WO2024048377A1 - シートの製造方法及びシート - Google Patents

シートの製造方法及びシート Download PDF

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Publication number
WO2024048377A1
WO2024048377A1 PCT/JP2023/030202 JP2023030202W WO2024048377A1 WO 2024048377 A1 WO2024048377 A1 WO 2024048377A1 JP 2023030202 W JP2023030202 W JP 2023030202W WO 2024048377 A1 WO2024048377 A1 WO 2024048377A1
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Prior art keywords
boron nitride
sheet
cells
region
boron
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English (en)
French (fr)
Japanese (ja)
Inventor
建治 宮田
麻菜 山本
祐輔 佐々木
遼 戎▲崎▼
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Denka Co Ltd
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Denka Co Ltd
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Priority to JP2024544159A priority Critical patent/JPWO2024048377A1/ja
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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
    • 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
    • C01B21/064—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 boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K3/38—Boron-containing compounds
    • 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 a sheet manufacturing method and a sheet.
  • boron nitride powder As a ceramic powder, boron nitride powder, which has characteristics such as high thermal conductivity, high insulation, and low dielectric constant, is attracting attention.
  • Boron nitride powder is generally composed of agglomerated particles (lump particles) formed by agglomerating scale-like boron nitride particles (primary particles).
  • agglomerated particles lump particles
  • primary particles agglomerating scale-like boron nitride particles
  • the shape of the aggregated particles is made more spherical to improve the filling property, and the powder strength is also improved.
  • a hexagonal boron nitride powder is disclosed which is said to have improved and stabilized withstand voltage.
  • a resin composition containing boron nitride powder and a resin is pressurized and formed into a sheet shape, but in this case, the nitride in the resin composition is The aggregated boron particles collapse, and the boron nitride particles (primary particles) that constituted the aggregated particles tend to be oriented parallel to the main surface of the sheet (perpendicular to the pressing direction). If the boron nitride particles are oriented in a direction parallel to the main surface of the sheet, the thermal conductivity in the thickness direction of the sheet may decrease, which may make the sheet unsuitable for use as a heat transfer sheet.
  • the main object of the present invention is to produce a sheet in which the orientation of boron nitride particles in the direction parallel to the main surface of the sheet is suppressed.
  • the present inventors formed a sheet using boron nitride powder obtained by a manufacturing method including hot isostatic pressing (HIP method), thereby forming boron nitride in a direction parallel to the main surface of the sheet. It has been discovered that it is possible to produce a sheet with suppressed particle orientation.
  • the present invention provides the following [1] to [3].
  • a method for manufacturing a sheet comprising: [2] Contains boron nitride particles and a resin, A sheet whose average value X calculated by the following steps (1) to (8) is 0.01 or more. (1) Obtain an observation image of an arbitrary cross section of the sheet observed with a SEM at a magnification of 1000 times.
  • the one cell is a boron nitride region, and if the area ratio is less than 20%, it is determined that the one cell is a resin region.
  • n is 1 to 200, calculate the ratio of the number of cells determined to be the boron nitride region.
  • n is 1 to 5
  • FIG. 1 is a flow diagram of steps (1) to (7).
  • FIG. 2(a) is a reference diagram when area A included in the binarized image is divided into a plurality of cells.
  • FIG. 2(b) is a schematic diagram when each of the plurality of cells in FIG. 2(a) is determined to be either a boron nitride region or a resin region. It is a SEM image of a cross section of the sheet of Example 1-1.
  • 3 is a SEM image of a cross section of a sheet of Comparative Example 1. Graph showing the relationship between the length of one side of one cell and the ratio of the number of cells determined to be boron nitride regions when the sheet of Example 4-1 and the sheet of Comparative Example 4 are divided into a plurality of cells. It is.
  • a method for manufacturing a sheet according to an embodiment of the present invention includes a step of nitriding boron carbide powder while hot isostatic pressing (also referred to as "hot isostatic pressing") to obtain boron carbonitride powder. (nitriding step), a step of decarburizing boron carbonitride powder to obtain boron nitride powder (decarburizing step), and a step of mixing boron nitride powder with resin to obtain a resin composition (mixing step). , a step of molding the resin composition into a sheet shape by applying pressure (molding step).
  • Boron carbide powder (boron carbide particles) can be produced, for example, by a known production method. For example, boric acid and acetylene black are mixed and then heated in an inert gas atmosphere at 1800 to 2400° C. for 1 to 10 hours to obtain coarse boron carbide powder containing lumpy boron carbide particles. Boron carbide powder is obtained by appropriately performing pulverization, sieving, washing, impurity removal, drying, etc. on the obtained boron carbide coarse powder.
  • the average particle diameter of the boron carbide powder may be, for example, 5 ⁇ m or more, 10 ⁇ m or more, or 15 ⁇ m or more, and 80 ⁇ m or less, 60 ⁇ m or less, or 40 ⁇ m or less.
  • the average particle size of boron carbide powder means the particle size (D50) at which the volume cumulative particle size distribution is 50%, and can be measured by a laser diffraction scattering method.
  • boron carbide powder is nitrided to obtain boron carbonitride powder by heating the container filled with boron carbide powder under hot isostatic pressure in an atmosphere that allows the nitriding reaction to proceed.
  • the container may be, for example, a carbon crucible.
  • the hot isostatic pressing can be performed using, for example, a hot isostatic pressing device (for example, manufactured by Kobe Steel, Ltd.).
  • the atmosphere in which the nitriding reaction proceeds in the nitriding step may be a nitriding gas atmosphere that nitrides boron carbide powder.
  • the nitriding gas may be nitrogen gas, ammonia gas, etc. Nitrogen gas may be used from the viewpoint of ease of nitriding boron carbide powder and from the viewpoint of cost.
  • the nitriding gas may be used alone or in combination of two or more, and the proportion of nitrogen gas in the nitriding gas may be 95% by volume or more, 99% by volume or more, or 99.9% by volume or more.
  • the pressure in the nitriding step may be 10 MPa or more, 30 MPa or more, or 100 MPa or more.
  • the pressure in the nitriding step may be 200 MPa or less or 150 MPa or less.
  • the heating temperature in the nitriding step may be 1600° C. or higher or 1700° C. or higher from the viewpoint of sufficiently nitriding the boron carbide powder.
  • the heating temperature in the nitriding step may be 2200°C or lower or 2000°C or lower.
  • the time for pressurizing and heating in the nitriding step may be 3 hours or more, 5 hours or more, or 8 hours or more from the viewpoint of sufficiently nitriding the boron carbide powder.
  • the time for pressurizing and heating in the nitriding step may be 30 hours or less, 20 hours or less, or 10 hours or less.
  • a mixture containing boron carbonitride powder (boron carbonitride particles) obtained in the nitriding step and a boron source is filled in a container and heated to decarburize the boron carbonitride powder.
  • the container may be, for example, a boron nitride crucible.
  • Boron sources include boric acid, boron oxide, or mixtures thereof.
  • the mixture may further contain other additives used in the art, if necessary.
  • the mixing ratio of boron carbonitride powder and boron source is selected as appropriate.
  • boric acid or boron oxide is used as a boron source, the proportion of boric acid or boron oxide may be, for example, 50 parts by mass or more or 80 parts by mass or more, and 300 parts by mass or less, based on 100 parts by mass of boron carbonitride. Or it may be 200 parts by mass or less.
  • the atmosphere in the decarburization process may be a normal pressure (atmospheric pressure) atmosphere or a pressurized atmosphere.
  • the pressure in the decarburization step may be, for example, 0.5 MPa or less or 0.3 MPa or less, and may be 0.01 MPa or more or 0.03 MPa or more.
  • the temperature is raised to a predetermined temperature (a temperature at which decarburization can start), and then the temperature is further raised to a holding temperature at the predetermined temperature.
  • the predetermined temperature temperature at which decarburization can start
  • the rate of temperature increase from a predetermined temperature (temperature at which decarburization can be started) to the holding temperature may be, for example, 5° C./min or less, 4° C./min or less, 3° C./min or less, or 2° C./min or less.
  • the holding temperature may be 1800° C. or higher or 2000° C. or higher from the viewpoint of facilitating good particle growth.
  • the holding temperature may be 2200°C or less or 2100°C or less.
  • the holding time at the holding temperature may be, for example, 0.5 hours or more, 1 hour or more, 3 hours or more, or 5 hours or more, from the viewpoint of facilitating particle growth.
  • the holding time at the holding temperature may be, for example, 40 hours or less, 30 hours or less, or 20 hours or less.
  • the boron nitride powder (boron nitride agglomerated particles) obtained as described above may be classified using a sieve (classification step) so as to obtain boron nitride powder having a desired particle size.
  • the boron nitride agglomerated particles are composed of, for example, a plurality of boron nitride pieces (boron nitride primary particles).
  • the boron nitride pieces are made of boron nitride and may have, for example, a scale-like shape.
  • the plurality of boron nitride pieces may be in physical contact with each other or may be chemically bonded.
  • the fact that the plurality of boron nitride pieces are chemically bonded to each other can be confirmed by using SEM, since no boundaries between the boron nitride pieces are observed at the joints between the boron nitride pieces.
  • the average thickness of the boron nitride pieces may be 0.5 ⁇ m or more, 1.0 ⁇ m or more, or 3.0 ⁇ m or more, and 10 ⁇ m or less.
  • the average length of the boron nitride pieces in the longitudinal direction may be, for example, 1 ⁇ m or more and 10 ⁇ m or less.
  • the average thickness and average length in the longitudinal direction of the boron nitride pieces can be determined using an SEM image of the cross section of the boron nitride agglomerated particles observed at a magnification of 1000 times using image analysis software (for example, "Mac" manufactured by Mountech Co., Ltd.). -view'') and is defined as the average value of the thickness and longitudinal length of 40 boron nitride pieces measured in the SEM image.
  • the boron nitride agglomerated particles may have a cross section that includes a region in which a plurality of boron nitride pieces are stacked.
  • the fact that multiple boron nitride pieces were stacked was confirmed by observing the cross section of the boron nitride agglomerated particles using SEM, and it was found that the multiple boron nitride pieces were arranged side by side in the thickness direction of the boron nitride pieces. You can check it.
  • the average particle diameter of the boron nitride powder may be, for example, 10 ⁇ m or more, 20 ⁇ m or more, or 30 ⁇ m or more, and 100 ⁇ m or less, 80 ⁇ m or less, or 60 ⁇ m or less.
  • the average particle size of boron nitride powder means the particle size (D50) at which the volume cumulative particle size distribution is 50%, and can be measured by a laser diffraction scattering method.
  • the bulk density of the boron nitride powder may be 0.7 g/ml or more, 0.72 g/ml or more, 0.74 g/ml or more, or 0.75 g/ml or more, and 0.9 g/ml or less, 0. It may be 8 g/ml or less, or 0.75 g/ml or less.
  • the boron nitride agglomerated particles may consist essentially only of boron nitride. It can be confirmed that the boron nitride aggregate particles are substantially composed only of boron nitride by detecting only a peak derived from boron nitride in X-ray diffraction measurement.
  • a resin composition is obtained by mixing the boron nitride powder obtained in the decarburization step and a resin.
  • the resin examples include epoxy resin, silicone resin, silicone rubber, acrylic resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluororesin, polyimide, polyamideimide, polyetherimide, polybutylene terephthalate, polyethylene terephthalate, Polyphenylene ether, polyphenylene sulfide, fully aromatic polyester, polysulfone, liquid crystal polymer, polyether sulfone, polycarbonate, maleimide modified resin, ABS (acrylonitrile-butadiene-styrene) resin, AAS (acrylonitrile-acrylic rubber/styrene) resin, and AES ( Examples include acrylonitrile, ethylene, propylene, diene rubber (styrene) resin.
  • the content of the boron nitride powder is 50 volume% or more, 55 volume% or more, based on the total volume of the resin composition, from the viewpoint of improving the thermal conductivity of the resin composition and easily obtaining excellent heat dissipation performance. It may be 60% by volume or more, 65% by volume or more, or 70% by volume or more.
  • the content of the boron nitride powder is 85% by volume or less, 80% by volume or less, based on the total volume of the resin composition, from the viewpoint of suppressing the generation of pores during molding and the decrease in insulation and mechanical strength. Alternatively, it may be 75% by volume or less.
  • the content of the resin may be 15% by volume or more, 20% by volume or more, or 25% by volume or more, and 50% by volume or less, 45% by volume or less, 40% by volume or less, based on the total volume of the resin composition. , 35% by volume or less, or 30% by volume or less.
  • the resin composition may further contain a curing agent for curing the resin.
  • the curing agent is appropriately selected depending on the type of resin.
  • examples of the curing agent include phenol novolac compounds, acid anhydrides, amino compounds, and imidazole compounds.
  • the content of the curing agent may be, for example, 0.5 parts by mass or more or 1.0 parts by mass or more, and 15 parts by mass or less or 10 parts by mass or less, based on 100 parts by mass of the resin.
  • the resin composition may further contain other components.
  • Other components may include a curing accelerator (curing catalyst), a coupling agent, a wetting and dispersing agent, a surface conditioner, and the like.
  • curing accelerators examples include phosphorus curing accelerators such as tetraphenylphosphonium tetraphenylborate and triphenyl phosphate, imidazole curing accelerators such as 2-phenyl-4,5-dihydroxymethylimidazole, and trifluorocarbon curing accelerators.
  • phosphorus curing accelerators such as tetraphenylphosphonium tetraphenylborate and triphenyl phosphate
  • imidazole curing accelerators such as 2-phenyl-4,5-dihydroxymethylimidazole
  • trifluorocarbon curing accelerators examples include amine curing accelerators such as boron monoethylamine.
  • Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminate coupling agents.
  • Chemical bonding groups contained in these coupling agents include vinyl groups, epoxy groups, amino groups, methacrylic groups, mercapto groups, and the like.
  • wetting and dispersing agents include phosphoric acid ester salts, carboxylic acid esters, polyesters, acrylic copolymers, block copolymers, and the like.
  • surface conditioners examples include acrylic surface conditioners, silicone surface conditioners, vinyl surface conditioners, fluorine surface conditioners, and the like.
  • the boron nitride powder and the resin can be mixed by a known method.
  • the resin composition obtained in the mixing step may further contain a solvent (for example, a solvent for dissolving the resin) as necessary, and may further contain the other components mentioned above.
  • Examples of the solvent include alcohol solvents, glycol ether solvents, aromatic solvents, ketone solvents, and the like.
  • Examples of alcoholic solvents include isopropyl alcohol and diacetone alcohol.
  • Examples of glycol ether solvents include ethyl cellosolve, butyl cellosolve, and the like.
  • Examples of aromatic solvents include toluene and xylene.
  • Examples of ketone solvents include methyl ethyl ketone and methyl isobutyl ketone.
  • the resin composition obtained in the mixing step is molded into a sheet by applying pressure to obtain a sheet.
  • the molding step may be, for example, a step of molding the resin composition into a sheet shape by applying the resin composition onto the base material using a film applicator and applying pressure.
  • the pressing force in the molding step may be, for example, 1 MPa or more or 5 MPa or more, or 100 MPa or less or 50 MPa or less.
  • a step (curing step) of curing part or all of the resin in the resin composition may be performed simultaneously with or after the molding.
  • the method for curing the resin is appropriately selected depending on the type of resin (and the curing agent used as necessary).
  • the resin when the resin is an epoxy resin and the above-mentioned curing agent is used together, the resin can be cured by heating in the curing step. In this case, the resin can be semi-cured by adjusting the heating temperature and heating time.
  • the resin composition contains a solvent, the resin may be cured and the solvent may be volatilized in the curing step.
  • boron nitride powder (boron nitride agglomerated particles) obtained by nitriding boron carbide powder under hot isostatic pressure to obtain boron carbonitride powder and then decarburizing the boron carbonitride powder is: Constructed from a relatively thick piece of boron nitride. Such boron nitride agglomerated particles tend to easily maintain their shape even when external force is applied.
  • each of the boron nitride pieces constituting the boron nitride aggregate particles is relatively thick, and the boron nitride aggregate particles have high density (low porosity).
  • the amount of boron nitride per particle is larger than that of conventional boron nitride agglomerated particles.
  • the amount per unit volume of the sheet is Since the number of boron nitride aggregated particles (or boron nitride pieces) is reduced, the frequency of compressive deformation of the boron nitride aggregated particles (or boron nitride pieces) during sheet formation is reduced.
  • Boron nitride agglomerated particles are difficult to break down and compressively deform less frequently during sheet formation, making it difficult for boron nitride pieces (boron nitride primary particles) to line up in a direction parallel to the main surface of the sheet, resulting in the formation of boron nitride particles in the sheet. It is presumed that the orientation is suppressed.
  • the mechanism of the present invention is not limited to the above reasons.
  • the sheet obtained by the above manufacturing method has a plurality of regions made of boron nitride particles and other regions in the cross section of the sheet.
  • the sheet obtained by the above manufacturing method is such that the boron nitride agglomerated particles maintain their shape to some extent in the sheet, so that the area of the region made of boron nitride particles in the cross section of the sheet (multiple regions made of boron nitride particles The area of each region of boron nitride particles tends to be larger than the area of the region of boron nitride particles in the cross section of a sheet made with the same content using conventional boron nitride agglomerated particles.
  • FIG. 1 shows a flow diagram of steps (1) to (7). (1) An observation image of an arbitrary cross section of the sheet is obtained by observing it at a magnification of 1000 times using an SEM.
  • the one cell is a boron nitride region, and if the area ratio is less than 20%, it is determined that the one cell is a resin region.
  • (6) In the steps (3) to (5) above, when n is 1 to 200, calculate the ratio of the number of cells determined to be the boron nitride region.
  • n is 1 to 5
  • the image format of the observation image to be acquired is bmp.
  • the image to be acquired may be one that is sharp enough to be binarized into a region made of boron nitride particles and other regions.
  • step (2) the observed image is imported into image processing software "imageJ” and filtered using a median filter (3x3 pixels). Thereafter, the region made of boron nitride particles and the other regions (for example, the region made of resin) are subjected to binarization processing using the Otsu method to obtain a binarized image.
  • step (3) the entire region A is included in the binarized image.
  • Area A is an area with a short side of 50 ⁇ m x a long side of 100 ⁇ m. Note that due to image processing, it is difficult to accurately specify the short side (50 ⁇ m ⁇ 5 ⁇ m) x long side (100 ⁇ m ⁇ 10 ⁇ m) as area A. , the influence on the calculation result of the average value X can be ignored, so this region can be regarded as region A.
  • step (3) area A is divided into a plurality of cells by dividing the short side of area A into n equal parts and dividing the long side of area A into 2n equal parts, where n is an integer greater than or equal to 1. .
  • the area A is divided into 2n2 cells, and each cell is a square with one side of 50/n ( ⁇ m).
  • FIG. 2(a) is a reference diagram when area A included in the binarized image is divided into a plurality of cells.
  • area A is divided into four equal parts along the short side and eight equal parts along the long side, and is divided into 32 square cells.
  • step (4) one cell among the plurality of cells is focused on, and the area ratio of the region made of boron nitride particles is calculated based on the total area of one cell.
  • the area ratio of the region consisting of boron nitride particles is 80% or more, it can be determined that the cell is an area occupied by boron nitride particles, and the area ratio of the area consisting of boron nitride particles is If it is less than 20%, it can be determined that the cell is an area occupied by components other than boron nitride particles (area not occupied by boron nitride particles).
  • region A by dividing region A into a plurality of cells and determining whether each cell is a region made of boron nitride particles (boron nitride region) or a region made of something else (resin region), it is possible to , it can be determined whether the area of each region among the plurality of regions made of boron nitride particles is relatively large.
  • FIG. 2(b) is a schematic diagram when each of the plurality of cells in FIG. 2(a) is determined to be either a boron nitride region or a resin region.
  • FIG. 2B cells determined to be boron nitride regions are shown as black cells, and cells determined to be resin regions are shown as white cells.
  • step (5) the determination in step (4) is performed for each of the plurality of cells, and the ratio of the number of cells determined to be boron nitride regions based on the total number of the plurality of cells is calculated. That is, the ratio of the number of cells determined to be boron nitride regions is calculated by dividing the total number of cells determined to be boron nitride regions by the total number of a plurality of cells.
  • the total value is calculated from the ratio of the number of cells determined to be boron nitride regions when n is 1 to 5. If the boron nitride agglomerated particles do not easily collapse during sheet production and the boron nitride agglomerated particles can maintain their shape to some extent in the sheet, since the area of the region made of boron nitride particles in the sheet cross section is relatively large, n Even when is 1 to 5 (that is, when area A is roughly divided), each cell is more likely to be determined to be a boron nitride area, and the proportion of cells determined to be boron nitride areas is large. There is a tendency to
  • step (8) obtain observation images of a total of 5 cross sections of the sheet, calculate the total value from each observation image according to steps (1) to (7), and calculate from each of the total 5 cross sections.
  • the average value X is calculated from the total value.
  • the average value X is 0.01 or more, 0.03 or more, 0.01 or more, 0.03 or more, from the viewpoint of suppressing the orientation of the boron nitride particles even when the boron nitride particles are packed in a large amount and easily obtaining a sheet with excellent heat dissipation performance. It may be 05 or more, 0.07 or more, 0.08 or more, 0.09 or more, or 0.10 or more, and from the viewpoint of suppressing a decrease in insulation properties and mechanical strength, 5 or less, 3 or less, 2 or less , 1.8 or less, 1.6 or less, 1.2 or less, 1 or less, 0.8 or less, 0.5 or less, 0.3 or less, or 0.2 or less.
  • the average value Y of the proportion of each boron nitride region is set to 0.0. It may be 5 or more, 0.52 or more, or 0.54 or more.
  • the average value Y may be 0.8 or less, 0.75 or less, 0.7 or less, or 0.65 or less from the viewpoint of suppressing a decrease in insulation properties and mechanical strength.
  • the orientation index of the sheet may be 15 or less, 13 or less, or 11.5 or less from the viewpoint of suppressing the orientation of boron nitride particles in a direction parallel to the main surface of the sheet.
  • the orientation index of the sheet may be 1 or more, 3 or more, or 5 or more.
  • the thickness of the sheet may be 50 ⁇ m or more, 80 ⁇ m or more, or 100 ⁇ m or more, and may be 500 ⁇ m or less, 400 ⁇ m or less, or 300 ⁇ m or less.
  • Example 1-1 Boron carbide powder with an average particle diameter (D50) of 26 ⁇ m was filled in a carbon crucible, and heated at 1800°C in a nitrogen gas atmosphere using a hot isostatic press device (manufactured by Kobe Steel, Ltd., 02-SYSTEM15X). The boron carbide powder was heated and pressurized under the conditions of 196 MPa for 1.5 hours using the HIP method to nitride the boron carbonitride powder (B 4 CN 4 ).
  • a naphthalene type epoxy resin manufactured by DIC Corporation, HP4032
  • an imidazole compound manufactured by Shikoku Kasei Co., Ltd., 2E4MZ-CN
  • a resin composition was obtained by mixing the powders so that the powder filling rate was 70% by volume. This resin composition was degassed under reduced pressure of 500 Pa for 10 minutes, and then applied onto a PET sheet to a thickness of 1.0 mm. Thereafter, press heating and pressing was performed for 60 minutes at a temperature of 150° C. and a pressure of 30 MPa to produce a sheet with a thickness of 0.5 mm.
  • Example 1-2 The procedure was repeated in the same manner as in Example 1, except that the amount of boric acid was changed to 100 parts by mass (50 mass%) to obtain boron nitride powder (average particle size 44.7 ⁇ m, bulk density 0.75 g/ml). A sheet was produced.
  • Example 1-3 Same as Example 1 except that the amount of boric acid was changed to 81.8 parts by mass (45% by mass) to obtain boron nitride powder (average particle size 51.5 ⁇ m, bulk density 0.74 g/ml). A sheet was prepared.
  • boron carbide powder is obtained by heating and pressurizing in a nitrogen gas atmosphere using a resistance heating furnace at 2000 ° C. and 0.85 MPa for 25 hours.
  • Boron nitride powder (average particle size 42.3 ⁇ m, bulk density 0.67 g/ml) was obtained in the same manner as in Example 1-1, except that boron carbonitride powder was obtained by nitriding, and a sheet was produced. did.
  • Example 2-1 A sheet was produced in the same manner as in Example 1-1, except that the sheet was produced by press heating and pressing for 60 minutes at a temperature of 150° C. and a pressure of 15 MPa.
  • Example 2-2 A sheet was produced in the same manner as in Example 1-2, except that the sheet was produced by press heating and pressing for 60 minutes at a temperature of 150° C. and a pressure of 15 MPa.
  • Comparative example 2 A sheet was produced in the same manner as in Comparative Example 1, except that the sheet was produced by press heating and pressing for 60 minutes at a temperature of 150° C. and a pressure of 15 MPa.
  • Example 3-1 A sheet was produced in the same manner as in Example 2-1, except that the filling rate of boron nitride powder was changed to 65% by volume to obtain a resin composition.
  • Example 3-2 A sheet was produced in the same manner as in Example 2-2, except that the filling rate of boron nitride powder was changed to 65% by volume to obtain a resin composition.
  • Example 3-3 A sheet was produced in the same manner as in Example 2-3, except that the filling rate of boron nitride powder was changed to 65% by volume to obtain a resin composition.
  • Comparative example 3 A sheet was produced in the same manner as Comparative Example 2 except that the filling rate of boron nitride powder was changed to 65% by volume to obtain a resin composition.
  • Example 4-1 A sheet was produced in the same manner as in Example 2-1, except that the filling rate of boron nitride powder was changed to 60% by volume to obtain a resin composition.
  • Example 4-2 A sheet was produced in the same manner as in Example 2-2, except that the filling rate of boron nitride powder was changed to 60% by volume to obtain a resin composition.
  • Example 4-3 A sheet was produced in the same manner as in Example 2-3, except that the filling rate of boron nitride powder was changed to 60% by volume to obtain a resin composition.
  • Comparative example 4 A sheet was produced in the same manner as Comparative Example 2 except that the filling rate of boron nitride powder was changed to 60% by volume to obtain a resin composition.
  • the X-ray diffraction peak was measured using an X-ray diffraction device (Ultima IV-N), and the peak intensity of the (002) plane/the peak intensity of the (100) plane was calculated as follows: It was measured as the orientation index of boron nitride particles in the sheet. The measurement results of the orientation index are shown in Tables 1 to 4.
  • Average values X and Y were calculated by the following procedure. The calculation results of the average values X and Y are shown in Tables 1 to 4. (1) The cross sections of the sheets produced in each of the Examples and Comparative Examples were observed using a SEM at a magnification of 1000 times to obtain observation images in bmp format. (2) The obtained observation image was imported into image processing software "imageJ" and filtered using a median filter (3 ⁇ 3 pixels). Next, the region made of boron nitride particles and the other region (resin region) were subjected to binarization processing using the Otsu method to obtain a binarized image.
  • area A of 50 ⁇ m on the short side x 100 ⁇ m on the long side in the obtained binarized image, draw a straight line that divides the short side of area A into n equal parts and the long side into 2n equal parts, and divide the area A into multiple cells. (However, n is an integer of 1 or more).
  • the calculated area ratio was 80% or more, it was determined that the one cell was a boron nitride region, and if the area ratio was less than 20%, it was determined that the one cell was a resin region.
  • the determination in (4) above was made for each of the two cells, and the ratio of the number of cells determined to be boron nitride regions based on the total number of cells (2) was calculated.
  • n was 2 to 200, the above (4) and (5) were performed, and the ratio of the number of cells determined to be in the boron nitride region was calculated.
  • a total value was calculated from the ratio of the number of cells determined to be in each boron nitride region when n was 1 to 5.
  • FIG. 3 shows a SEM image of the cross section of the sheet of Example 1-1
  • FIG. 4 shows a SEM image of the cross section of the sheet of Comparative Example 1.
  • the measurement result of the thermal conductivity of Example 1-2 was 24.4 W/(m K), and the measurement result of the thermal conductivity of Comparative Example 1 was 17.2 W/(m K). .

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013543834A (ja) * 2010-11-10 2013-12-09 イーエスケイ セラミクス ゲーエムベーハー アンド カンパニー カーゲー 窒化ホウ素凝集体、その製造方法およびその使用
WO2020004600A1 (ja) * 2018-06-29 2020-01-02 デンカ株式会社 塊状窒化ホウ素粒子、窒化ホウ素粉末、窒化ホウ素粉末の製造方法、樹脂組成物、及び放熱部材
WO2021079912A1 (ja) * 2019-10-23 2021-04-29 デンカ株式会社 窒化ホウ素粉末及びその製造方法、炭窒化ホウ素粉末、並びに、複合材及び放熱部材
JP2022106113A (ja) * 2021-01-06 2022-07-19 デンカ株式会社 窒化ホウ素粉末、熱伝導性樹脂組成物、放熱シート及び電子部品構造体

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013543834A (ja) * 2010-11-10 2013-12-09 イーエスケイ セラミクス ゲーエムベーハー アンド カンパニー カーゲー 窒化ホウ素凝集体、その製造方法およびその使用
WO2020004600A1 (ja) * 2018-06-29 2020-01-02 デンカ株式会社 塊状窒化ホウ素粒子、窒化ホウ素粉末、窒化ホウ素粉末の製造方法、樹脂組成物、及び放熱部材
WO2021079912A1 (ja) * 2019-10-23 2021-04-29 デンカ株式会社 窒化ホウ素粉末及びその製造方法、炭窒化ホウ素粉末、並びに、複合材及び放熱部材
JP2022106113A (ja) * 2021-01-06 2022-07-19 デンカ株式会社 窒化ホウ素粉末、熱伝導性樹脂組成物、放熱シート及び電子部品構造体

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