[go: up one dir, main page]

WO2024202735A1 - Poudre de nitrure de silicium et composition de résine faisant appel à celle-ci - Google Patents

Poudre de nitrure de silicium et composition de résine faisant appel à celle-ci Download PDF

Info

Publication number
WO2024202735A1
WO2024202735A1 PCT/JP2024/006300 JP2024006300W WO2024202735A1 WO 2024202735 A1 WO2024202735 A1 WO 2024202735A1 JP 2024006300 W JP2024006300 W JP 2024006300W WO 2024202735 A1 WO2024202735 A1 WO 2024202735A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon nitride
nitride powder
atom
powder
less
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/JP2024/006300
Other languages
English (en)
Japanese (ja)
Inventor
上原 みちる 大門
邦彦 中田
和人 原田
好晴 鏡
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.)
Combustion Synthesis Co Ltd
Sumitomo Chemical Co Ltd
Original Assignee
Combustion Synthesis Co Ltd
Sumitomo Chemical 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 Combustion Synthesis Co Ltd, Sumitomo Chemical Co Ltd filed Critical Combustion Synthesis Co Ltd
Priority to KR1020257035321A priority Critical patent/KR20250165636A/ko
Priority to CN202480018109.XA priority patent/CN120858072A/zh
Publication of WO2024202735A1 publication Critical patent/WO2024202735A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • 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

Definitions

  • This disclosure relates to silicon nitride powder and a resin composition using the same.
  • Heat generated by passing current through an electronic component is dissipated via a heat sink.
  • a technique is known in which a heat dissipation material is filled between the electronic component and the heat sink.
  • One type of heat dissipation material is a resin composition containing a resin and inorganic particles, and it is known that silicon nitride powder can be used as the inorganic particles (for example, Patent Document 1).
  • Patent Document 2 discloses silicon nitride powder for other applications.
  • Patent Document 2 discloses silicon nitride powder having an internal oxygen content of 0.6 mass % or less as a silicon nitride powder from which a silicon nitride sintered body having high thermal conductivity can be obtained.
  • one embodiment of the present invention aims to provide a silicon nitride powder that is used as a filler for a resin composition and that exhibits water resistance. Furthermore, another embodiment of the present invention aims to provide a resin composition that uses the silicon nitride powder according to one embodiment.
  • Aspect 1 of the present invention is The silicon nitride powder contains a plurality of silicon nitride particles and satisfies the following formula (1): 0% ⁇
  • X (nm) is the thickness of the SiO2 coating converted from the total oxygen content TO (mass%) of the silicon nitride powder
  • Y (nm) is the thickness of the SiO2 coating converted from the surface oxygen ratio SO (atom%) of the silicon nitride particles.
  • Aspect 2 of the present invention is The silicon nitride powder according to aspect 1, which satisfies the following formula (2): 0 ⁇ X(nm) ⁇ 50.0 (2)
  • Aspect 3 of the present invention is The silicon nitride powder according to aspect 1 or 2, which satisfies the following formula (3): SO(atom%)/SA( m2 /g)>10.1(atom% /(m2 /g)) (3)
  • SA (m 2 /g) is the specific surface area of the silicon nitride powder.
  • Aspect 4 of the present invention is The silicon nitride powder according to any one of aspects 1 to 3, wherein the total oxygen content TO (mass%) of the silicon nitride powder satisfies the following formula (4): TO (mass%) ⁇ 1.21 (4)
  • Aspect 5 of the present invention is The silicon nitride powder according to any one of Aspects 1 to 4, wherein the surface oxygen ratio SO (atom %) of the silicon nitride particles satisfies the following formula (5): SO(atom%)>10.0 (5)
  • Aspect 6 of the present invention is A silicon nitride powder according to any one of Aspects 1 to 5, having a specific surface area of less than 2.66 m 2 /g.
  • Aspect 7 of the present invention is The silicon nitride powder according to any one of Aspects 1 to 6, having a surface roughness Ra of less than 0.97 nm.
  • Aspect 8 of the present invention is The silicon nitride powder according to any one of Aspects 1 to 7, wherein the ⁇ -formation rate is 65% or more.
  • Aspect 9 of the present invention is The silicon nitride powder according to any one of aspects 1 to 8, wherein the ratio (L2/L1) of the total length L2 of the internal boundary lines to the length L1 of the outer edge is 1% or less, and the maximum particle size of the silicon nitride particles is 6.8 ⁇ m or more.
  • Aspect 10 of the present invention is A resin composition comprising a resin and the silicon nitride powder according to any one of Aspects 1 to 9.
  • the silicon nitride powder according to one embodiment of the invention can exhibit sufficient water resistance by controlling the ratio of the amount of oxygen present on the particle surface to the amount of oxygen present in the entire powder.
  • a resin composition according to another embodiment of the present invention can exhibit high water resistance because it uses the silicon nitride powder according to one embodiment.
  • Silicon nitride powder The present inventors have conducted extensive research to obtain silicon nitride powder that can achieve excellent water resistance. They have found that silicon nitride powder with excellent water resistance can be obtained by significantly localizing oxygen on the surface of the silicon nitride particles that constitute the silicon nitride powder. In order to indirectly know the water resistance of the silicon nitride powder, the present inventors have newly introduced an index that indicates the degree of surface localization of oxygen, and have made it possible to obtain silicon nitride powder with high water resistance based on the index.
  • the silicon nitride powder according to the embodiment includes a plurality of silicon nitride particles and further satisfies the following formula (1): 0% ⁇
  • X (nm) is the thickness of the SiO2 coating converted from the total oxygen content TO (mass%) of the silicon nitride powder
  • Y (nm) is the thickness of the SiO2 coating converted from the surface oxygen ratio SO (atom%) of the silicon nitride particles.
  • the method of calculating the thicknesses X and Y will be described in detail later.
  • /Y ⁇ 100" (%) written in the middle of formula (1) is a new index that indicates the degree to which oxygen is localized on the surface of silicon nitride particles. This is called the "oxygen localization index.”
  • the thickness X is the thickness of the SiO2 coating calculated from the total oxygen content TO (mass%) of the silicon nitride powder. If a large amount of oxygen is contained inside the silicon nitride particle, the thickness X becomes large.
  • the thickness Y is the thickness of the SiO2 coating calculated from the oxygen content (surface oxidation rate SO) contained on the surface of the silicon nitride particle (up to a depth of about 10 nm). Even if a large amount of oxygen is contained inside the silicon nitride particle (parts other than the surface), the effect on the thickness Y is small.
  • the present inventors have found that when the oxygen localization index is equal to or greater than 0% and less than 240.0%, the effect of oxygen localizing on the surface is exerted, and the water resistance of the silicon nitride powder can be improved.
  • the oxygen localization index is preferably 0% or more and 230.0% or less, more preferably 0.01% or more and 220.0% or less, even more preferably 0.1% or more and 200.0% or less, still more preferably 0.5% or more and 180.0% or less, and particularly preferably 1.0% or more and 170.0% or less.
  • the total oxygen content TO (mass%) of the silicon nitride powder refers to the total amount of oxygen in the silicon nitride powder, and is measured by an inert gas fusion-infrared absorption method in accordance with JIS G 1239:2014.
  • the total oxygen content TO (mass %) of the silicon nitride powder can be set to, for example, less than 1.21 mass % (i.e., satisfying the following formula (4)). TO (mass%) ⁇ 1.21 (4)
  • the total oxygen content TO (mass%) of the silicon nitride powder may be 1.00 mass% or less, 0.70 mass% or less, 0.60 mass% or less, or even 0.50 mass% or less.
  • the lower limit of the total oxygen content TO is not particularly limited, but in order to better exert the effect of water resistance, it is preferably 0.05 mass% or more, more preferably 0.10 mass% or more, even more preferably 0.20 mass% or more, and particularly preferably 0.25 mass% or more.
  • the method for converting the total oxygen content TO (mass%) of the silicon nitride powder into the thickness X (nm) of the SiO2 coating is as follows. First, it is assumed that the silicon nitride particles constituting the silicon nitride powder are composed of spheres made of Si3N4 and SiO2 unevenly distributed on the surface, and that the volume density of Si3N4 and SiO2 are the same. In addition, the particle size D50 of the cumulative 50% from the fine particle side of the cumulative particle size distribution on a volume basis is used as the silicon nitride particle size. The method for measuring D50 will be described later.
  • silicon content l (mol%), oxygen content m (mol%), and nitrogen content n (mol%) relative to the total oxygen content TO (mass%) in silicon nitride can be calculated as follows:
  • the proportions (mol %) of the amounts of substance occupied by Si 3 N 4 and SiO 2 in the silicon nitride can be calculated from the following formulas (16) and (17).
  • the film thickness (thickness X) of the SiO2 coating is expressed by the following formula (19) using the particle diameter D50 (nm).
  • SiO2 coating thickness (thickness X) (nm) D50 ⁇ (1-k) / 2 (19)
  • equations (14) and (15) into equation (18) the thickness of the SiO2 coating can be calculated.
  • the thickness X (nm) of the SiO2 coating calculated from the total oxygen content TO (mass%) of the silicon nitride powder, is preferably more than 0 nm and less than 50 nm. In other words, it is preferable to satisfy the following formula (2).
  • Such silicon nitride powder can have improved water resistance.
  • the thickness X is more preferably greater than 0 nm and equal to or less than 30 nm, even more preferably 0.5 nm or more and 15.0 nm or less, even more preferably 1.0 nm or more and 11.0 nm or less, even more preferably 3.0 nm or more and 10.0 nm or less, even more preferably 6.1 nm or more and 10.0 nm or less, and particularly preferably 7.1 nm or more and 10.0 nm or less.
  • the surface oxygen ratio SO (atom%) of silicon nitride particles refers to the amount of oxygen localized on the surface of silicon nitride particles contained in silicon nitride powder.
  • XPS measurement of silicon nitride powder (more precisely, silicon nitride particles) is performed to measure the content of each element of Si, N, C, and O present on the silicon nitride particle surface.
  • the surface oxygen ratio SO (atom%) is the content (atom%) of O element when the total content of these four elements is 100 atom%. That is, SO can be calculated by the following equation (20).
  • the measurement target of the XPS measurement is the portion from the surface of the silicon nitride particle to a depth of 10 nm, and it is considered that the elements contained in the XPS measurement portion are all detected with equal intensity regardless of the depth from the surface.
  • the XPS measurement of the silicon nitride particle surface is performed, for example, using a JFS-9010 model manufactured by JEOL Ltd., with excitation X-ray: AlK ⁇ , X-ray output of 110 W, photoelectron escape angle of 45 degrees, and pass energy of 50 EV to measure the contents of the elements Si, N, C, and O on the silicon nitride particle surface.
  • the surface oxygen ratio SO (atom %) of the silicon nitride particles is preferably, for example, more than 10.0 atom % (i.e., satisfying the following formula (5)). This increases the amount of localized oxygen present on the surface of the silicon nitride particles, and can improve the water resistance of the silicon nitride powder.
  • the surface oxygen ratio SO (atom%) of the silicon nitride particles may be 11.0 atom% or more, 13.0 atom% or more, 15.0 atom% or more, or 20.0 atom% or more.
  • the upper limit of the surface oxygen ratio SO of the silicon nitride particles is not particularly limited, but is, for example, 60.0 atom% or less.
  • the method for converting the surface oxygen ratio SO (atom%) of the silicon nitride particles into the thickness Y (nm) of the SiO2 coating is as follows. First, among the elements measured by XPS, all N elements are derived from Si3N4 , and all O elements are derived from SiO2 . It is assumed that the film is composed of spheres made of Si3N4 and SiO2 unevenly distributed on the surface, and that the volume density of Si3N4 and SiO2 are the same. It is also assumed that the film thickness of the SiO2 film and the Si3N4 film are proportional to the Si content contained in each film. Based on these assumptions, equation (21) is obtained.
  • the measurement results of the N content [N] (atom%) and the O content [O] (atom%) on the surface of the silicon nitride particles are substituted into the following formula (21) to determine the thickness Y (nm) of the SiO2 coating.
  • Y (nm) 10 x ([O]/2)/(3[N]/4+[O]/2) (21)
  • “[O]/2” is the content (atom%) of silicon derived from SiO2
  • "3[N]/ 4 " is the content (atom%) of silicon derived from Si3N4
  • “([O]/2)/(3[N]/4+[O]/2)” is the ratio of the content of silicon derived from SiO2 to the total content of silicon.
  • the thickness Y is preferably 1.0 nm or more, more preferably 1.5 nm or more, even more preferably 2.0 nm or more, even more preferably 2.6 nm or more, and particularly preferably 3.6 nm or more.
  • the value (SO/SA value) obtained by dividing the surface oxygen ratio SO (atom%) of the silicon nitride particles by the specific surface area SA ( m2 /g) of the silicon nitride powder is preferably more than 10.1 (atom%/( m2 /g)) (i.e., satisfying the following formula (3)). If the value of SO/SA is large, that is, if the amount of surface oxygen per unit specific surface area is large, the oxide film will become thicker, and it is expected that the water resistance will improve. SO(atom%)/SA( m2 /g)>10.1(atom% /(m2 /g)) (3)
  • SO/SA is more preferably 11.0 (atom %/(m 2 /g)) or more, even more preferably 15.0 (atom %/(m 2 /g)) or more, still more preferably 20.0 (atom %/(m 2 /g)) or more, and particularly preferably 22.0 (atom %/(m 2 /g)) or more.
  • the method for measuring the specific surface area SA (m 2 /g) of the silicon nitride powder will be described later.
  • the specific surface area SA of the silicon nitride powder according to the embodiment is the BET specific surface area measured by the krypton adsorption method based on JIS Z 8830:2013.
  • the specific surface area SA of the silicon nitride powder is preferably less than 2.66 m 2 /g, and the surface of the silicon nitride particles constituting the silicon nitride powder can be covered with a small amount of SiO 2.
  • the smaller the specific surface area the thicker the SiO 2 film formed on the surface can be. Therefore, it is expected that the water resistance of the silicon nitride powder will be improved.
  • the specific surface area of the silicon nitride powder is more preferably 2.00 m2 /g or less, even more preferably 1.50 m2 /g or less, and even more preferably less than 1.36 m2 /g.
  • the lower limit of the specific surface area is not particularly limited, but may be, for example, 0.01 m2 /g or more, 0.10 m2 /g or more, or 0.50 m2 /g or more.
  • the surface roughness Ra (arithmetic mean roughness) of the silicon nitride powder is preferably less than 0.97 nm. If the surface roughness Ra is less than 0.97 nm, the surface area is small, so the SiO2 film becomes thicker and water resistance can be improved. Furthermore, the small surface area reduces the contact area with water, so water resistance can be improved.
  • the surface roughness Ra is preferably less than 0.97 nm, more preferably 0.95 nm or less, even more preferably less than 0.93 nm, still more preferably 0.90 nm or less, even more preferably 0.80 nm or less, and particularly preferably 0.50 nm or less.
  • a measurement area of 100 nm x 100 nm is observed on the surface of any silicon nitride particle using a scanning probe microscope (SPM).
  • SPM scanning probe microscope
  • the surface roughness Ra is calculated from the obtained shape image.
  • the surface roughness Ra is measured for four silicon nitride particles, and the average value is taken as the surface roughness Ra of the silicon nitride powder.
  • the ⁇ -phase rate of the silicon nitride powder is preferably 65% or more. When the ⁇ -phase rate is 65% or more, the water resistance of the silicon nitride powder can be improved.
  • the ⁇ -formation rate is more preferably 70% or more, further preferably 80% or more, even more preferably 85% or more, and particularly preferably 90% or more.
  • ⁇ -type rate refers to the content (volume %) of ⁇ -type silicon nitride relative to the total silicon nitride contained in the silicon nitride powder.
  • the silicon nitride powder is measured by powder X-ray diffraction, and the diffraction pattern is analyzed by the Gazzara & Messier method (G.P. Gazzara and D.P. Messier, "Determination of Phase Content of Si3N4 by X - ray Diffraction Analysis", Am. Ceram. Soc. Bull., 56[9]777-80 (1977)), to calculate the ⁇ -phase ratio.
  • the maximum particle size of silicon nitride particles having a ratio (L2/L1) of the total length L2 of the internal boundary lines to the length L1 of the outer edge of 1% or less is 6.8 ⁇ m or more
  • L1 and L2 are obtained by observing the cross section of the silicon nitride particle.
  • the "grain boundary” and "boundary line” refer to a boundary (also called a high-angle grain boundary) whose crystal orientation difference (oblique angle) exceeds 15° as a result of EBSD analysis.
  • silicon nitride particles with a small value of L2/L1 are silicon nitride particles with a low content of boundary lines.
  • silicon nitride particles with an L2/L1 of 1% or less are considered to be silicon nitride particles made of a single crystal (these are referred to as "single crystal particles").
  • the maximum particle size of silicon nitride particles with L2/L1 of 1% or less is preferably 6.8 ⁇ m or more, more preferably 10.0 ⁇ m or more, and even more preferably 15.0 ⁇ m or more.
  • the silicon nitride particles contained in the silicon nitride powder preferably have an average aspect ratio of the minor axis to the major axis of more than 0.50, more preferably more than 0.60, even more preferably 0.70 or more, and even more preferably 0.72 or more.
  • the average aspect ratio of the silicon nitride particles is preferably less than 0.87, more preferably 0.85 or less, and even more preferably 0.80 or less.
  • the average aspect ratio of the silicon nitride particles is measured as follows. SEM images of silicon nitride particles contained in the silicon nitride powder are analyzed using image processing software (e.g., Image J (manufactured by the National Institute of Health)). The maximum particle size of the silicon nitride particles (referred to as the "major axis") is identified, and the particle size in the direction perpendicular to the major axis is regarded as the "minor axis”. The major and minor axes are measured for 20 random silicon nitride particles, and the ratio of the minor axis to the major axis (minor axis/major axis) is determined for each particle. The arithmetic mean value of these ratios is regarded as the average aspect ratio of the silicon nitride particles.
  • the silicon nitride powder preferably has a particle size D50 (hereinafter sometimes simply referred to as "D50") of 1.5 ⁇ m or more, more preferably 2.0 ⁇ m or more, at the cumulative 50% particle size from the fine particle side of the cumulative particle size distribution based on volume.
  • D50 particle size D50
  • the upper limit is not particularly limited, but is, for example, preferably 500.0 ⁇ m or less, more preferably 300.0 ⁇ m or less, and even more preferably 200.0 ⁇ m or less.
  • the D50 of silicon nitride powder is measured by the laser diffraction method. Specifically, the powder dispersed in water is irradiated with a laser beam, and the diffraction is measured to determine each particle size. A measuring device such as the CILAS 1090L can be used.
  • Silicon nitride powder is (1) synthesizing a silicon nitride composite crystal by a combustion synthesis method under a nitrogen atmosphere using a raw material containing Si; (2) crushing the silicon nitride synthetic crystals to obtain a coarsely pulverized silicon nitride powder; and (3) finely pulverizing the coarsely pulverized silicon nitride powder to obtain a finely pulverized silicon nitride powder.
  • a step of heat treating the finely pulverized silicon nitride powder may be included.
  • Step (1) Step of synthesizing silicon nitride synthetic crystal
  • Si powder is used as the raw material containing Si.
  • the average particle diameter D50 of the raw material is, for example, within the range of 2 to 10 ⁇ m. This makes it possible to suppress the amount of oxygen impurities and increase the combustion speed to raise the synthesis temperature, thereby obtaining good crystal growth.
  • the average particle diameter D50 of Si is 5 ⁇ m.
  • the diluent is used to adjust the amount of Si in the raw materials. Separately prepared silicon nitride powder is used as the diluent.
  • the diluent may be either ⁇ -type silicon nitride powder or ⁇ -type silicon nitride powder, or a mixture of these may be used.
  • the average particle diameter D50 of the diluent is preferably in the range of 0.5 to 2.0 ⁇ m. As an example, the average particle diameter D50 of the diluent is 1.0 ⁇ m.
  • the amount of diluent added is less than 10 mass% of the entire raw materials (including the diluent). As an example, the diluent is added in an amount of 5 to 8 mass% of the entire raw materials.
  • a diluent is mixed into the raw materials and filled into an insulating heat-resistant container.
  • the thermal conductivity of this insulating heat-resistant container is 1 W/mK or less, and the material can be alumina or zirconia, but carbon is preferred in consideration of the inclusion of impurities.
  • the container is covered with a lid made of the same material as the insulating heat-resistant container.
  • the thickness of the mixed raw materials is made to be more than 100 mm, preferably more than 100 mm and not more than 150 mm.
  • Combustion synthesis is performed in a nitrogen atmosphere in the range of 0.5 to 1 MPa (for example, 0.9 MPa). By adjusting the pressure range within the above range, efficient synthesis can be achieved while suppressing increases in equipment costs.
  • a layer of powder (silicon nitride) with a thickness of 1 mm to 80 mm is placed on the bottom and sides of the crucible, the mixed raw materials are then filled, and the top surface is covered with a layer of powder with a thickness of 1 mm to 80 mm.
  • the mixed raw materials can be kept warm, and a specified amount of silicon nitride particles with oxygen localized on the surfaces of the silicon nitride particles can be produced.
  • a catalyst may be used, for example, about 0.01 to 0.1 mass % of Y 2 O 3 , Fe 2 O 3 , CaO, Ni, Co, C, etc. is added.
  • external auxiliary heating in the range of 500° C. to 1700° C. (for example, 1500° C.) is performed to increase the combustion temperature in the combustion synthesis method by self-ignition.
  • Step (2) Obtaining a coarsely pulverized silicon nitride powder
  • the silicon nitride composite crystal is in the form of an aggregate of multiple silicon nitride particles.
  • the silicon nitride composite crystal is crushed to obtain a coarsely pulverized silicon nitride powder.
  • the composite is crushed using a general crushing device such as a hammer mill or a disk mill until it passes through a sieve with a predetermined mesh size (for example, a sieve with a mesh size in the range of 400 ⁇ m to 500 ⁇ m).
  • Step (3) Step of obtaining finely pulverized silicon nitride powder
  • the coarsely pulverized silicon nitride powder is further pulverized to obtain finely pulverized silicon nitride powder.
  • the pulverization is carried out using a pulverizing device such as a jet mill or a ball mill. If necessary, the obtained finely pulverized powder may be classified. The classification may be carried out by sieving, wet classification, or the like.
  • the resulting finely pulverized powder may be used as it is as silicon nitride powder, or the finely pulverized powder may be subjected to a heat treatment step (step (4) described below) before being used as silicon nitride powder.
  • the finely pulverized silicon nitride powder may be heat treated.
  • oxygen can be further localized on the surface, and an oxide film is formed on the surface of the silicon nitride particles. This has the effect of chemically stabilizing the silicon nitride particles, and a silicon nitride powder with excellent water resistance is obtained.
  • the heat treatment is performed in air at 500°C or higher and 1200°C or lower, preferably 550°C or higher and 1100°C or lower, and particularly preferably more than 800°C and 1000°C or lower.
  • the heat treatment time can be appropriately adjusted according to the heat treatment temperature.
  • the heat treatment time is, for example, 5 hours.
  • the heat generated by the combustion synthesis method is used to synthesize silicon nitride composite crystals, which are then crushed, classified, and finely pulverized to produce the silicon nitride powder according to this embodiment.
  • the silicon nitride powder according to the embodiment of the present invention has excellent water resistance and is therefore suitable as a filler for a resin composition.
  • the resin composition contains a resin and the silicon nitride powder according to the embodiment of the present invention.
  • the compounding ratio of the silicon nitride powder and the resin according to the embodiment of the present invention can be appropriately determined depending on the purpose and application.
  • the ratio of the resin to the silicon nitride powder may be 5 to 75 volume % and 95 to 25 volume % relative to the resin composition (composite).
  • the filling rate of the silicon nitride powder in the resin composition refers to the content (volume %) of the silicon nitride powder when the volume of the resin composition (including the silicon nitride powder) is taken as 100 volume %.
  • a resin composition can be obtained by mixing silicon nitride powder and a resin using a commonly used known method.
  • the resin when the resin is liquid (such as liquid epoxy resin), the resin composition can be obtained by mixing the liquid resin, silicon nitride powder, and a curing agent, and then curing with heat or ultraviolet light.
  • Known curing agents, mixing methods, and curing methods can be used.
  • the resin when the resin is solid, the silicon nitride powder and the resin are mixed, and then kneaded by a known method such as melt kneading to obtain the desired resin composition.
  • the resin used in the resin composition may be a known resin such as an epoxy resin.
  • the type of resin may be selected from thermoplastic resins, thermoplastic elastomers, and thermosetting resins.
  • the resin may be used alone or in combination of two or more types.
  • these resin compositions may contain, as necessary, one or more of known additives such as plasticizers, curing accelerators, coupling agents, fillers, pigments, flame retardants, antioxidants, surfactants, compatibilizers, weather resistance agents, antiblocking agents, antistatic agents, leveling agents, and release agents, within the scope of the invention that does not impair the effects of the invention.
  • additives such as plasticizers, curing accelerators, coupling agents, fillers, pigments, flame retardants, antioxidants, surfactants, compatibilizers, weather resistance agents, antiblocking agents, antistatic agents, leveling agents, and release agents, within the scope of the invention that does not impair the effects of the invention.
  • the amount of diluent added was 5 to 8 mass% of the total raw material (including diluent).
  • the mixed powder was filled in a carbonaceous heat-insulating heat-resistant container with a layer of powder having a thickness of 1 mm to 80 mm on the bottom and sides so that the raw material layer thickness was more than 100 mm and 150 mm or less, and the raw material layer was further covered with a layer of powder having a thickness of 1 mm to 80 mm or less. Then, a lid made of a carbonaceous heat-insulating heat-resistant material was placed, and synthesis was performed under a nitrogen atmosphere of 0.9 MPa. After synthesis, coarse pulverization (disintegration) was performed in a mortar until the powder passed through a sieve with a predetermined opening. The openings of the sieve for each sample are shown in Table 1.
  • the obtained coarsely pulverized powder was further finely pulverized using a Nano Jet Mizer (manufactured by Aisin Nano Technologies Co., Ltd.).
  • a Nano Jet Mizer manufactured by Aisin Nano Technologies Co., Ltd.
  • the obtained finely pulverized powder was classified by the method shown in Table 1. Note that classification was not performed for sample No. 2.
  • the resulting classified powders (samples No. 1, 3, and 6) and finely pulverized powder (sample No.
  • Example 2 2) were then placed in an alumina crucible and heat-treated in an air atmosphere using a small programmable electric powder furnace (MMF series manufactured by AS ONE) under the conditions (heat treatment temperature, heat treatment time) listed in Table 1 to obtain silicon nitride powders (samples No. 1 to 3 and 6).
  • the classified powder (sample No. 5) was not heat-treated and was used as it was as silicon nitride powder (sample No. 5).
  • Example No. 4 a commercially available silicon nitride powder (manufactured by Aldrich, silicon nitride (predominantly ⁇ -phase, ⁇ 10 micron primary particle size, product code 248622); hereafter referred to as "Sample No. 4").
  • the maximum particle size of silicon nitride particles having an L2/L1 ratio of 1% or less (the maximum particle size of single crystal particles)
  • a sample for cross-sectional observation was prepared using the sample (silicon nitride particles).
  • the silicon nitride particles were embedded in resin, and then the resin and silicon nitride particles were cut with a diamond cutter. Thereafter, Pt was vapor-deposited on the cross-section as a protective film, the cross-section was prepared by Ar ion milling, and the sample was fixed to the SEM sample stage with Cu double-sided tape, and SEM-EBSD measurement was performed without vapor deposition.
  • the observation position was determined so that two or more silicon nitride particles were completely contained within the observation area (i.e., two or more silicon nitride particles were not in contact with the frame of the observation area).
  • the measurement was performed with ⁇ -type silicon nitride particles.
  • Ion milling device E-3500 (manufactured by Hitachi High-Tech Corporation)
  • Ion sputtering device E-1030 (manufactured by Hitachi, Ltd.)
  • Schottky scanning electron microscope SU5000 (Hitachi High-Tech Corporation)
  • Backscattered electron diffraction device Velocity (manufactured by METEK Corporation)
  • total boundary length L2 is the sum of the boundary lines contained inside the silicon nitride particle, and does not include the outer edge of the silicon nitride particle.
  • the total boundary length L2 was calculated by adding the total length of the grain boundaries inside the silicon nitride particle and the total length of the inner walls of the cavity (if there is a cavity inside the silicon nitride particle).
  • Such measurements were carried out once for 20 random silicon nitride particles, and silicon nitride particles with an L2/L1 ratio of 1% or less were regarded as single crystal particles, and the length of their major axis was measured and recorded as the "maximum particle size of the single crystal particle.” If the 20 silicon nitride particles measured contained multiple single crystal particles, the arithmetic average of their maximum particle sizes was calculated.
  • the surface roughness Ra was measured using a scanning probe microscope SPA300HV manufactured by Seiko Instruments Inc. The measurement conditions were as follows: Probe station/unit SPI4000/SPA300HV Cantilever: SI-DF20 Scanner: 20 ⁇ m Data type: Shape image Observation mode: DFM (Dynamic Force Mode Microscope) Scanning area: 100 nm x 100 nm Scanning frequency: 0.25Hz Analysis software: (included with the measuring device)
  • the thickness X (nm) of the SiO2 coating was obtained from the measurement results of the total oxygen content TO (mass%) of the silicon nitride powder
  • the thickness Y (nm) of the SiO2 coating was obtained from the measurement results of the surface oxygen ratio SO (atom%) of the silicon nitride particles.
  • the D50 of the silicon nitride powder, which is necessary for determining the thickness, was measured as follows.
  • the particle size distribution of the sample was measured, and the cumulative 50% particle size D50 was determined.
  • the particle size distribution of silicon nitride powder was measured by laser diffraction. A sample dispersed in water was irradiated with a laser beam, and the diffraction was measured to determine the particle size.
  • the measuring device used was a CILAS 1090L model.
  • the particle size was taken as the equivalent circle particle size.
  • the equivalent circle particle size is the particle size of a perfect circle that has the same area as a projected particle image. The particle size was based on volume.
  • the oxygen localization index (
  • Ratio of surface oxygen content SO of silicon nitride particles to specific surface area SA of silicon nitride powder The surface oxygen ratio SO (atom %) of the silicon nitride particles was divided by the specific surface area SA (m 2 /g) of the silicon nitride powder measured by the method described below to obtain SO/SA.
  • Ratio of the total oxygen content TO of the silicon nitride powder to the specific surface area SA of the silicon nitride powder (TO/SA)
  • the total oxygen content TO (mass %) of the silicon nitride powder was divided by the specific surface area SA (m 2 /g) of the silicon nitride powder measured by the method described below to obtain TO/SA.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Products (AREA)

Abstract

Cette poudre de nitrure de silicium contient de multiples particules de nitrure de silicium et satisfait la formule (1).　(1) : 0 % ≤|X-Y|/Y × 100 < 240,0 %, dans laquelle X (nm) représente l'épaisseur d'un film de revêtement SiO2 telle que calculée à partir de la quantité totale d'oxygène TO (% en masse) dans la poudre de nitrure de silicium, et Y (nm) représente l'épaisseur du film de revêtement SiO2 telle que calculée à partir du pourcentage d'oxygène de surface SO (% atomique) des particules de nitrure de silicium.
PCT/JP2024/006300 2023-03-31 2024-02-21 Poudre de nitrure de silicium et composition de résine faisant appel à celle-ci Pending WO2024202735A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020257035321A KR20250165636A (ko) 2023-03-31 2024-02-21 질화규소 분말 및 이를 이용한 수지 조성물
CN202480018109.XA CN120858072A (zh) 2023-03-31 2024-02-21 氮化硅粉末和使用其的树脂组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2023058618 2023-03-31
JP2023-058618 2023-03-31

Publications (1)

Publication Number Publication Date
WO2024202735A1 true WO2024202735A1 (fr) 2024-10-03

Family

ID=92905091

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2024/006300 Pending WO2024202735A1 (fr) 2023-03-31 2024-02-21 Poudre de nitrure de silicium et composition de résine faisant appel à celle-ci

Country Status (4)

Country Link
KR (1) KR20250165636A (fr)
CN (1) CN120858072A (fr)
TW (1) TW202500502A (fr)
WO (1) WO2024202735A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05221617A (ja) * 1992-02-14 1993-08-31 Shin Etsu Chem Co Ltd 窒化ケイ素粉末の製造方法
JPH05230181A (ja) * 1992-02-18 1993-09-07 Toshiba Chem Corp エポキシ樹脂組成物および半導体封止装置
JPH07267614A (ja) * 1994-03-29 1995-10-17 Ngk Insulators Ltd 窒化珪素粉末の製造方法、窒化珪素焼結体及びその製造方法
JPH11166074A (ja) * 1997-12-04 1999-06-22 Sumitomo Bakelite Co Ltd 半導体封止用エポキシ樹脂組成物及び半導体装置
JPH11268903A (ja) * 1998-03-24 1999-10-05 Denki Kagaku Kogyo Kk 窒化珪素質充填材及び半導体封止用樹脂組成物
JP2015081205A (ja) * 2013-10-21 2015-04-27 独立行政法人産業技術総合研究所 窒化ケイ素フィラー、樹脂複合物、絶縁基板、半導体封止材
WO2019167879A1 (fr) * 2018-02-28 2019-09-06 株式会社トクヤマ Méthode de fabrication de poudre de nitrure de silicium
WO2022168630A1 (fr) * 2021-02-05 2022-08-11 住友化学株式会社 Film de revêtement durci et produit stratifié

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05221617A (ja) * 1992-02-14 1993-08-31 Shin Etsu Chem Co Ltd 窒化ケイ素粉末の製造方法
JPH05230181A (ja) * 1992-02-18 1993-09-07 Toshiba Chem Corp エポキシ樹脂組成物および半導体封止装置
JPH07267614A (ja) * 1994-03-29 1995-10-17 Ngk Insulators Ltd 窒化珪素粉末の製造方法、窒化珪素焼結体及びその製造方法
JPH11166074A (ja) * 1997-12-04 1999-06-22 Sumitomo Bakelite Co Ltd 半導体封止用エポキシ樹脂組成物及び半導体装置
JPH11268903A (ja) * 1998-03-24 1999-10-05 Denki Kagaku Kogyo Kk 窒化珪素質充填材及び半導体封止用樹脂組成物
JP2015081205A (ja) * 2013-10-21 2015-04-27 独立行政法人産業技術総合研究所 窒化ケイ素フィラー、樹脂複合物、絶縁基板、半導体封止材
WO2019167879A1 (fr) * 2018-02-28 2019-09-06 株式会社トクヤマ Méthode de fabrication de poudre de nitrure de silicium
WO2022168630A1 (fr) * 2021-02-05 2022-08-11 住友化学株式会社 Film de revêtement durci et produit stratifié

Also Published As

Publication number Publication date
KR20250165636A (ko) 2025-11-26
CN120858072A (zh) 2025-10-28
TW202500502A (zh) 2025-01-01

Similar Documents

Publication Publication Date Title
JP2011219309A (ja) ＡｌＮ改質層を備えたアルミナ粒子の製造方法、及び改質アルミナ粉末
Kvashnin et al. Large‐scale synthesis and applications of hafnium–tantalum carbides
EP4084060B1 (fr) Corps fritté au nitrure de bore, corps composite, procédé de production dudit corps fritté au nitrure de bore et procédé de production dudit corps composit
WO2024202735A1 (fr) Poudre de nitrure de silicium et composition de résine faisant appel à celle-ci
Yu et al. Microanalysis of single-phase AlN nanocrystals and AlN-Al nanocomposites prepared by DC arc-discharge
WO2024202729A1 (fr) Poudre de nitrure de silicium et composition de résine l&#39;utilisant
WO2024202726A1 (fr) Poudre de nitrure de silicium et composition de résine l&#39;utilisant
WO2024202733A1 (fr) Poudre de nitrure de silicium et composition de résine l&#39;utilisant
WO2024202736A1 (fr) Poudre de nitrure de silicium et composition de résine l&#39;utilisant
WO2024202734A1 (fr) Poudre de nitrure de silicium et composition de résine utilisant celle-ci
WO2025178081A1 (fr) Composition de résine
WO2024202728A1 (fr) Poudre de nitrure de silicium et composition de résine l&#39;utilisant
WO2021200868A1 (fr) Poudre de nitrure de silicium et procédé pour produire un corps fritté de nitrure de silicium
WO2025178086A1 (fr) Composition de résine
TW202534120A (zh) 樹脂組成物
WO2025178088A1 (fr) Poudre inorganique et composition de résine l&#39;utilisant
TW202436230A (zh) 氧化鋁粒子及使用其的樹脂組成物
Zhou Phase formation and thermal conductivity of zirconium carbide
WO2025178082A1 (fr) Composition de résine
WO2025178089A1 (fr) Poudre inorganique et composition de résine l&#39;utilisant
TW202426393A (zh) 氧化鋁粒子及使用其的樹脂組成物
EP4206123A1 (fr) Poudre de carbonitrure de bore et son procédé de production, composition de poudre, comprimé fritté de nitrure de bore et son procédé de production, et complexe et son procédé de production
TW202423838A (zh) 氧化鋁粒子及使用其的樹脂組成物

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: 24778878

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 202480018109.X

Country of ref document: CN

ENP Entry into the national phase

Ref document number: 2025509951

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2025509951

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: KR1020257035321

Country of ref document: KR

WWP Wipo information: published in national office

Ref document number: 202480018109.X

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE