • the raw material powder is put into a high-temperature flame and melted and spheroidized.
  • An example of the manufacturing apparatus is basically composed of a spheroidizing furnace and a collection device connected to the furnace.
  • the spherical inorganic oxide powder produced in the spheroidizing furnace is pneumatically transported by a blower or the like and collected by a collection device.
  • the spherical inorganic oxide powder is classified as necessary before and/or after collection by the collection device. It is preferable that the main body of the spheroidizing furnace, the transportation piping, etc. are water-cooled by a water-cooling jacket system.
  • a cyclone, gravity sedimentation, louver, bag filter, or the like is used as a collection device.
  • the collection temperature is determined by the amount of heat generated by the amount of combustible gas and the suction amount of the blower, and is adjusted by the amount of cooling water, the intake amount of outside air provided in the line, and the like.
  • Aluminum hydroxide, alumina, metal aluminum and the like are used as raw materials for producing spherical alumina powder. It is desirable to adjust the particle size of the raw material powder in advance to the product particle size (the same particle size as the target inorganic oxide powder), but the particle size can be adjusted by classifying after the spheroidizing treatment. Further, even if the spherical inorganic powder has the same composition, several kinds of raw materials with different particle diameters can be separated, melted into spheres, and then mixed and adjusted. Mixing can be performed, for example, under normal temperature conditions using a known device such as a blender or mixer.
  • the inorganic oxide powder is subjected to surface treatment with a silane coupling agent or the like to reduce the water absorption of the powder, increase the strength of the resin composition, and further reduce the interfacial resistance between the resin and the powder. Thermal conductivity can be further improved.
  • Silane coupling agents include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ (3,4-epoxysynchrohexyl)ethyltrimethoxysilane, ⁇ -glycidoxysilane.
  • Other surface treatment agents such as Zr chelate, titanate coupling agent, aluminum cup A ring agent or the like can be used.
  • Inorganic oxide powders can be preferably used in the production of semiconductor encapsulating materials, adhesives, heat-dissipating sheets, and the like for electronic devices.
  • a resin composition having a low ratio of viscosity under low shear to viscosity under high shear can be obtained, it can be preferably used for the production of compression-molded articles.
  • the resin composition according to the present embodiment contains the above inorganic oxide powder and resin.
  • the inorganic oxide powder is as described above.
  • the content of the inorganic oxide powder in the resin composition is preferably 80 to 95% by mass, more preferably 85 to 95% by mass, and still more preferably 90% by mass, from the viewpoint of heat resistance, mechanical strength, etc. ⁇ 95% by mass.
  • the content of the inorganic oxide powder may be more than 80% by mass and 95% by mass or less in the resin composition.
  • Resins include epoxy resins, silicone resins, phenolic resins, melamine resins, urea resins, unsaturated polyesters, fluorine resins, polyamides such as polyimides, polyamideimides and polyetherimides, polyesters such as polybutylene terephthalate and polyethylene terephthalate, and polyphenylene ethers.
  • polyphenylene sulfide wholly 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) Examples include resins, and it is preferable to include one or more selected from these.
  • an epoxy resin As the resin, it is preferable to use an epoxy resin as the resin. Any epoxy resin having two or more epoxy groups in one molecule can be used as the epoxy resin. Specific examples thereof include phenol novolak type epoxy resins, ortho-cresol novolak type epoxy resins, epoxidized novolak resins of phenols and aldehydes, glycidyl ethers such as bisphenol A, bisphenol F and bisphenol S, phthalic acid and the like.
  • Glycidyl ester acid epoxy resins obtained by reacting polybasic acids such as dimer acid with epochlorhydrin, linear aliphatic epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, alkyl-modified polyfunctional epoxy resins, ⁇ -naphthol novolak type epoxy resin, 1,6-dihydroxynaphthalene type epoxy resin, 2,7-dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, bishydroxybiphenyl type epoxy resin, and for imparting flame retardancy Epoxy resin into which halogen such as bromine is introduced.
  • the resin content is preferably 5-20% by mass, more preferably 5-15% by mass, and even more preferably 5-10% by mass.
  • phenol aralkyl resin Phenol novolac type resin obtained by reacting the above mixture with formaldehyde, paraformaldehyde or paraxylene in the presence of an oxidation catalyst
  • polyparahydroxystyrene resin bisphenol compounds such as bisphenol A and bisphenol S
  • functional phenols acid anhydrides such as maleic anhydride, phthalic anhydride and pyromellitic anhydride
  • aromatic amines such as metaphenylenediamine, diaminodiphenylmethane and diaminodiphenylsulfone.
  • a curing accelerator can be added to accelerate the reaction with the curing agent.
  • Curing accelerators include 1,8-diazabicyclo(5,4,0)undecene-7, triphenylphosphine, benzyldimethylamine, 2-methylimidazole and the like.
  • additives can be added to the resin composition as needed.
  • Other additives include rubber-like substances such as silicone rubber, polysulfide rubber, acrylic rubber, butadiene rubber, styrenic block copolymers and saturated elastomers, and various thermoplastics other than the above-mentioned resins.
  • resins resinous materials such as silicone resins, and resins obtained by partially or entirely modifying epoxy resins and phenolic resins with aminosilicone, epoxysilicone, alkoxysilicone, etc., and flame retardant aids such as Sb 2 O 3 , Sb 2 O 4 , Sb 2 O 5 and the like; flame retardants such as halogenated epoxy resins and phosphorus compounds; and coloring agents such as carbon black, iron oxide, dyes and pigments.
  • the resin composition has a small ratio of viscosity at low shear and high shear, it has excellent moldability even when compression molding is performed, and it can seal workpieces such as semiconductor chips without gaps. can do.
  • the resin composition has a low shear viscosity of 20% by mass of a bisphenol F type epoxy resin (epoxy equivalent: 170, viscosity: 4 Pa s) and 80% by mass of inorganic oxide powder.
  • the viscosity is preferably 45 to 70 Pa ⁇ s, more preferably 45 to 65 Pa ⁇ s, measured at a temperature of 30° C. and a rotation speed of 1 rpm using an E-type viscometer.
  • the resin composition is an E-type resin composition composed of 20% by mass of a bisphenol F-type epoxy resin (epoxy equivalent: 170, viscosity: 4 Pa s) and 80% by mass of inorganic oxide powder, as the viscosity at high shear.
  • the viscosity measured with a viscometer at a temperature of 30° C. and a rotation speed of 10 rpm is preferably 35 to 55 Pa ⁇ s, more preferably 40 to 55 Pa ⁇ s.
  • the resin composition preferably has a ratio of viscosity at low shear to viscosity at high shear (viscosity at low shear/viscosity at high shear) of less than 1.5. It is more preferably 4 or less, and even more preferably 1.3 or less.
  • the production of the resin composition can be carried out by stirring, dissolving, mixing, and dispersing predetermined amounts of each of the above materials.
  • a device for mixing, stirring and dispersing these mixtures a laikai machine equipped with a stirring and heating device, a three-roll mill, a ball mill, a planetary mixer and the like can be used. Moreover, you may use these apparatuses in combination suitably.
  • the resin composition can be preferably used for producing semiconductor encapsulating materials, adhesives, heat-dissipating sheets, and the like for electronic devices.
  • the ratio of the viscosity at low shear to the viscosity at high shear is small, it can be preferably used for the production of compression molded articles.
  • a compression-molded article according to the present embodiment includes the resin composition described above.
  • a known compression molding method can be used as a method for manufacturing the compression-molded product.
  • the resin composition can be produced by compression molding by heat curing under conditions of a temperature of 180° C. and a pressure of 8 MPa.
  • the compression-molded product contains a resin composition having a small ratio of the viscosity at low shear and the viscosity at high shear, it is possible to seal workpieces such as semiconductor chips without gaps and with extremely few voids. has the characteristics of Therefore, the compression-molded product can be preferably used as a semiconductor encapsulant, an adhesive member, a heat dissipation sheet, and the like for electronic devices.
  • Examples 1 to 6, Comparative Examples 1 to 6 Alumina raw material powder having an average particle size (D 50 ) having a maximum value in the range of 2 to 45 ⁇ m is introduced into a high-temperature flame formed by using LPG as a fuel gas and oxygen as a combustion support gas, and is melted and spheroidized. Inorganic oxide powder (spherical alumina powder) was thus produced. The cumulative frequency of each particle size range was adjusted to the value shown in Table 1 by adjusting the blending amount of the raw material powder, sieving, classification, and the like.
  • each of the obtained inorganic oxide powders was mixed with the following materials in the following amounts using a Henschel mixer ("FM-20C/I” manufactured by Nippon Coke Kogyo Co., Ltd.) at room temperature and a rotation speed of 2000 rpm. to obtain a resin composition.
  • a Henschel mixer (“FM-20C/I” manufactured by Nippon Coke Kogyo Co., Ltd.) at room temperature and a rotation speed of 2000 rpm.
  • the resulting inorganic oxide powder was measured for viscosity (at low shear and at high shear) when blended with an epoxy resin by the method described below. Using the obtained values, the value of the ratio of the viscosity at low shear to the viscosity at high shear was calculated. Table 1 shows the results.
  • a resin composition comprising 20% by mass of a bisphenol F type epoxy resin (manufactured by Mitsubishi Chemical Corporation: Epicoat 807, epoxy equivalent 170, viscosity 4 Pa s) and 80% by mass of the spherical alumina powder prepared above was prepared.
  • the viscosity of the resin composition was measured using an E-type viscometer (trade name “TVE-10” manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 1 rpm.
  • the viscosity of the resin composition under high shear was measured using an E-type viscometer (trade name "TVE-10” manufactured by Toki Sangyo Co., Ltd.) at a temperature of 30° C. and a rotation speed of 10 rpm.
  • the resin compositions containing the inorganic oxide powder (spherical alumina powder) obtained in Examples had a ratio of viscosity at low shear to viscosity at high shear of less than 1.5. , the ratio of low-shear viscosity to high-shear viscosity is small. Therefore, the viscosity is kept low from the beginning to the end when the work is pressed against the resin composition in the compression molding method. As a result, a compression-molded article can be produced with excellent moldability.

Abstract

La présente invention vise à fournir : une poudre d'oxyde inorganique par laquelle il est possible de fournir une composition de résine dans laquelle le rapport entre la viscosité à faible cisaillement et la viscosité à cisaillement élevé est faible ; une composition de résine contenant ladite poudre d'oxyde inorganique ; et un article moulé par compression obtenu par moulage de ladite composition de résine. La présente invention concerne par conséquent une poudre d'oxyde inorganique : dans une distribution de fréquence des tailles des particules basée sur le volume, la valeur du rapport de la fréquence cumulée pour une seconde région, où la taille des particules est située dans la plage de 0,001 à 20 µm, à la fréquence cumulée pour une première région, où la taille des particules est située dans la plage de 0,001 à 10 µm (fréquence cumulée pour la seconde région divisée par la fréquence cumulée pour la première région) étant de 1,2 à 1,4 ; la fréquence cumulée lorsque la taille des particules est de 20 à 46 μm est de 15 à 45 % en volume ; et la viscosité d'une composition de résine comprenant 20 % en masse d'une résine époxy de type bisphénol F (un équivalent époxy de 170, une viscosité de 4 Pa・s) et 80 % en masse d'une poudre d'oxyde inorganique est de 45 à 70 Pa・s telle que mesurée à une température de 30 °C et à une vitesse de rotation de 1 tr/min en utilisant un viscosimètre de type E.
PCT/JP2022/012147 2021-03-26 2022-03-17 Poudre d'oxyde inorganique, composition de résine et article moulé par compression WO2022202584A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023509090A JPWO2022202584A1 (fr) 2021-03-26 2022-03-17

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021053526 2021-03-26
JP2021-053526 2021-03-26

Publications (1)

Publication Number Publication Date
WO2022202584A1 true WO2022202584A1 (fr) 2022-09-29

Family

ID=83397227

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/012147 WO2022202584A1 (fr) 2021-03-26 2022-03-17 Poudre d'oxyde inorganique, composition de résine et article moulé par compression

Country Status (3)

Country Link
JP (1) JPWO2022202584A1 (fr)
TW (1) TW202300579A (fr)
WO (1) WO2022202584A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07278415A (ja) * 1994-04-13 1995-10-24 Shin Etsu Chem Co Ltd 半導体封止用樹脂組成物及び半導体装置
JPH09194242A (ja) * 1996-01-16 1997-07-29 Denki Kagaku Kogyo Kk アルミナセメント及びそれを用いた不定形耐火物
JPH09210570A (ja) * 1995-11-30 1997-08-12 Kawasaki Steel Corp 火炎溶射方法
JP2001064522A (ja) * 1999-08-27 2001-03-13 Toray Ind Inc 半導体封止用樹脂組成物
JP2002128520A (ja) * 2000-10-20 2002-05-09 Shiraishi Chuo Kenkyusho:Kk 球状カルシウムアルミネート及びその製造方法
JP2003003074A (ja) * 2001-06-20 2003-01-08 Mitsui Chemicals Inc シリカ含有樹脂組成物およびその精密成形体
JP2005089293A (ja) * 2003-08-13 2005-04-07 Sakai Chem Ind Co Ltd ペロブスカイト化合物粉体の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07278415A (ja) * 1994-04-13 1995-10-24 Shin Etsu Chem Co Ltd 半導体封止用樹脂組成物及び半導体装置
JPH09210570A (ja) * 1995-11-30 1997-08-12 Kawasaki Steel Corp 火炎溶射方法
JPH09194242A (ja) * 1996-01-16 1997-07-29 Denki Kagaku Kogyo Kk アルミナセメント及びそれを用いた不定形耐火物
JP2001064522A (ja) * 1999-08-27 2001-03-13 Toray Ind Inc 半導体封止用樹脂組成物
JP2002128520A (ja) * 2000-10-20 2002-05-09 Shiraishi Chuo Kenkyusho:Kk 球状カルシウムアルミネート及びその製造方法
JP2003003074A (ja) * 2001-06-20 2003-01-08 Mitsui Chemicals Inc シリカ含有樹脂組成物およびその精密成形体
JP2005089293A (ja) * 2003-08-13 2005-04-07 Sakai Chem Ind Co Ltd ペロブスカイト化合物粉体の製造方法

Also Published As

Publication number Publication date
TW202300579A (zh) 2023-01-01
JPWO2022202584A1 (fr) 2022-09-29

Similar Documents

Publication Publication Date Title
JP5380290B2 (ja) シリカ粉末の製造方法
JP5568399B2 (ja) 球状アルミナ粉末、その製造方法及び用途
JP5351513B2 (ja) シリカ粉末及びその用途
KR101191590B1 (ko) 알루미나질 섬유 집합체, 그 제조 방법 및 용도
JP2004244491A (ja) 高熱伝導性無機質粉末およびその樹脂組成物
JP2001048521A (ja) 微細球状シリカ粉末とその製造方法および用途
JP5526027B2 (ja) 非晶質シリカ質粉末、その製造方法、樹脂組成物、及び半導体封止材
JP2001158614A (ja) 球状無機質粉末及びその用途
JP2005139295A (ja) 金属酸化物粉末、その製造方法、用途
JPWO2008078706A1 (ja) 非晶質シリカ質粉末、その製造方法及び半導体封止材
WO2022202584A1 (fr) Poudre d'oxyde inorganique, composition de résine et article moulé par compression
WO2022202583A1 (fr) Poudre d'oxyde inorganique, composition de résine et article moulé par compression
WO2022202592A1 (fr) Poudre d'oxyde inorganique, composition de résine et produit moulé par compression
JP2002252314A (ja) 球状無機質粉末及びその用途
JP3721285B2 (ja) 球状無機質粉末及びその用途
JP2019182715A (ja) 非晶質シリカ粉末、樹脂組成物、及び半導体封止材
TWI457281B (zh) 氧化矽質粉末、其製造方法及用途
JP2000319633A (ja) エポキシ樹脂系封止材料用シリカ系充填材
JP5345787B2 (ja) 半導体封止材用シリカ・アルミナ複合酸化物超微粉末の製造方法
JP4131620B2 (ja) シリカ粉末及びその用途
JP4342036B2 (ja) シリカ質充填材用助剤の製造方法
JPH0525397A (ja) 樹脂組成物
WO2023189589A1 (fr) Poudre inorganique, procédé de production associé et composition de résine
WO2022210260A1 (fr) Poudre inorganique sphérique et matériau d'étanchéité liquide
EP4317067A1 (fr) Poudre inorganique, composition inorganique, et composition de résine

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22775372

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2023509090

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22775372

Country of ref document: EP

Kind code of ref document: A1