WO2024257788A1 - Silice sphérique fusionnée de haute pureté, composition de résine pour dispositif électronique la contenant, et produit cosmétique la contenant - Google Patents

Silice sphérique fusionnée de haute pureté, composition de résine pour dispositif électronique la contenant, et produit cosmétique la contenant Download PDF

Info

Publication number
WO2024257788A1
WO2024257788A1 PCT/JP2024/021304 JP2024021304W WO2024257788A1 WO 2024257788 A1 WO2024257788 A1 WO 2024257788A1 JP 2024021304 W JP2024021304 W JP 2024021304W WO 2024257788 A1 WO2024257788 A1 WO 2024257788A1
Authority
WO
WIPO (PCT)
Prior art keywords
spherical silica
silica particles
purity fused
particles
resin composition
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
PCT/JP2024/021304
Other languages
English (en)
Japanese (ja)
Inventor
友祐 渡辺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Admatechs Co Ltd
Original Assignee
Admatechs Co Ltd
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 Admatechs Co Ltd filed Critical Admatechs Co Ltd
Publication of WO2024257788A1 publication Critical patent/WO2024257788A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/25—Silicon; Compounds thereof
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

  • the present invention relates to high-purity fused spherical silica, a resin composition for electronic devices containing the same, and cosmetics containing the same, and in particular to high-purity fused spherical silica with reduced impurity content and improved mixability with resin materials, as well as the resin composition and cosmetics containing the same.
  • Insulating materials used to seal precision electronic parts such as semiconductors contain inorganic fillers added to the resin composition. Fillers are required to have insulating properties and a low coefficient of thermal expansion. Generally, silica (silicon oxide) is used.
  • Silica is processed into fillers by crushing natural high-purity ores to a specified particle size.
  • impurities other than silicon oxide
  • silica derived from natural products uranium and thorium elements are present.
  • Patent Document 1 a method for producing spherical silica powder that combines crushing and exposure to flame has been proposed.
  • Patent Document 1 contributes to the reduction of uranium elements through pulverization and exposure to flame.
  • processing precision and integration are being further promoted with the aim of improving the processing speed of semiconductors.
  • the impact of external electromagnetic noise on semiconductors is becoming more of a problem than ever before.
  • silica derived from natural products it is known that alpha rays and the like are generated by the radioactive decay of uranium and thorium elements, and are thought to be the cause of malfunctions.
  • it since it is possible to reduce natural radiation, it can be said that there is also less impact of exposure on the human body.
  • silica particles used as a filler must be easily mixed with resin. Furthermore, there is a demand for the suppression of voids (hollow spaces within the particles) in order to reduce the electrical conductivity of the silica particles themselves.
  • the inventors conducted extensive research and have now discovered a method to more effectively remove uranium and thorium elements from high-purity natural ores, thereby reducing alpha rays and other emissions that originate from the raw materials.
  • the present invention has been made in consideration of the above points, and provides high-purity fused spherical silica and a resin composition for electronic devices that reduce the amount of impurities contained in silica particles that serve as a filler to be added to encapsulants, improves the kneadability of the particles into the encapsulant resin, and further suppresses hollow spaces within the particles in order to control the electrical conductivity of the silica particles themselves. In addition, it also provides a material for cosmetic applications that reduces natural radiation and thus reduces radiation exposure.
  • the high-purity fused spherical silica of an embodiment is characterized in that the uranium content in the spherical silica particles is 5 ppb or less, and the thorium content in the spherical silica particles is 5 ppb or less, the circularity of the spherical silica particles is 0.98 or more, the residual silicon oxide crystal rate in the spherical silica particles is 0.01% or less, and the number of hollow portions having a diameter of 5 ⁇ m or more present in each spherical silica particle is 2 or less within an observation area of 9 mm2 using an electron microscope.
  • the sodium element content in the spherical silica particles may be 10 ppm or less.
  • the spherical silica particles may be made from metallic silicon.
  • the spherical silica particles may have been dissolved in a basic solution of metallic silicon.
  • the spherical silica particles may be exposed to a flame.
  • the resin composition for electronic devices according to the embodiment is characterized by having high-purity fused spherical silica and a resin composition.
  • the cosmetic of the embodiment is characterized in that it contains high-purity fused spherical silica.
  • the cosmetic product may be a powder, an ointment, or a lotion.
  • the uranium content in the spherical silica particles is 5 ppb or less
  • the thorium content in the spherical silica particles is 5 ppb or less
  • the circularity of the spherical silica particles is 0.98 or more
  • the residual silicon oxide crystal rate in the spherical silica particles is 0.01% or less
  • the number of hollow parts with a diameter of 5 ⁇ m or more present in each spherical silica particle is 2 or less within an observation area of 9 mm2 using an electron microscope.
  • the amount of impurities contained in the silica particles to be used as a filler in a sealant is reduced, the kneadability with the sealant resin is improved, and further, the hollow parts within the particles can be suppressed in terms of controlling the electrical conductivity of the silica particles themselves.
  • the resin composition for electronic devices makes it possible to reduce the dose of particle radiation and electromagnetic waves emitted from the spherical particles contained in the resin composition, suppressing disturbance factors such as noise and reducing malfunctions of equipment.
  • the high-purity fused spherical silica of the present invention can also be used as an additive in cosmetics to reduce natural radiation, thereby further reducing the effects of exposure to the human body, and even the effects of crystalline silica.
  • FIG. 1A is an electron microscope photograph of a pulverized product after a pulverization process in Test Example 4, and FIG. 1B is an electron microscope photograph of spherical particles after a melt-spheroidization process.
  • 1 is an electron microscope photograph of the high-purity fused spherical silica of Test Example 6.
  • 1 is an electron microscope photograph of silica particles of Test Example 13.
  • the following processing method is used to obtain the high-purity fused spherical silica of the embodiment. Therefore, the high-purity fused spherical silica will be explained starting from the manufacturing method.
  • the raw silicon metal material is prepared and dissolved in a basic solution.
  • the silicon metal is dissolved in a basic solution to prepare a raw material solution in which the raw silicon metal material is dissolved (the "dissolving process").
  • the basic solution is a solution that does not contain alkali metals or alkaline earth metals.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide are strongly alkaline.
  • any alkali metal remains in the basic solution, it will lower the purity of the final silica particles, which is undesirable.
  • Aqueous solutions of amine compounds are therefore used as solutions that do not contain alkali metals or alkaline earth metals.
  • amine compounds include ammonia, primary amines, secondary amines, tertiary amines, quaternary ammonium hydroxides (ammonium salts), arylamines, silazanes, and hydrazines.
  • the amine compound is one or more compounds selected from ammonia, methylamine, ethylamine, propylamine, dimethylamine, diethylamine, pyrrolidine, trimethylamine, triethylamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, methyltributylammonium hydroxide, pyrrolidine, piperidine, pyridine, quinoline, imidazole, indole, pyrimidine, hexamethyldisilazane, hydrazine, diazabicycloundecene, diazabicyclononene, etc.
  • the amine compound may be a single type or a mixture of two or more types.
  • the concentration of the amine compound in the aqueous solution is set to an optimal concentration and pH depending on the type of raw material, and the solution is stirred.
  • the liquid temperature during dissolution is also adjusted. Since some of the compound remains undissolved during dissolution, filtration is also added as necessary.
  • the dissolved components of the raw material solution which is prepared by dissolving them in a basic solution, are solidified to prepare a solidified product (the "solidification process").
  • an acidic solution is added to prepare a solidified product.
  • the raw material solution is basic, and adding an acidic solution to it promotes neutralization of the acid and base, resulting in the formation of a precipitate. This precipitate becomes the desired solidified product.
  • the resulting solidified product is washed with water and dried.
  • acidic solutions that can be used include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, formic acid, and organic acids such as citric acid. Of these, acetic acid is preferred as the acidic solution due to its tendency to volatilize and decompose in subsequent processes.
  • the solidified material After drying, the solidified material is calcined to form a calcined product, and excess moisture such as bound water is removed (the "calcination process").
  • the calcination temperature is 300 to 1200°C, and the calcination time is 1 to 3 hours.
  • the silicon hydroxide produced by precipitation is oxidized to silicon oxide (silica) through calcination.
  • the fired product produced by the firing process is pulverized to prepare a pulverized product (the "pulverization process").
  • Either wet pulverization or dry pulverization may be used for pulverization.
  • known devices for pulverizing solids such as ball mills, vibration mills, jet mills, and atomizers, are used as pulverizers.
  • the solidified product and alumina balls are placed in a pulverization pod, and the pod is rotated to perform wet pulverization. The rotation time of the pod (pulverization time) is adjusted according to the target particle size.
  • the pulverized product collected from the pod is dried by spray drying or the like.
  • the purpose of the crushing process is to control the particle size before the subsequent melt-spheroidizing process.
  • the sintered product is amorphous and not uniform in size due to the fusion of particles. If the product is sent to the melt-spheroidizing process in this state, particles with a wide range of particle sizes will be produced. In addition, it will be difficult to obtain a spherical shape due to the non-uniform shape. This results in a high yield during the process (a decrease in yield).
  • the average particle size of the pulverized material means the median diameter ( D50 ) measured by a known particle size measurement method such as a laser diffraction scattering method or a dynamic scattering method. Therefore, the average particle size ( D50 ) of the pulverized material is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less. By making the particle size finer, melting in the melt-spheroidizing step becomes easier.
  • the pulverized material prepared in the pulverization process is put into a flame, and the pulverized material flies through the flame.
  • the pulverized material i.e., spherical silica particles, melts when exposed to the flame, and the surface tension during melting promotes spheroidization to obtain spherical particles ("melt spheroidization process").
  • the spherical particles thus obtained are the oxide particles.
  • the spherical particles also have a suitable particle size.
  • the average particle size ( D50 ) of the spherical particles is 30 ⁇ m or less, more preferably 20 ⁇ m or less.
  • the average particle size (D50) of the spherical particles also means the median size ( D50 ) measured by a known particle size measurement method such as a laser diffraction scattering method or a dynamic scattering method.
  • the flame in the melting and spheroidizing process is formed by mixing combustible gas with a combustion supporting gas containing oxygen and burning it.
  • the temperature of the furnace's refractory structure is in the range of 900°C to 1500°C at the highest point (furnace body temperature).
  • the furnace body temperature preferably has a lower limit of 900°C to 1100°C and an upper limit of 1300°C to 1500°C.
  • Air and oxygen are used as the combustion supporting gas.
  • the flow rate of the combustible gas is preferably 10 m/s or more, more preferably 15 m/s or more, and even more preferably 20 m/s or more.
  • the flow rate of the combustion supporting gas is preferably 10 m/s or more, more preferably 15 m/s or more, and even more preferably 20 m/s or more.
  • the flow rate ratio of combustible gas/combustion supporting gas is preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.0 or less.
  • the supply amounts of the combustible gas and the combustion supporting gas are determined by the amount of the combustible gas that can form a flame large enough to sufficiently heat the raw material particles to be supplied, and the amount of the combustion supporting gas that can sufficiently combust the combustible gas.
  • the amount of the combustible gas is 0.5 Nm 3 /kg to 5 Nm 3 /kg per unit weight of the pulverized material to be processed, and the amount of oxygen as the combustion supporting gas is about 1 Nm 3 /kg to 5 Nm 3 /kg.
  • the method for supplying the raw material particles into the flame is not particularly limited, and the raw material particles are supplied to the flame in a dispersed state in a carrier gas.
  • the carrier gas include air, oxygen, and nitrogen.
  • the spherical silica particles produced from the raw material silicon metal through the melting, solidification, firing, crushing, and melt-spheroidizing processes have a significantly reduced total amount of uranium and thorium elements compared to the raw material stage.
  • the spherical silica particles that are the embodiment of the high purity fused spherical silica of the embodiment have a uranium (U) content of 5 ppb or less, and a thorium (Th) content of 5 ppb or less. This content is reduced to 1/10 or less, or even 5/100 or less, of the total amount of uranium and thorium contained in the raw material. This makes it possible to further reduce the dose of particle rays such as alpha rays and beta rays, and electromagnetic waves such as gamma rays, emitted from the nuclides in the spherical silica particles, thereby reducing the impact on electronic components, etc.
  • particle rays such as alpha rays and beta rays
  • electromagnetic waves such as gamma rays
  • the raw silicon metal When the raw silicon metal is dissolved in the basic solution, the original raw material changes from metal to hydroxide. At this point, the amount of impurities contained in the raw material is thought to be less than the amount of silicon metal that dissolves in the basic solution.
  • Heavy elements such as U (uranium) and Th (thorium) are not amphoteric elements, so they are difficult to dissolve in basic solutions and remain as insoluble components. This ease of dissolution in basic solutions makes it possible to separate impurity components such as uranium and thorium elements. This makes it possible to reduce impurities even further than in the previous preparation of oxides for fillers.
  • the sodium (Na) content in the spherical silica particles is 10 ppm or less.
  • the sodium content is mentioned because it is a representative impurity component, and if the sodium content is low, it can be determined that the amounts of other impurities are also low. Because an amine compound is used when dissolving the raw silicon metal in a basic solution, there is almost no residual alkali metal such as sodium hydroxide. Also, because the raw silicon metal is dissolved in a basic solution, the dissolution of impurities is suppressed and the purity is increased, as mentioned above.
  • each spherical silica particle is 0.98 or more, and the shape is extremely similar to a sphere.
  • the circularity of a perfect sphere (true sphere) is 1.0.
  • the circularity is evaluated by calculating the ratio of the length of the short axis to the long axis (aspect ratio), the ratio of the circle equivalent diameter to the maximum diameter, and the like. In the embodiment described below, measurements were taken using a flow-type particle image analyzer. The closer the circularity of the spherical silica particles is to a true sphere, the easier it is to fill the coating material into circuit boards, etc. after mixing with resin and preparing it into a sealing material, etc.
  • the residual crystal rate of silicon oxide (silicon dioxide: SiO 2 ) in the spherical silica particles is 0.01% or less, preferably below the detection limit.
  • the spherical silica particles are mainly formed of amorphous silicon oxide. A small amount of crystalline silicon oxide may be present in the particles.
  • the residual crystal rate indicates the weight ratio of crystalline silicon oxide to the total weight of the spherical silica particles.
  • the presence of crystalline silicon oxide affects the conductivity as a filler.
  • findings suggesting the carcinogenicity of crystalline silicon oxide (silica) have been reported, so it is desirable to suppress crystalline silicon oxide as much as possible in order to reduce the impact.
  • the number of hollows with a diameter of 5 ⁇ m or more present in each spherical silica particle is 2 or less, preferably 1 or less, more preferably 0, in an observation area of 9 mm2 by an electron microscope. If an extremely large hollow part (void, bubble) exists in a spherical silica particle, the conductivity of the spherical silica particle near the hollow part will change. In other words, the insulating property may be reduced by the hollow part, and the performance as a filler used in a sealing material may be reduced. Therefore, it is desirable to reduce the hollow part in the spherical silica particle as much as possible to densify the particle itself.
  • the number and size (diameter) of hollow spaces inside the spherical silica particles were observed under magnification using an electron microscope. Note that when observing the number of hollow spaces with a diameter of 5 ⁇ m or more, the magnification of the electron microscope was set to 2000 times.
  • the high-purity fused spherical silica (spherical silica particles) of the embodiments described so far is mainly used as a filler for electronic materials.
  • the high-purity fused spherical silica (spherical silica particles) is added to a resin to prepare a resin composition for electronic devices (resin composition containing filler for electronic materials).
  • Resins to which it can be added include thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, other olefin resins, polyimide resins, and liquid crystal polymers, fluororesins, urea resins, phenolic resins, and thermosetting resins such as polyphenylene ether and bismaleimide. It can also be added to elastic resins such as styrene butadiene rubber and isoprene rubber, silicone resins, and the like. For example, epoxy resins are used as resins when manufacturing resin substrates such as packaging substrates for electronic components and interlayer insulating films.
  • thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polystyrene, other olefin resins, polyimide resins, and liquid crystal polymers, fluororesins, urea resins, phenolic resins, and thermosetting
  • Epoxy resins used in the resin composition include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol novolac type epoxy resins, naphthalene type epoxy resins, and phenoxy type epoxy resins.
  • the weight of high-purity fused spherical silica (spherical silica particles) blended into the resin composition is preferably large from the viewpoints of heat resistance and thermal expansion coefficient. It is desirable to add 80 mass% or more of high-purity fused spherical silica (spherical silica particles) to the total mass of the resin composition.
  • the high purity fused spherical silica (spherical silica particles) of the embodiment i.e., the filler for electronic materials
  • the filler for electronic materials can be prepared as a slurry for electronic materials by dispersing the filler for electronic materials and having a liquid dispersion medium that is substantially free of moisture.
  • a solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, toluene, N-methylpyrrolidone, ⁇ -butyrolactone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.
  • the dispersion medium can also be used alone or in combination. It is also possible to use an appropriate dispersant.
  • the characteristic property of the resin composition for electronic devices is that it is possible to reduce the dose of particle rays and electromagnetic waves emitted from the silica particles contained in the resin composition. This makes it possible to reduce the effects of particle rays and electromagnetic waves on electronic components and the like from the processed parts of the resin composition. As a result, it is expected that disturbance factors such as noise will be suppressed and problems such as malfunctions of equipment will be reduced.
  • the properties of the high-purity fused spherical silica (spherical silica particles) itself make it possible to satisfy the effects of kneading with resin and suppressing electrical conductivity.
  • the high-purity fused spherical silica (spherical silica particles) of the embodiment is also suitable for use as an additive to cosmetics.
  • the content of heavy elements such as U (uranium) and Th (thorium) is extremely low, so the dose of natural radiation caused by the high-purity fused spherical silica (spherical silica particles) is suppressed, and the impact of exposure to the human body is suppressed.
  • U uranium
  • Th thorium
  • the properties of crystalline silicon oxide (silica) have begun to be viewed as problematic, so the high-purity fused spherical silica (spherical silica particles) of the embodiment is highly effective in reducing the impact due to the reduction in crystallinity, and is promising as an alternative material to existing cosmetic additives such as microplastics.
  • the cosmetics are not particularly limited as long as they are in a form that can be applied to the skin, such as a powder, ointment, lotion, cream, etc.
  • the cosmetic is an ointment
  • the high-purity fused spherical silica is added to and kneaded with a base material of oil and fat components such as petrolatum.
  • the cosmetic is an lotion or cream
  • the high-purity fused spherical silica is added to a base material of water, alcohol, glycerin, various oils and fats, etc., and homogenized.
  • the cosmetic When the cosmetic is a powder, it is assumed that it will be added to, for example, a foundation, and it is added to and kneaded with oils and fats, wax, moisturizers, water, etc. Of course, when preparing it as a cosmetic, surfactants, preservatives such as paraben, fragrances, etc. are blended as necessary.
  • test examples 1 to 15 were prepared and the physical properties of each test example were evaluated. The following describes the raw materials used, the production method, and the measurement and evaluation methods in that order. For details of each prototype example, see Tables 1 to 4 below.
  • Metallic silicon and silicon oxide powder (silica powder, crystalline silica) were used as raw materials.
  • the raw materials used in each test example are shown in the table.
  • the metallic silicon powder used in Test Examples 1 to 10 had an average particle size of 20 ⁇ m.
  • the crystalline silica used in Test Examples 11 to 15 had an average particle size of 30 ⁇ m.
  • TMAH Tetramethylammonium hydroxide
  • DBU Diazabicycloundecene
  • the pH was adjusted by adding 90% acetic acid solution dropwise to the basic silicic acid solution while stirring, and stirring was continued.
  • the precipitate was collected and dried at 120°C, then fired at 800°C for 2 hours. Note that firing was omitted for test example 3.
  • the resulting fired product, an appropriate amount of silica powder and water, and alumina balls with a particle size of 5 mm were placed in a grinding pod made of high-purity alumina, and grinding continued until the target particle size was reached.
  • the ground product was then collected using a 4 mm sieve and appropriately dried. The difference between each test example was the particle size during grinding, which was created by adjusting the grinding time.
  • Test Examples 9 and 10 dimethylamine was replaced with TMAH, and the amounts and treatments of the reagents were the same as in Test Example 6.
  • Test Example 10 dimethylamine was replaced with DBU, and the amounts and treatments of the reagents were the same as in Test Example 6.
  • Test Examples 11 to 15 are control groups in which the process of dissolving in a basic solution and neutralizing is omitted, and the raw material is crushed and exposed to flame.
  • the crushing method is the same as when the high-purity alumina pot described above is used, and the crushing time is adjusted to produce different samples.
  • the exposure to flame is also the same.
  • Test Example 16 described in Table 4 is a sample prepared from silicon metal powder by a method of producing spherical oxide fine particles by utilizing the deflagration phenomenon of metal powder, known as the VMC method (Vaporized Metal Combustion Method).
  • BET specific surface area 1.0 g of spherical silica particles of each test example was weighed out and placed in a measurement cell. After pretreatment, the BET specific surface area was measured by nitrogen adsorption. For the measurement, an automatic specific surface area/pore distribution measuring device TriStar (registered trademark)-II3020 manufactured by Shimadzu Corporation was used. The pretreatment was carried out under the following conditions. Degassing temperature: 200°C Degassing time: 30 minutes Cooling time: 4 minutes
  • IPC inductively coupled plasma atomic emission spectrometry
  • ICP-MS for U and Th
  • ICP-OES for silica and other impurities
  • ICP-AES for alumina and other impurities
  • Circularity Measurement A flow type particle image analyzer (FPIA-3000) manufactured by Sysmex Corporation was used. Sodium hexametaphosphate was dissolved in sheath liquid (particle sheath "PSE-900A") to prepare a solution, and the spherical silica particles of each test example were mixed into the solution, and after ultrasonic dispersion, the solution was subjected to measurement. The measurement was performed using the H mode of the same device.
  • Crystalline silica content SmartLab (registered trademark) manufactured by Rigaku Corporation was used as an X-ray crystal structure analyzer (XRD).
  • XRD X-ray crystal structure analyzer
  • the peak intensity value at 2 ⁇ 26.6 ° was obtained for the spherical silica particle samples of each test example.
  • the peak intensity value at 2 ⁇ 26.6 ° of 100% crystalline silica was obtained.
  • the peak intensity value of each test example sample was then divided by the peak intensity value of crystalline silica to obtain a quotient, which was expressed as a percentage.
  • the spherical silica particles of each test example were added to an epoxy resin, and a hardener was added and mixed to prepare a resin mixture. At this time, the spherical silica particles (i.e., the filler component) were equivalent to 75% by weight of the resin mixture.
  • the resin mixture of each test example was heated to 170°C and hardened. After hardening, the resin was cut and the cut surface was polished.
  • An ion milling device (IM4000Plus, manufactured by Hitachi High-Tech Corporation) was used to polish the cut surfaces. After polishing, osmium oxide gas was introduced to apply an osmium coat to the polished surfaces of each test example. Then, the polished surfaces of each test example were observed using an electron microscope (SEM). The observation range of the electron microscope was 9 mm2 , and the number of particles containing hollows (voids) in spherical silica particles with a diameter (major axis) of 5 ⁇ m or more within the same range was counted. Then, the number of particles containing hollows (voids) in spherical silica particles with a diameter (major axis) of 5 ⁇ m or more was counted.
  • Tables 1 to 3 The results of Test Examples 1 to 15 are shown in Tables 1 to 3. In each table, from the top, the type of raw material, the amount of uranium and thorium in the raw material (ppb), the type of base, the ratio of base to silicon (mol), the yield (%), the calcination temperature (°C), the particle size after grinding and after melting ( D10 , D50 , D90 in ⁇ m), the specific surface area ( m2 /g), the amount of sodium after melting (ppm), the amount of uranium and thorium after melting (ppb), the circularity, the crystal residual rate (%), and the number of hollows of 5 ⁇ m or more when magnified 2000 times by an electron microscope (pieces/9 mm2 ) are shown. Table 4 shows the composition analysis of the contained elements (expressed in ppb and ppm).
  • Figure 1 shows Test Example 4 after crushing (5,000x) and after melting (10,000x).
  • Figure 2 shows a cross section of Test Example 6, with electron microscope photographs (2,000x) of different observation areas.
  • Figure 3 shows a cross section of Test Example 13, with electron microscope photographs (2,000x) of different observation areas.
  • Test Examples 9 and 10 show that the types of amine compounds that can be used when preparing a basic solution can be expanded. Selection can be made taking into consideration the type of raw material to be dissolved, ease of dissolution (reactivity), raw material costs, etc.
  • Test Examples 1 to 10 (excluding Test Example 3) and Test Examples 11 to 15 was 0.98, which is extremely close to a perfect sphere.
  • Test Examples 1 to 10 could be made to have a high circularity from an amorphous state by dissolving them in a basic solution. The more spherical the filler, the better the fluidity of the coating material, which is preferable.
  • the residual rate of silicon oxide crystals was below the measurement limit in Test Examples 1 to 10 (except Test Example 3), and can be considered to be practically non-existent.
  • the rate of hollow spaces of 5 ⁇ m or more was below the measurement limit in Test Examples 1 to 10 (except Test Example 3), and can be considered to be practically non-existent.
  • high-purity fused spherical silica for use as a filler in resin compositions for electronic devices, it contains few impurities, including uranium and thorium, making it possible to reduce the radiation source associated with radioactive decay. It is also extremely nearly spherical, making it easier to ensure the fluidity of the coating. Furthermore, there are no relatively large hollow spaces (voids) in the particles, so insulation and other performance properties are also guaranteed.
  • high-purity fused spherical silica for use in cosmetics it contains few impurities, including uranium and thorium, and also contains little crystalline silica, making it highly valuable as an additive for cosmetics that are applied directly to the skin.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Silicon Compounds (AREA)
  • Cosmetics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne : une silice sphérique fusionnée de haute pureté qui réduit la quantité d'impuretés contenues dans des particules de silice servant de charge à ajouter à un matériau d'étanchéité, améliore les propriétés de malaxage par rapport à une résine servant de matériau d'étanchéité, et supprime des parties creuses dans les particules en vue de réguler la conductivité des particules de silice elles-mêmes ; et une composition de résine pour un dispositif électronique et un produit cosmétique qui le contiennent. La teneur en uranium dans les particules sphériques de silice est de maximum 5 ppb, la teneur en thorium dans les particules sphériques de silice est de maximum 5 ppb, la circularité des particules sphériques de silice est de minimum 0,98, le rapport résiduel cristallin de l'oxyde de silicium dans les particules sphériques de silice est de maximum 0,01 %, et le nombre de parties creuses, qui ont un diamètre d'au moins 5 µm et sont présentes dans chaque particule des particules sphériques de silice, est de maximum deux dans une plage d'observation de 9 mm2 telle qu'observée au moyen d'un microscope électronique.
PCT/JP2024/021304 2023-06-14 2024-06-12 Silice sphérique fusionnée de haute pureté, composition de résine pour dispositif électronique la contenant, et produit cosmétique la contenant Pending WO2024257788A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023097977A JP2024179264A (ja) 2023-06-14 2023-06-14 高純度溶融球状シリカ、及びこれを含む電子機器用樹脂組成物、並びにこれを含む化粧品
JP2023-097977 2023-06-14

Publications (1)

Publication Number Publication Date
WO2024257788A1 true WO2024257788A1 (fr) 2024-12-19

Family

ID=93852146

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/021304 Pending WO2024257788A1 (fr) 2023-06-14 2024-06-12 Silice sphérique fusionnée de haute pureté, composition de résine pour dispositif électronique la contenant, et produit cosmétique la contenant

Country Status (3)

Country Link
JP (1) JP2024179264A (fr)
TW (1) TW202500508A (fr)
WO (1) WO2024257788A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01230422A (ja) * 1988-03-10 1989-09-13 Nippon Chem Ind Co Ltd 高純度シリカ及びその製造方法
JPH03223107A (ja) * 1990-01-30 1991-10-02 Nitto Chem Ind Co Ltd 球状シリカの製造方法
JPH1160234A (ja) * 1997-08-08 1999-03-02 Denki Kagaku Kogyo Kk 低ウラン球状シリカ粉末の製造方法、及びシリカ粉末
JP2010052974A (ja) * 2008-08-27 2010-03-11 Jgc Catalysts & Chemicals Ltd 球状シリカ系粒子、その製造方法および該シリカ系粒子を含有してなる化粧料
JP2012206870A (ja) * 2011-03-29 2012-10-25 Admatechs Co Ltd 球状シリカ粉体の製造方法及び半導体封止材の製造方法
JP2015117138A (ja) * 2013-12-16 2015-06-25 株式会社アドマテックス シリカ粒子の製造方法
JP2022523589A (ja) * 2019-03-12 2022-04-25 浙江三時紀新材科技有限公司 球状のシリカ粉末フィラーの製造方法ならびにこれによって得られた球状のシリカ粉末フィラーおよびその応用
JP2023520185A (ja) * 2020-03-27 2023-05-16 ソッキョン エイ ティー シーオー エルティディー 大口径ＳｉＯ２粉末の製造方法及びそれを含む化粧料組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01230422A (ja) * 1988-03-10 1989-09-13 Nippon Chem Ind Co Ltd 高純度シリカ及びその製造方法
JPH03223107A (ja) * 1990-01-30 1991-10-02 Nitto Chem Ind Co Ltd 球状シリカの製造方法
JPH1160234A (ja) * 1997-08-08 1999-03-02 Denki Kagaku Kogyo Kk 低ウラン球状シリカ粉末の製造方法、及びシリカ粉末
JP2010052974A (ja) * 2008-08-27 2010-03-11 Jgc Catalysts & Chemicals Ltd 球状シリカ系粒子、その製造方法および該シリカ系粒子を含有してなる化粧料
JP2012206870A (ja) * 2011-03-29 2012-10-25 Admatechs Co Ltd 球状シリカ粉体の製造方法及び半導体封止材の製造方法
JP2015117138A (ja) * 2013-12-16 2015-06-25 株式会社アドマテックス シリカ粒子の製造方法
JP2022523589A (ja) * 2019-03-12 2022-04-25 浙江三時紀新材科技有限公司 球状のシリカ粉末フィラーの製造方法ならびにこれによって得られた球状のシリカ粉末フィラーおよびその応用
JP2023520185A (ja) * 2020-03-27 2023-05-16 ソッキョン エイ ティー シーオー エルティディー 大口径ＳｉＯ２粉末の製造方法及びそれを含む化粧料組成物

Also Published As

Publication number Publication date
JP2024179264A (ja) 2024-12-26
TW202500508A (zh) 2025-01-01

Similar Documents

Publication Publication Date Title
US11912847B2 (en) Spherical magnesium oxide, manufacturing method thereof, thermal conductive filler and resin composition
CN113677458A (zh) 混合银粉和包含其的导电糊
TW201202144A (en) Method for producing spherical alumina powder
US20250339897A1 (en) Method of producing silver powder
JP2003238141A (ja) 表面改質球状シリカ及びその製造方法、並びに半導体封止用樹脂組成物
WO2024257755A1 (fr) Particule d'alumine de haute pureté et sa méthode de production, et composition de résine pour dispositifs électroniques et sa méthode de production
TW202419399A (zh) 球狀矽石粒子、漿料組成物、樹脂組成物及球狀矽石粒子的製造方法
WO2019177112A1 (fr) Poudre et poudre mélangée
KR101394808B1 (ko) 비정질 실리카질 분말, 그 제조 방법 및 반도체 봉지재
WO2024257788A1 (fr) Silice sphérique fusionnée de haute pureté, composition de résine pour dispositif électronique la contenant, et produit cosmétique la contenant
WO2013146223A1 (fr) Particules d'hydroxyde de magnésium et composition de résine contenant celles-ci
US20250100890A1 (en) Method for producing spherical silica powder
WO2024257754A1 (fr) Méthode de production de particules d'oxyde et méthode de production d'une composition de résine pour dispositifs électroniques
TW202419400A (zh) 球狀矽石粒子的製造方法
TW202408939A (zh) 氧化鎂粉末及使用其之樹脂組成物
CN118510725A (zh) 氧化镁颗粒及其制造方法
JP7584225B2 (ja) 熱伝導性樹脂組成物用アルミナフィラー、熱伝導性樹脂組成物、および熱伝導性樹脂組成物用アルミナフィラーの製造方法
TW201908241A (zh) 矽酸鹽化合物微粒子及其製造方法
WO2025258248A1 (fr) Composition inorganique sphérique, composition de résine, composition de barbotine, charge pour matériau d'étanchéité de boîtier de semi-conducteur, et procédé d'analyse des vides dans une composition inorganique sphérique
WO2025173531A1 (fr) Composition de silice sphérique, composition de résine, composition de boue, charge pour matériau de scellement pour boîtier semi-conducteur, et procédé d'analyse de vides dans une composition de silice sphérique
JP2023120508A (ja) 粉末及び粉末の製造方法
TW202506543A (zh) 氮化鋁粉末
KR20250106299A (ko) 구형 질화 붕소 분말, 수지용 충전제, 수지 조성물 및 구형 질화 붕소 분말의 제조 방법
WO2025258651A1 (fr) Procédé de production de particules de silice calcinées et particules de silice
WO2025249332A1 (fr) Poudre d'argent sphérique, procédé de production de la poudre d'argent sphérique et pâte conductrice

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: 24823403

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE