WO2020241902A1 - Particules sphériques de silice cristalline, mélange de particules sphériques de silice et matériau composite - Google Patents

Particules sphériques de silice cristalline, mélange de particules sphériques de silice et matériau composite Download PDF

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WO2020241902A1
WO2020241902A1 PCT/JP2020/021662 JP2020021662W WO2020241902A1 WO 2020241902 A1 WO2020241902 A1 WO 2020241902A1 JP 2020021662 W JP2020021662 W JP 2020021662W WO 2020241902 A1 WO2020241902 A1 WO 2020241902A1
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silica particles
spherical silica
mass
spherical
crystalline
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PCT/JP2020/021662
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Japanese (ja)
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克昌 矢木
睦人 田中
正徳 阿江
泰宏 青山
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日鉄ケミカル＆マテリアル株式会社
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Priority to JP2021521923A priority Critical patent/JPWO2020241902A1/ja
Priority to KR1020217039161A priority patent/KR102644020B1/ko
Priority to SG11202113322TA priority patent/SG11202113322TA/en
Priority to CN202080040363.1A priority patent/CN113905984A/zh
Publication of WO2020241902A1 publication Critical patent/WO2020241902A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/06—Quartz; Sand
    • C04B14/062—Microsilica, e.g. colloïdal silica
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • 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

Definitions

  • the present invention comprises spherical crystalline silica particles having excellent dielectric properties, which are suitable for forming a semiconductor encapsulant for high frequencies corresponding to a high frequency signal having a frequency of 3 GHz or more, and a wiring substrate, and spherical silica containing the same. It relates to a particle mixture and a composite material obtained by combining this with a resin.
  • the frequency is increasing due to the increase in the amount of information due to the sophistication of communication technology and the rapid expansion of the use of millimeter wave bands such as millimeter wave radar.
  • Semiconductors that handle these high-frequency signals and circuit boards that transmit them are composed of electrodes and dielectrics that form a circuit pattern. Since suppression of signal propagation delay is important for high-speed signal transmission, a low relative permittivity ( ⁇ r) is required.
  • ⁇ r relative permittivity
  • the dielectric loss tangent (tan ⁇ ) of the dielectric material is small. For low dielectric loss, the dielectric material must have low polarity and low dipole moments.
  • thermal characteristics such as thermal conductivity and coefficient of thermal expansion from suppression of mismatch of thermal expansion with the electrode material, high bending strength, etc. Therefore, mechanical properties are also important.
  • ceramic fillers, resins, and composites obtained by combining them are mainly used.
  • ceramic fillers and resins having even lower ⁇ r and lower tan ⁇ are required.
  • the resin has a relatively small ⁇ r and is suitable for high frequencies, but has a tan ⁇ and a coefficient of thermal expansion larger than those of the ceramic filler. Therefore, in the composite in which the filler for the millimeter wave band and the resin are combined, (1) the ceramic filler itself has a low ⁇ r and low tan ⁇ , and (2) the ceramic filler is highly filled and the amount of the resin showing a large tan ⁇ is increased. It is suitable to reduce.
  • Silica (SiO 2 ) particles have been conventionally used as ceramic fillers. If the shape of the silica particles is angular, the fluidity, dispersibility, and filling property in the resin are deteriorated, and the manufacturing equipment is also worn. In order to improve these, spherical silica particles are widely used. It is considered that the closer the spherical silica filler is to a true sphere, the better the filling property, fluidity, and mold wear resistance, and a filler having a high circularity has been pursued. Furthermore, further improvement of filling property has been studied by optimizing the particle size distribution of the filler.
  • the filling rate is increased too much by spheroidizing the filler shape and optimizing the particle size distribution, the fluidity of the composite as a sealing material is lowered, and the moldability is deteriorated.
  • Thermal spraying is known as a method for producing spherical silica.
  • crushed silica particles as a raw material are passed through a flame of 2000 ° C. or higher to melt the particles, and the shape of the particles becomes spherical due to surface tension.
  • the molten spheroidized particles are transported by air flow so as not to fuse with each other and collected, and the particles after thermal spraying are rapidly cooled.
  • This silica (molten silica) has an amorphous structure because it is rapidly cooled from the molten state.
  • this spherical molten silica is amorphous, its coefficient of thermal expansion and thermal conductivity are low.
  • the coefficient of thermal expansion of amorphous silica is 0.5 ppm / K, and the thermal conductivity is 1.4 W / mK.
  • These physical properties are substantially the same as the coefficient of thermal expansion of quartz glass, which has an amorphous structure and does not have a crystal structure. Therefore, by mixing with a resin having a high coefficient of thermal expansion, the effect of lowering the thermal expansion of the sealing material itself can be obtained.
  • the coefficient of thermal expansion of the composite as a sealing material to a value close to Si, it is possible to suppress deformation due to thermal expansion behavior when sealing an IC chip.
  • the encapsulant (composite) filled with amorphous silica which has a low coefficient of thermal expansion, may have a smaller coefficient of thermal expansion than Si, and the heating temperature during reflow and the operating temperature of the semiconductor device. This may cause warpage or cracks. Further, due to the low thermal conductivity, the dissipation of heat generated from the semiconductor device is also a problem.
  • the characteristics required for a silica filler compatible with high frequencies of 3 GHz or higher include excellent dielectric properties, and fillability and fluidity that can be blended in a large amount with a resin to maintain the performance as a sealing material. All requirements such as thermal properties, mechanical strength performance and mold wear resistance had to be met, but such silica fillers and silica-resin composites did not exist.
  • the present inventors are excellent in devices and substrates for 5G (fifth generation mobile communication system) having a frequency of 3 GHz or more, and in-vehicle radars using a millimeter wave band of 60 GHz or more.
  • 5G next generation mobile communication system
  • An object of the present invention is to provide a spherical silica particle, a spherical silica particle mixture, and a composite material, which have excellent dielectric properties and can also have excellent thermal properties and fluidity.
  • spherical molten (amorphous) silica is required. It was found that it is effective to heat-treat and crystallize to obtain a specific crystal structure. That is, it was confirmed for the first time that the spherical silica particles of the present invention had a dielectric loss tangent at a high frequency of 3 GHz or higher significantly lower than that of amorphous particles and exhibited high thermal conductivity, and the present invention was completed.
  • the spherical silica particles according to the present invention have a specific crystal structure, they have excellent dielectric properties (low dielectric constant and dielectric loss tangent), and have excellent thermal properties () as compared with conventional spherical crystalline silica particles. Shown. Further, since it is spherical, has a narrow particle size distribution, and can have a high circularity, both high flow / high dispersibility and high filling property are achieved. Therefore, high-frequency signal transmission is performed as a filler. It can be suitably used for semiconductors, substrates, etc.
  • FIG. 1 is a diagram for explaining the calculation of the photographing area and the peripheral length of the particles.
  • the present invention provides the following aspects.
  • a total of 60% or more of a crystalline cristobalite phase and a crystalline quartz phase is contained, and the average diameter of the polycrystalline grains constituting the crystalline cristobalite phase or the quartz phase is 2 ⁇ m or more, and the blocking cylindrical waveguide method (JIS R1660-).
  • the spherical silica particles according to [1] which contains aluminum in an amount of more than 0.5% by mass and 2.0% by mass or less in terms of oxide.
  • the crystal structure of silica includes cristobalite, quartz, tridymite and the like. Silica having these crystal structures has a higher coefficient of thermal expansion and thermal conductivity than amorphous silica. Therefore, by replacing the molten (amorphous) silica with crystalline silica in an appropriate amount, it is possible to improve the thermal conductivity while suppressing the difference in thermal expansion from the IC chip. Further, by optimizing the particle size distribution of the molten (amorphous) silica and the crystalline silica, a silica filler (spherical silica particles) exhibiting higher filling property can be obtained.
  • the spherical silica particles of the present invention contain a total of 60% or more of a crystalline cristobalite phase and a crystalline quartz phase (hereinafter, collectively referred to as “crystalline phase”). That is, the content of the crystalline phase in the spherical silica particles is 60% or more. If it is 60% or more, excellent dielectric properties are exhibited. In general, the higher the proportion of crystalline silica, the better the dielectric properties. Silica other than crystalline silica is amorphous.
  • the crystalline phase may be either a crystalline cristobalite phase or a crystalline quartz phase, or the crystalline cristobalite phase and the crystalline quartz phase may coexist.
  • the spherical silica particles of the present invention may contain crystalline tridymite in addition to the crystalline cristobalite phase and the crystalline quartz phase.
  • the abundance ratio of crystalline phases such as cristobalite and quartz can be measured by, for example, X-ray diffraction (XRD).
  • XRD X-ray diffraction
  • it can be calculated by the following formula from the sum of the integrated intensities of the crystalline peak (Ic) and the integrated intensities of the amorphous halo portion (Ia).
  • the ratio of various crystal phases in the crystal phase contained in the spherical silica particles according to the present invention is measured by XRD as described below.
  • XRD X-ray diffraction
  • the crystalline cristobalite phase and the crystalline quartz phase are composed of a large number of microcrystals, that is, polycrystalline grains.
  • the average diameter of polycrystalline grains is 2 ⁇ m or more.
  • the average diameter was obtained by cutting the cross section after filling the sample with resin and averaging the area of the polycrystalline grain appearing on the cross section by area weighting.
  • Crystalline silica can be expected to have higher thermal conductivity than amorphous silica, but if the grain size of the polycrystal is too small, sufficient thermal conductivity cannot be obtained due to scattering due to grain boundaries. .. Therefore, in order to obtain sufficient thermal conductivity, the average diameter of the polycrystalline grain size needs to be 2 ⁇ m or more.
  • the polycrystalline grain size (average diameter) is measured by dispersion-filling crystalline powder in an epoxy resin, cutting out a cross section thereof, and measuring it by an EBSD method (Electron Backscatter Diffraction Pattern).
  • a heat conductive sheet can be prepared by kneading the resin and the spherical silica particles of the present invention, and the thermal conductivity can be measured.
  • the spherical silica particles are mixed with a silicone resin (CY52-276A / B manufactured by Dow Corning Co., Ltd.) at a filler ratio of 80% by mass, vacuum degassed to 5 Torr or less, and kneaded. Then, it is molded with a mold. The mold is heated to 120 ° C., molded at 6 to 7 MPa, and molded for 40 minutes.
  • the resin composition is taken out from the mold and cured at 140 ° C. for 1 hour. After cooling to room temperature, the resin composition is sliced to a thickness of 1.5, 2.5, 4.5, 6.5, 7.5, 8.5 mm, respectively, and processed into a 2 cm square sheet-shaped sample.
  • the thermal resistance of each sample was measured according to ASTM D5470. The sample is sandwiched between blocks made of SUS304, compressed at 0.123 MPa, and the thickness after compression is recorded. The relationship between the thermal resistance value obtained in this way and the thickness after compression can be linearly approximated, and the thermal conductivity can be derived from the slope.
  • the spherical silica particles of the present invention have a dielectric loss tangent of 0.0020 or less at 10 GHz obtained by the blocking cylindrical waveguide method (JIS R1660-1: 2004).
  • the spherical silica particles of the present invention have the above-mentioned crystal structure (crystal phase ratio and polycrystalline grain size), so that the dielectric is significantly lower than that of amorphous particles. It is considered that it has a normal contact and a high thermal conductivity can be obtained.
  • a method for measuring the dielectric constant and the dielectric loss tangent of the spherical silica particles of the present invention will be described.
  • the measurement is performed using a composite material.
  • the composite material is prepared by using a powder of spherical silica particles and an epoxy resin (YX-4000H manufactured by Mitsubishi Chemical Corporation), and using spherical silica particles at a temperature of 100 ° C. , Kneaded with two roll mills.
  • the sample after kneading was crushed with a mortar and pestle.
  • the crushed sample was filled in a mold (50 ⁇ ) and set in a press. After pressurizing at a molding temperature of 175 ° C. for about 1 minute at 1 MPa, the mixture was held at 5 MPa for 9 minutes.
  • silica-resin plate was taken out from the mold.
  • the produced silica-resin plate was cut with an outer peripheral blade and processed to a size of about 10 mm ⁇ 10 mm.
  • it was ground by high-precision surface grinding (SGM-5000 manufactured by Hidewa Kogyo), and the thickness was varied between 0.2 mm and 1.0 mm.
  • the silica-resin composite was measured in the 10 GHz frequency band based on the blocking cylindrical waveguide method (JIS R1660-1: 2004). From the relationship between the composite with spherical silica particles of 0, 30, 50, 83 to 89% by mass with respect to the epoxy resin and the dielectric loss tangent, the numerical value of 100% spherical silica particles is externalized, and the obtained numerical value is spherical. The dielectric loss tangent of the silica particles was used.
  • the spherical silica particles according to the present invention are prepared by filling an alumina container with silica particle powder (amorphous) produced by an atmospheric spraying method and heat-treating time in a temperature range of 800 ° C to 1600 ° C. Can be produced by processing in an air atmosphere for 50 minutes to 16 hours.
  • the preferred heat treatment time is 1-12 hours. Crystallization may not be sufficient if it is less than 1 hour, and if the heat treatment time exceeds 12 hours, the burden of manufacturing cost becomes large.
  • the amount of Al added is preferably more than 0.5% by mass and 2.0% by mass or less in terms of oxide. Within this range, a sufficient crystallinity can be obtained, and spherical silica particles in which an increase in alkali content and an increase in specific gravity due to Al are suppressed can be obtained. If it is 0.5% by mass or less, the crystallinity tends to decrease, and if it exceeds 2.0% by mass, the alkali component and the specific gravity increase remarkably, and as a result, the resin curing characteristics are adversely affected. In addition, it tends to be difficult to apply to mobile devices and in-vehicle applications that require weight reduction.
  • Patent Document 1 and Patent Document 2 the amount of aluminum added is limited to 5000 mass ppm (0.5 mass%) or less in terms of oxide, and heat treatment at a higher temperature for a longer period of time is required to achieve sufficient crystallization. Was required, and the particles were sometimes easily fused to each other.
  • alkali metal or alkaline earth metal is added and treated at 800 to 1150 ° C, which is lower than the cristobalite crystallization temperature, and quartz appears as the main phase.
  • the amount of the alkali metal or alkaline earth metal added may be 0.1 to 3% by mass in terms of oxide. If it is too small, quartzization will not be promoted, and if it is too large, the purity of silica particles will decrease.
  • alkali metals and alkaline earth metals include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, and radium.
  • Li and Ca are more preferable.
  • the contents of aluminum, alkali metal and alkaline earth metal can be measured by, for example, atomic absorption spectrometry or ICP mass spectrometry (ICP-MS).
  • the ratio of the crystalline quartz phase in the spherical silica particles may be 30% by mass or more. Since cristobalite has a phase transition point between a low temperature phase and a high temperature phase at 200 to 250 ° C., it is effectively accompanied by a large thermal expansion, which may be an obstacle depending on the intended use. When emphasizing such a point, it is desirable that the quartz phase is 30% by mass or more. Quartz does not pose a practical obstacle because the phase transition point between the low temperature phase and the high temperature phase is 500 ° C. or higher. Within this range, spherical silica particles having thermal expansion characteristics suitable for a semiconductor package can be obtained. If it is less than 30% by mass, the thermal expansion due to the phase transition of the cristobalite phase becomes too large.
  • the spherical silica particles (amorphous) powder which is the raw material of the spherical silica particles of the present invention, can be produced by a thermal spraying method. Specifically, a burner with a tubular structure consisting of a flammable gas supply pipe, a flammable gas supply pipe, and a crushed high-purity silica (quartz) supply pipe is installed at the top of the manufacturing furnace, while the lower part of the manufacturing furnace.
  • Spherical silica particle (amorphous) powder was produced by thermal spraying using a device connected to a collection system (the produced powder was sucked with a blower and collected with a bag filter).
  • LPG was supplied from the flammable gas supply pipe and oxygen was supplied from the flammable gas supply pipe to form a high-temperature flame in the production furnace.
  • the crushed silica powder (quartz) was supplied from the silica supply pipe, and the spherical silica powder was collected by a bag filter.
  • the spherical silica particles obtained by thermal spraying can have a circularity of 0.83 or more. The higher the circularity, the higher the fluidity. Therefore, the circularity is preferably 0.83 or more. If it is a thermal spraying means, particles having a high circularity can be easily obtained.
  • the temperature of the flame at the time of thermal spraying is silica. Must be higher than the melting temperature.
  • the flame temperature is 2000 ° C. or higher.
  • silica particles in thermal spraying come into contact with each other, the particles tend to bond with each other to form a distorted shape. Therefore, when supplying the raw material into the flame, the raw material is dispersed in the gas stream or supplied. It is desirable to adjust the supply amount.
  • the spherical silica particles of the present invention maintain the circularity of the spherical silica particles (amorphous) obtained by thermal spraying without decreasing the circularity of most of the circularity before and after the heat treatment for crystallization described above. can do.
  • the circularity is measured for 6000 pieces of 10 um or more in size using FPIA-3000 manufactured by Malvern PANalytical.
  • the resolution of the measuring device is generally insufficient, and the circularity may be calculated higher. In that case, the circularity cannot be adopted as an index of liquidity. Therefore, the circularity is measured for a size of 10 ⁇ m or more.
  • 10 g of a powder sample such as silica particles to be measured and 200 ml of distilled water are placed in a beaker, and ultrasonic waves are set to 150 to 500 W at a frequency of 20 to 30 kHz by an ultrasonic homogenizer, and dispersion treatment is performed for 30 seconds or more.
  • the required amount is taken out from here with a pipette or the like and measured with an optical measuring device.
  • the particle size is defined as the equivalent diameter of a circle. This is a circular diameter with an area equal to the projected area on the measured image, Calculated by.
  • the projected area is calculated by image processing, but as shown in FIG. 1, the particles are image-processed such as binary imaging, and the center of each pixel cell in the outline of the particle is connected by a straight line and surrounded. Defined as area.
  • the objective lens of the measuring device was selected to be about 0.5-1 ⁇ m / pixel according to the number of pixels.
  • the spherical silica particles include 95% by mass or more and 99.9% by mass or less of the spherical silica particles and 0.1% by mass or more and 5% by mass or less of ultrafine particles having an average particle size of 0.1 ⁇ m or less.
  • a mixture is provided.
  • the blending ratio of the spherical silica particles and the ultrafine particles is preferably 95% by mass or more and 99.9% by mass or less for the spherical silica particles, and 0.1% by mass or more and 5% by mass or less for the ultrafine particles. If the ratio of the ultrafine particles is too low, the gaps between the spherical silica particles will not be filled and the filling rate will not be improved. If the ratio of ultrafine particles is too high, the gaps between the spherical silica particles will overflow and the total volume will increase.
  • the ultrafine particles refer to spherical silica particles having a particle size of 0.1 ⁇ m or less.
  • spherical silica particles those having a particle size of 0.1 ⁇ m or less (ultrafine particles) can be separated, and a predetermined amount of ultrafine particles can be blended at the time of final product production. It is also possible to adjust the particle size distribution of the spherical silica particles. By adjusting the particle size distribution of the crushed silica powder (quartz) used as the thermal spraying raw material, the particle size distribution of the spherical silica particles (amorphous) after thermal spraying can be adjusted.
  • the spherical silica particles obtained by the heat treatment for crystallization may have a particle size distribution slightly different from that of the spherical silica particles (amorphous), but the amount of change in the particle size distribution can be predicted, and later. It is also possible to adjust the particle size distribution of the spherical silica particles of the present invention by sieving in the process.
  • the silica particles of the present invention may have an average particle size (D50) of 1 to 100 ⁇ m. If the average particle size exceeds 100 ⁇ m, when used as a filler for semiconductor encapsulants, the particle size may become too coarse and cause gate clogging or mold wear, and the average particle size is less than 1 ⁇ m.
  • a more preferable upper limit of the average particle size is 50 ⁇ m, and even more preferably 40 ⁇ m.
  • the more preferable lower limit of the average particle size is 3 ⁇ m, and more preferably 5 ⁇ m.
  • the average particle size here can be obtained by measuring the particle size distribution by a wet laser diffraction method (laser diffraction / scattering method).
  • the average particle size referred to here is called the median diameter, and the particle size distribution is measured by a laser diffraction method, and the particle size at which the cumulative frequency of particle sizes is 50% is defined as the average particle size (D50).
  • the average particle size related to the particle size distribution of spherical silica particles, ultrafine particles, etc. is determined by measuring the particle size distribution by a laser diffraction method or the like.
  • the particle size distribution by the laser diffraction method can be measured by, for example, CILAS 920 manufactured by CILAS.
  • the average particle size referred to here is called the median diameter, and the particle size at which the cumulative frequency of particle sizes is 50% by measuring the particle size distribution by a method such as laser diffraction is the average particle size (D50).
  • D50 average particle size
  • a composite material of the spherical silica particles and a resin is provided.
  • the filling rate (filler filling rate) of the silica filler in the resin composite it is necessary to increase the filling rate (filler filling rate) of the silica filler in the resin composite to reduce the amount of the resin having a low dielectric constant property (for example, epoxy resin). It is valid.
  • a filler filling rate of 85% by mass or more and less than 95% by mass can be achieved while maintaining high fluidity.
  • the silica particles of the present invention have a filling rate of 0.1 ⁇ m.
  • the filling rate can be further increased.
  • the filler filling rate is increased, the fluidity decreases, but when the addition amount of ultrafine particles of 0.1 ⁇ m or less is 0.1% by mass or more and 5% by mass or less, both high filling property and high fluidity are realized. it can.
  • the composite material of the spherical silica particles and the resin is included.
  • the composition of the composite material will be described.
  • an epoxy resin is not particularly limited, and examples thereof include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, and phenoxy type epoxy resin.
  • bisphenol A type epoxy resin is particularly preferable from the viewpoint of availability and handleability.
  • a known resin when manufacturing a semiconductor-related material such as a packaging substrate or an interlayer insulating film, a known resin can be applied as the resin used in the resin composite composition, but it is preferable to use an epoxy resin.
  • the 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 and the like. Can be used. One of these types can be used alone, or two or more types having different molecular weights can be used in combination. Among these, an epoxy resin having two or more epoxy groups in one molecule is preferable from the viewpoint of curability, heat resistance and the like.
  • biphenyl type epoxy resin phenol novolac type epoxy resin, orthocresol novolac type epoxy resin, epoxyized phenols and aldehydes novolak resin, glycidyl ethers such as bisphenol A, bisphenol F and bisphenol S, Glycydyl esteric acid epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, alkyl-modified polyfunctional Epoxy resin, ⁇ -naphthol novolac type epoxy resin, 1,6-dihydroxynaphthalene type epoxy resin, 2,7-dihydroxynaphthalene type epoxy resin, bishydroxybiphenyl type epoxy resin, and bromine to impart flame retardancy, etc.
  • examples thereof include an epoxy resin into which the halogen of the above is introduced.
  • the bisphenol A type epoxy resin is particularly preferable.
  • a resin used for a resin composite composition such as a prepreg for a printed circuit board and various engineering plastics for applications other than a composite material for a semiconductor encapsulant
  • a resin other than an epoxy-based resin can also be applied.
  • polyamide such as silicone resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyimide, polyamideimide, polyetherimide, etc .; polybutylene terephthalate, polyethylene terephthalate, etc.
  • Polyester Polyphenylene sulfide, aromatic polyester, polysulfone, liquid crystal polymer, polyether sulfone, polycarbonate, maleimide modified resin, ABS resin, AAS (acrylonitrile-acrylic rubber / styrene) resin, AES (acrylonitrile / ethylene / propylene / diene rubber-styrene) ) Resin can be mentioned.
  • AAS acrylonitrile-acrylic rubber / styrene
  • AES acrylonitrile / ethylene / propylene / diene rubber-styrene
  • a known curing agent may be used to cure the resin, but a phenolic curing agent can be used.
  • a phenol novolak resin, an alkylphenol novolak resin, polyvinylphenols and the like can be used alone or in combination of two or more.
  • the amount of the phenolic curing agent blended is preferably less than 1.0 and 0.1 or more in equivalent ratio with the epoxy resin (phenolic hydroxyl group equivalent / epoxy group equivalent). As a result, the unreacted phenol curing agent does not remain, and the hygroscopic heat resistance is improved.
  • the amount of spherical silica particles blended in the composite material is preferably large from the viewpoint of heat resistance and coefficient of thermal expansion. It is usually suitable 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 with respect to the total mass of the composite material. This is because if the blending amount of the silica powder is too small, it is difficult to obtain effects such as improving the strength of the sealing material and suppressing thermal expansion, and conversely, if it is too large, it is related to the surface treatment of the silica powder. This is because segregation due to aggregation of silica powder is likely to occur in the composite material, and the viscosity of the composite material becomes too large, which makes it difficult to put it into practical use as a sealing material.
  • silane coupling agent a known coupling agent may be used, but one having an epoxy-based functional group is preferable.
  • Example 1-4 Spherical molten (amorphous) silica particles having an average particle size of 29 ⁇ m were prepared by a thermal spraying method. Calcium oxide and alumina were added to the raw material powder at the time of spraying so that the calcium concentration and the aluminum concentration in the silica particles were 1% by mass and 0.6% by mass in terms of oxides, respectively. The prepared silica particles were placed in an alumina container and heat-treated at 1400-900 ° C. The conditions of each example and the measurement results obtained are shown in detail in Table 1.
  • Example 5-8 Spherical molten (amorphous) silica particles having an average particle size of 9 ⁇ m (the amount of ultrafine particles added of 0.1 ⁇ m or less is 3.0 mass) were prepared in the same manner as in Example 1-4 except that they were prepared by the spraying method. The silica particles were placed in an alumina container and heat-treated at 1400-900 ° C. The conditions of each example and the measurement results obtained are shown in detail in Table 1.
  • Examples 3, 9-10, Comparative Example 9 Spherical silica particles were prepared under the same conditions as in Example 3 except for the heat treatment time. Further, the prepared spherical silica particles were filled in silicone resin in an amount of 80% by mass as described above, and the polycrystalline grain size distribution was measured by EBSD of the cross-sectional sample. Moreover, the thermal conductivity was measured from the sample cut out from the same sample. Under the conditions of Comparative Example 9, the growth of crystal grains was insufficient, resulting in a slightly inferior thermal conductivity, but in Examples 3, 9 and 10, sufficient thermal conductivity was obtained. Table 3 summarizes these conditions and measurement results.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Civil Engineering (AREA)
  • Silicon Compounds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Le problème décrit par la présente invention est de fournir : des particules sphériques de silice qui ont d'excellentes propriétés diélectriques et qui peuvent avoir à la fois d'excellentes propriétés thermiques et une excellente fluidité ; un mélange de particules sphériques de silice ; et un matériau composite. La solution selon l'invention porte sur : des particules sphériques de silice caractérisées en ce qu'elles contiennent au moins 60 % au total de phase cristobalite cristalline et de phase de quartz cristalline dans lesquelles la taille moyenne des grains polycristallins constituant la phase cristobalite ou la phase de quartz cristalline est de 2 μm ou plus et une tangente de perte diélectrique à 10 GHz est de 0,0020 ou moins telle que déterminée par la méthode de guide d'onde circulaire de coupure (JIS R1660-1:2004) ; un mélange de particules sphériques de silice les contenant ; et un matériau composite.
PCT/JP2020/021662 2019-05-31 2020-06-01 Particules sphériques de silice cristalline, mélange de particules sphériques de silice et matériau composite WO2020241902A1 (fr)

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SG11202113322TA SG11202113322TA (en) 2019-05-31 2020-06-01 Spherical crystalline silica particles, spherical silica particle mixture, and composite material
CN202080040363.1A CN113905984A (zh) 2019-05-31 2020-06-01 球状结晶性二氧化硅颗粒、球状二氧化硅颗粒混合物以及复合材料

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JP2022114351A (ja) * 2021-01-26 2022-08-05 信越化学工業株式会社 低誘電金属張フッ素樹脂基板及びその製造方法
JP2022117128A (ja) * 2021-01-29 2022-08-10 信越化学工業株式会社 ミリ波用高速通信低誘電基板
WO2023112928A1 (fr) * 2021-12-13 2023-06-22 日鉄ケミカル＆マテリアル株式会社 Particules sphériques de silice cristalline, leur méthode de production, et composition de composite de résine et composite de résine les contenant
WO2023153357A1 (fr) * 2022-02-09 2023-08-17 デンカ株式会社 Poudre de silice sphérique
WO2023189589A1 (fr) * 2022-03-28 2023-10-05 デンカ株式会社 Poudre inorganique, procédé de production associé et composition de résine

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JP2012102016A (ja) * 2012-01-23 2012-05-31 Sumitomo Chemical Co Ltd シリカ粒子およびその製造方法
WO2016031823A1 (fr) * 2014-08-25 2016-03-03 新日鉄住金マテリアルズ株式会社 Particules sphériques de silice cristalline et leur procédé de production
WO2017188301A1 (fr) * 2016-04-28 2017-11-02 株式会社アドマテックス Matériau particulaire de silice cristalline et procédé pour sa fabrication, composition de suspension contenant un matériau particulaire de silice cristalline et composition de résine contenant un matériau particulaire de silice cristalline
WO2018186308A1 (fr) * 2017-04-05 2018-10-11 新日鉄住金マテリアルズ株式会社 Particules sphériques de silice cristalline et leur procédé de production

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JP2012102016A (ja) * 2012-01-23 2012-05-31 Sumitomo Chemical Co Ltd シリカ粒子およびその製造方法
WO2016031823A1 (fr) * 2014-08-25 2016-03-03 新日鉄住金マテリアルズ株式会社 Particules sphériques de silice cristalline et leur procédé de production
WO2017188301A1 (fr) * 2016-04-28 2017-11-02 株式会社アドマテックス Matériau particulaire de silice cristalline et procédé pour sa fabrication, composition de suspension contenant un matériau particulaire de silice cristalline et composition de résine contenant un matériau particulaire de silice cristalline
WO2018186308A1 (fr) * 2017-04-05 2018-10-11 新日鉄住金マテリアルズ株式会社 Particules sphériques de silice cristalline et leur procédé de production

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022114351A (ja) * 2021-01-26 2022-08-05 信越化学工業株式会社 低誘電金属張フッ素樹脂基板及びその製造方法
JP7478679B2 (ja) 2021-01-26 2024-05-07 信越化学工業株式会社 低誘電金属張フッ素樹脂基板及びその製造方法
JP2022117128A (ja) * 2021-01-29 2022-08-10 信越化学工業株式会社 ミリ波用高速通信低誘電基板
WO2023112928A1 (fr) * 2021-12-13 2023-06-22 日鉄ケミカル＆マテリアル株式会社 Particules sphériques de silice cristalline, leur méthode de production, et composition de composite de résine et composite de résine les contenant
WO2023153357A1 (fr) * 2022-02-09 2023-08-17 デンカ株式会社 Poudre de silice sphérique
WO2023189589A1 (fr) * 2022-03-28 2023-10-05 デンカ株式会社 Poudre inorganique, procédé de production associé et composition de résine

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CN113905984A (zh) 2022-01-07
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KR20220003066A (ko) 2022-01-07
KR102644020B1 (ko) 2024-03-07

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