WO2019073690A1 - 窒化ホウ素粉末、その製造方法及びそれを用いた放熱部材 - Google Patents
窒化ホウ素粉末、その製造方法及びそれを用いた放熱部材 Download PDFInfo
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- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
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Definitions
- the present invention relates to a boron nitride (BN) powder, a method of producing the same and a use thereof.
- the present invention relates to a boron nitride powder, a method for producing the same, and a thermally conductive resin composition using the same.
- heat-generating electronic components such as power devices, transistors, thyristors, and CPUs
- heat radiation measures (1) high thermal conductivity of the insulating layer of the printed wiring board on which the heat-generating electronic component is mounted, (2) printed wiring on which the heat-generating electronic component or heat-generating electronic component is mounted
- thermal interface materials As an insulating layer and a thermal interface material of a printed wiring board, those in which a ceramic powder is filled in a silicone resin or an epoxy resin are used.
- the insulating layer used tends to be thinner than the conventional several hundred ⁇ m and may be several tens of ⁇ m or more and 100 ⁇ m or less, and the filler corresponding thereto is also the conventional It is required to reduce the particle diameter to an average particle diameter of several tens to several hundreds ⁇ m to 20 ⁇ m or less.
- hexagonal boron nitride (Hexagonal Boron Nitride) powder that has excellent properties as an electrical insulating material, such as high thermal conductivity, high insulation, and low relative dielectric constant, attracts attention. There is.
- hexagonal boron nitride particles have a thermal conductivity of 400 W / (m ⁇ K) in the in-plane direction (a-axis direction), the thermal conductivity in the thickness direction (c-axis direction) is 2 W / (M ⁇ K), and the anisotropy of the thermal conductivity derived from the crystal structure and scaly is large. Furthermore, when hexagonal boron nitride powder is filled in a resin, the particles are aligned in the same direction and oriented.
- the in-plane direction (a-axis direction) of the hexagonal boron nitride particles is perpendicular to the thickness direction of the thermal interface material, and the in-plane direction of the hexagonal boron nitride particles (a-axis direction ) could not be fully utilized.
- Patent Document 1 proposes that the in-plane direction (a-axis direction) of the hexagonal boron nitride particles is oriented in the thickness direction of the high thermal conductivity sheet, and the in-plane direction of the hexagonal boron nitride particles (a-axis direction Can take advantage of the high thermal conductivity of
- Patent Document 1 it is necessary to laminate oriented sheets in the next step, and the manufacturing process tends to be complicated; (2) it is necessary to cut thinly into sheets after laminating and curing There is a problem that it is difficult to secure the dimensional accuracy of the thickness of the sheet.
- the hexagonal boron nitride particles have a scaly shape, the viscosity increases at the time of filling into the resin, and the flowability deteriorates, so high filling is difficult.
- Patent Document 2 proposes the use of a boron nitride powder in which hexagonal boron nitride particles of primary particles are aggregated without being oriented in the same direction, and it is believed that the anisotropy of the thermal conductivity can be suppressed.
- Patent Document 3 spherical boron nitride (Patent Document 3) produced by a spray-drying method or boron nitride (Patent Document 4) or agglomerates produced using boron carbide as a raw material
- Patent Document 5 agglomerated boron nitrides which have been repeatedly produced.
- they could only produce bulk boron nitride powder having a particle size of more than 20 ⁇ m in practice, and could not obtain bulk boron nitride having a particle size smaller than that.
- SGPS (trade name, manufactured by Denka Co., Ltd.) is commercially available as agglomerated boron nitride powder having an average particle size of 20 ⁇ m or less.
- this SGPS has insufficient particle strength and has a high orientation index. Was inadequate.
- Patent Document 6 a method of obtaining spherical boron nitride fine powder using a vapor phase synthesis method has been reported (Patent Document 6), but since the particles obtained by this method have a small average particle diameter, the heat dissipation is insufficient. Met.
- the above-mentioned prior art can not solve the problem that the produced agglomerated particles generally exceed 20 ⁇ m, and agglomerated particles having a particle diameter smaller than that can not be produced. For this reason, in the prior art, it was difficult to produce a massive boron nitride powder having a degree of orientation and a large crushing strength and a size of 20 ⁇ m or less.
- an object of the present invention is to provide a boron nitride powder having an average particle diameter of 2 ⁇ m to 20 ⁇ m, which is excellent in thermal conductivity and high in particle strength.
- a boron nitride powder having excellent thermal conductivity and high particle strength and having a high average particle diameter of 2 ⁇ m to 20 ⁇ m can be produced by a specific production method. It reached.
- the embodiments of the present invention can provide the following.
- the average particle diameter of the boron nitride powder is 2 ⁇ m or more and 20 ⁇ m or less.
- the orientation index obtained from X-ray diffraction of the boron nitride powder is 20 or less.
- the fired product obtained by the pressure nitriding and firing step is mixed with a boron source and raised to a temperature at which decarburization can be started, and then raised to a holding temperature of at least 1800 ° C. at a heating rate of 5 ° C./min or less.
- the boron nitride powder obtained according to the embodiment of the present invention exhibits an effect of having an average particle diameter of 2 ⁇ m to 20 ⁇ m and excellent in thermal conductivity and high in particle strength.
- the photograph by electron microscope observation of the boron nitride powder obtained by the manufacturing method of Example 1 of this invention is shown.
- the high-resolution photograph (enlarged view) by electron microscope observation of the boron nitride powder obtained by the manufacturing method of Example 1 of this invention is shown.
- the photograph by electron microscope observation of the boron nitride powder obtained by the manufacturing method of Example 2 of this invention is shown.
- the high-resolution photograph (enlarged view) by electron microscope observation of the boron nitride powder obtained by the manufacturing method of Example 2 of this invention is shown.
- the boron nitride powder according to an embodiment of the present invention includes massive boron nitride in which scaly hexagonal boron nitride primary particles are agglomerated to form a lump having the following characteristics.
- mass boron nitride particles or “mass particles” which are not according to the prior art refer to particles of boron nitride in which scaly hexagonal boron nitride primary particles are aggregated to form a mass.
- the massive boron nitride particles have a particle strength (single granule crushing strength) determined in accordance with JIS R 1639-5: 2007 of 5.0 MPa or more when the cumulative fracture rate is 63.2%.
- the particle strength at a cumulative fracture rate of 63.2% of the massive particles may be 6.0 MPa or more, and more preferably 7.0 MPa or more.
- the upper limit value of the particle strength at a cumulative fracture rate of 63.2% of the massive particles is not particularly limited, but can be prepared to be, for example, 30 MPa or less and 20 MPa or less.
- the “boron nitride powder” may have an average particle diameter of 2 ⁇ m or more, more preferably 4 ⁇ m or more, and still more preferably 5 ⁇ m or more.
- the average particle diameter of the boron nitride powder may be 20 ⁇ m or less, more preferably 19 ⁇ m or less, and still more preferably 18 ⁇ m or less.
- the range of the average particle diameter of the boron nitride powder can be 2 ⁇ m or more and 20 ⁇ m or less, and more preferably 4 ⁇ m or more and 18 ⁇ m or less.
- the average particle size is too small, less than 2 ⁇ m, a problem of the thermal conductivity decreasing may occur.
- the average particle size is more than 20 ⁇ m and too large, the difference between the thickness of the sheet and the average particle size of the boron nitride powder decreases when producing a sheet having a thickness of several tens of ⁇ m, There is a risk that the preparation of the sheet may be difficult.
- the orientation index of the boron nitride powder according to an embodiment of the present invention can be determined from X-ray diffraction, and the value is 20 or less, preferably 19 or less, more preferably 18 or less.
- orientation index is more than 20 and is too large, there is a problem that the thermal conductivity is lowered.
- the lower limit of the orientation index is not particularly limited, but in general, it is considered to be about 6 even if completely random.
- the boron nitride powder can have a thermal conductivity of 6 W / (m ⁇ K) or more.
- a thermal conductivity 6 W / (m ⁇ K) or more.
- the boron nitride powder according to an embodiment of the present invention can be manufactured by any of the following two types of techniques.
- the method (a) includes a pressure nitriding firing step, a decarburization crystallization step, and a grinding step.
- boron carbide having a carbon content of 18% to 21% and an average particle diameter of 5 ⁇ m to 15 ⁇ m is used as a raw material.
- Boron carbonitride can be obtained by performing pressure nitriding at an atmosphere of specific firing temperature and pressure conditions described later, for the boron carbide raw material.
- the average particle diameter of the boron carbide raw material is 5 ⁇ m or more and 15 ⁇ m or less in order to affect the average particle diameter of the finally obtained bulk boron nitride. It is desirable that the boron carbide raw material does not contain the impurities boric acid and free carbon except unavoidable ones, or, if contained, in a small amount.
- the lower limit value of the average particle diameter of the boron carbide raw material can be preferably 6 ⁇ m or more, more preferably 8 ⁇ m or more.
- the average particle size is less than 5 ⁇ m, there arises a problem that the orientation index of the formed bulk particles is large.
- the upper limit of the average particle diameter of boron carbide can be preferably 14 ⁇ m or less, more preferably 13 ⁇ m or less. If the average particle size is larger than 15 ⁇ m, the formed agglomerates become too large, and coarse particles are likely to remain even after pulverization, which is not preferable. In addition, if grinding is performed until such coarse particles are completely eliminated, a problem that the orientation index becomes large occurs, which is also not preferable.
- the carbon content of the boron carbide raw material used in the pressure nitriding / baking step is desirably lower than B 4 C (21.7%) in composition, preferably in the range of 18.0% to 20.5%. be able to.
- the lower limit of the carbon content of the boron carbide may preferably be 19% or more.
- the upper limit of the carbon content of the boron carbide may preferably be 20.5% or less. If the amount of carbon exceeds 21%, the amount of carbon volatilized during the decarburization and crystallization step described later becomes too large, and dense massive boron nitride can not be formed, and finally carbon of boron nitride which can be formed It is not preferable because the problem occurs that the amount is too high. Moreover, it is difficult to produce stable boron carbide having a carbon content of less than 18% because the deviation from the theoretical composition becomes too large.
- a known production method can be applied to the method for producing boron carbide, and boron carbide having a desired average particle size and carbon content can be obtained.
- heating can be performed at 1800 to 2400 ° C. for 1 to 10 hours in an inert gas atmosphere to obtain a boron carbide lump.
- the boron carbide lump can be crushed, sieved, washed, impurities removed, dried and the like as appropriate to produce a boron carbide powder.
- a mixture of boric acid and acetylene black, which are raw materials of boron carbide, is preferably 25 to 40 parts by mass of acetylene black with respect to 100 parts by mass of boric acid.
- the atmosphere for producing boron carbide is preferably an inert gas, and examples of the inert gas include argon gas and nitrogen gas, and these can be used alone or in combination as appropriate. Among these, argon gas is preferable.
- a common grinder or disintegrator can be used to grind the boron carbide lump, and for example, an appropriate particle size can be obtained by grinding for about 0.5 to 3 hours.
- the ground boron carbide is preferably sieved to a particle size of 75 ⁇ m or less using a sieve screen.
- the firing temperature in the pressure nitriding and firing step is 1800 ° C. or more, preferably 1900 ° C. or more. Further, the upper limit value of the firing temperature can be preferably 2400 ° C. or less, more preferably 2200 ° C. or less. The range of the calcination temperature in a preferred embodiment may be 1800 to 2200 ° C.
- the pressure in the pressure nitriding / baking step is 0.6 MPa or more, more preferably 0.7 MPa or more.
- the upper limit of the pressure is preferably 1.0 MPa or less, and more preferably 0.9 MPa or less.
- the pressure range in the preferred embodiment can also be 0.7 to 1.0 MPa. If the pressure is less than 0.6 MPa, there arises a problem that the nitriding of boron carbide does not proceed sufficiently. In terms of cost, the pressure is preferably 1.0 MPa or less, but it is also possible to set the pressure to a value higher than this.
- the firing temperature and pressure conditions in the pressure nitriding and firing step in the preferred embodiment can be a firing temperature of 1800 to 2200 ° C. and 0.7 to 1.0 MPa. When the pressure is less than 0.7 MPa at a firing temperature of 1800 ° C., nitriding of boron carbide may not proceed sufficiently.
- a gas in which a nitriding reaction proceeds is required, and examples thereof include nitrogen gas and ammonia gas, and these can be used alone or in combination of two or more. Among them, nitrogen gas is preferable in view of the easiness of nitriding and the cost.
- the atmosphere preferably contains at least 95% (V / V) or more of nitrogen gas, more preferably 99.9% (V / V) or more.
- the firing time in the pressure nitriding and firing step is not particularly limited as long as the nitriding proceeds sufficiently, but it may be preferably 6 to 30 hours, more preferably 8 to 20 hours.
- the boron carbonitride obtained in the pressure nitriding and firing step is heated to a holding temperature at a specific temperature rising rate described later in an atmosphere of normal pressure or higher.
- a specific temperature rising rate described later in an atmosphere of normal pressure or higher.
- the temperature at which decarburization can be initiated in the decarburization crystallization step is a temperature that can be set according to the system, but can be set, for example, in the range of 1000 to 1500 ° C., more preferably in the range of 1000 to 1200 ° C. It is. Further, the atmosphere above normal pressure may mean normal pressure (atmospheric pressure) or may be pressurized, but when pressurized, for example, it may be 0.5 MPa or less, preferably 0.3 MPa or less .
- the temperature rising rate to the holding temperature is 5 ° C./min (that is, degree Celsius per minute) or less, preferably 4 ° C./min or less, 3 ° C./min. Alternatively, the temperature may be less than or equal to 2 ° C./min.
- the holding temperature after the above-mentioned temperature rise is 1800 ° C. or higher, and more preferably 2000 ° C. or higher.
- the upper limit value of the holding temperature is not particularly limited, but may preferably be 2200 ° C. or less, more preferably 2100 ° C. or less. If the holding temperature is too low, less than 1800 ° C., grain growth may not occur sufficiently, and the thermal conductivity may be reduced. On the other hand, when the holding temperature is 1800 ° C. or more, grain growth is likely to occur favorably, and the thermal conductivity is likely to be improved.
- the holding time at the holding temperature is not particularly limited as long as crystallization proceeds sufficiently, and in a preferred embodiment, for example, the range of more than 0.5 hours and less than 40 hours, more preferably the range of 1 to 30 hours It can be done.
- the holding time may be preferably 1 hour or more, more preferably 3 hours or more, still more preferably 5 hours or more, and still more preferably 10 hours or more.
- the upper limit of the holding time may be preferably 30 hours or less, more preferably 20 hours or less.
- the holding time is 1 hour or more, grain growth is expected to occur well, and if the holding time is 30 hours or less, it is possible to reduce the progress of the grain growth and the decrease in particle strength, and also the firing It can be expected that the long time makes it possible to reduce industrial disadvantages as well.
- decarburization crystallization is performed by mixing a boron source in addition to the boron carbonitride obtained in the pressure nitriding and firing step as a raw material.
- the boron source includes boric acid, boron oxide, or a mixture thereof (and, optionally, other additives used in the art).
- the mixing ratio of the boron carbonitride and the boron source can be appropriately set according to the molar ratio.
- boric acid or boron oxide is used as the boron source, for example, 100 to 300 parts by mass of boric acid ⁇ boron oxide, more preferably 150 to 250 parts by mass of boric acid ⁇ boron oxide are used with respect to 100 parts by mass of boron carbonitride be able to.
- a general pulverizer or disintegrator can be used, and examples thereof include a ball mill, a vibration mill, a jet mill and the like.
- “crushing” also includes “crushing”.
- Procedure (b) comprises a gas phase reaction step, a crystallization step, and a grinding step.
- an intermediate can be obtained by performing vapor phase synthesis at a reaction temperature of 750 ° C. or more using boric acid alkoxide gas and ammonia gas as raw materials.
- a tubular furnace the furnace temperature, ie, the gas phase reaction temperature can be 750 to 1,600 ° C.
- an inert gas stream is used as a carrier gas, and the inert gas
- a vapor phase reaction with ammonia gas can be effected by volatilizing the boric acid alkoxide in a stream of air.
- Examples of the inert gas stream include nitrogen gas and rare gases (such as neon and argon).
- the reaction time of the boric acid alkoxide gas and the ammonia gas is preferably within 30 seconds in order to set the average particle diameter of the obtained boron nitride powder within a predetermined range.
- the boric acid alkoxide is not particularly limited.
- “alkyl group (R)” of “alkoxide (RO—)” is each independently a linear or branched alkyl chain and has 1 to 5 carbon atoms .
- Specific examples of boric acid alkoxides include trimethyl borate, triethyl borate, triisopropyl borate and the like. Among these, trimethyl borate is preferable in terms of reactivity with ammonia and availability.
- the molar ratio of boric acid alkoxide to ammonia used in the gas phase reaction step can be preferably in the range of 1: 1 to 10, in order to bring the average particle diameter of the boron nitride powder into a predetermined range, more preferably It can be 1: 1 to 2.
- the intermediate obtained in the gas phase reaction step is scaly boron nitride.
- the temperature is raised up to 1000 ° C. under an ammonia atmosphere containing 20 volume% or less of ammonia gas, more preferably 15 volume% or less, up to 1000 ° C.
- the ammonia atmosphere contains an inert gas as another gas, preferably nitrogen or argon.
- the temperature is raised until the firing temperature is reached under an ammonia atmosphere containing 50% by volume or more of ammonia gas from the viewpoint of reducing the amount of oxygen and maximizing the yield.
- the said calcination temperature is 1500 degreeC or more, More preferably, it can be 1600 degreeC or more, More preferably, it can be 1700 degreeC or more.
- the ammonia atmosphere contains an inert gas as another gas, and nitrogen is preferable.
- the holding time at the firing temperature is preferably 1 to 20 hours.
- Heat conductive resin composition According to an embodiment of the present invention, the above-described boron nitride powder may be used to produce a heat conductive resin composition. A well-known manufacturing method can be used for the manufacturing method of this heat conductive resin composition. The obtained heat conductive resin composition can be widely used for a heat radiating member etc.
- the resin used for the heat conductive resin composition examples include epoxy resin, silicone resin, silicone rubber, acrylic resin, phenol resin, melamine resin, urea resin, unsaturated polyester, fluorine resin, polyamide (for example, polyimide, polyamide imide, Polyetherimide etc.), polyester (eg polybutylene terephthalate, polyethylene terephthalate etc), polyphenylene ether, polyphenylene sulfide, wholly aromatic polyester, polysulfone, liquid crystal polymer, polyether sulfone, polycarbonate, maleimide modified resin, ABS resin, AAS ( Acrylonitrile-acrylic rubber / styrene resin, AES (acrylonitrile-ethylene-propylene-diene rubber-styrene) resin, etc.
- polyamide for example, polyimide, polyamide imide, Polyetherimide etc.
- polyester eg polybutylene terephthalate, polyethylene terephthalate etc
- polyphenylene ether polypheny
- an epoxy resin (preferably a naphthalene type epoxy resin) is suitable as an insulating layer of a printed wiring board because of its excellent heat resistance and adhesion strength to a copper foil circuit.
- silicone resin is suitable as a thermal interface material because it is excellent in heat resistance, flexibility, adhesion to a heat sink and the like.
- the curing agent in the case of using an epoxy resin include phenol novolac resin, acid anhydride resin, amino resin, and imidazoles. Among these, imidazoles are preferred.
- the content of the curing agent is preferably 0.5 parts by mass or more and 15 parts by mass or less, and more preferably 1.0 parts by mass or more and 10 parts by mass or less.
- volume% or more and 85 volume% or less are preferable, and, as for the usage-amount of the boron nitride powder in 100 volume% of heat conductive resin compositions, 40 volume% or more and 80 volume% or less are more preferable.
- the use amount of the boron nitride powder is 30% by volume or more, the thermal conductivity is improved, and it is easy to obtain sufficient heat dissipation performance.
- the content of the boron nitride powder is 85% by volume or less, the formation of voids during molding can be reduced, and the reduction in insulation and mechanical strength can be reduced.
- Average Particle Size The average particle size was measured using a laser diffraction scattering particle size distribution analyzer (LS-13 320) manufactured by Beckman Coulter, without applying a homogenizer to the sample before the measurement processing. Moreover, the obtained average particle diameter is an average particle diameter by a volumetric statistic value.
- Particle Strength Measurement was carried out according to JIS R 1639-5: 2007.
- a micro compression tester (“MCT-W500” manufactured by Shimadzu Corporation) was used.
- the measurement was performed on 20 particles or more using the formula of ⁇ P / ( ⁇ ⁇ d 2 ), and the value at the cumulative failure rate of 63.2% was calculated. In addition, when the average particle diameter was less than 2 ⁇ m, calculation of particle strength was impossible.
- Thermal conductivity measured the sheet
- Thermal conductivity H: unit W / (m ⁇ K)
- thermal diffusivity A: unit m 2 / sec
- density B: unit kg / m 3
- specific heat capacity C: unit J / ( From kg ⁇ K)
- H A ⁇ B ⁇ C.
- the thermal diffusivity was obtained by processing a sheet as a measurement sample to a width of 10 mm ⁇ 10 mm ⁇ a thickness of 0.05 mm by a laser flash method.
- the measurement apparatus used the xenon flash analyzer ("LFA447NanoFlash” by NETZSCH).
- the density was determined using the Archimedes method.
- the specific heat capacity was determined using a DSC ("ThermoPlus Evo DSC 8230" manufactured by RIGAKU Co., Ltd.).
- the pass value of the thermal conductivity was set to 5 W / (m ⁇ K) or more.
- Example 1 produced boron nitride powder according to method (a). Moreover, the prepared boron nitride powder was filled in a resin and evaluated.
- boron carbide synthesis 100 parts of Nippon Denko orthoboric acid (hereinafter abbreviated as "boric acid”) and 35 parts of Denka Co., Ltd. acetylene black (trade name HS100) are mixed using a Henschel mixer and then filled in a graphite crucible The resultant was heated in an arc furnace at 2200 ° C. for 5 hours in an argon atmosphere to synthesize boron carbide (B 4 C).
- boric acid Nippon Denko orthoboric acid
- acetylene black trade name HS100
- the synthesized boron carbide block is ground by a ball mill for 1 hour and 40 minutes, sieved to a particle size of 75 ⁇ m or less using a sieve network, and further washed with a nitric acid aqueous solution to remove impurities such as iron, filtered and dried to obtain an average particle size.
- a 10 ⁇ m boron carbide powder was made.
- the carbon content of the obtained boron carbide powder was 19.9%.
- the characteristics of the obtained boron nitride powder as a filler to a resin were evaluated.
- a mixture of 100 parts of a naphthalene type epoxy resin (manufactured by DIC, trade name: HP 4032) and 10 parts of imidazole (trade name: 2E4MZ-CN, manufactured by Shikoku Kasei Co., Ltd.) as a curing agent is 100 vol.
- the mixture was mixed to give a thickness of 0.3 mm on a PET sheet, and then vacuum degassing at 500 Pa was performed for 10 minutes. Thereafter, press heating and pressing were performed for 60 minutes under conditions of a temperature of 150 ° C. and a pressure of 160 kg / cm 2 to obtain a 0.05 mm sheet.
- Example 2 In Example 2, boron nitride powder was synthesized according to the method (b) and then loaded into a resin.
- TMB-R Trimethyl borate
- ammonia gas purity 99.9% or more
- the recovered white powder is filled in a crucible made of boron nitride and set in an induction heating furnace, and then heated in a mixed atmosphere of nitrogen and ammonia up to a temperature of 1000 ° C. in an atmosphere containing 10 vol% ammonia gas, 1000 The temperature was raised to 1,800 ° C., which is the holding temperature, in an atmosphere containing 50% by volume of ammonia gas at temperatures above 0 ° C. It heated at the said holding
- the resin was charged under the same conditions as in Example 1 and evaluated.
- Example 3 produced agglomerated boron nitride powder under the same conditions as Example 1, except that the grinding during boron carbide synthesis was changed to 1 hour and 20 minutes, and "boron carbide having an average particle diameter of 14 ⁇ m" was synthesized. .
- Example 4 manufactured the boron nitride powder on the conditions similar to Example 1 except having made jet-mill crushing pressure 0.5 Mpa.
- Example 5 changes the grinding at the time of boron carbide synthesis to 1 hour and 20 minutes, synthesizes "boron carbide (19.8% of carbon content) having an average particle diameter of 14 ⁇ m", and jets crush pressure of agglomerated boron nitride
- a boron nitride powder was produced under the same conditions as in Example 1 except that the powder was ground at 5 MPa.
- Example 6 manufactured the boron nitride powder on the conditions similar to Example 1 except having made the temperature increase rate from 1000 degreeC into 0.5 degree-C / min.
- Example 7 manufactured the boron nitride powder on the conditions similar to Example 1 except having made the temperature increase rate from 1000 degreeC into 5 degrees C / min.
- Comparative Example 1 is a boron nitride under the same conditions as in Example 1 except that grinding at the time of boron carbide synthesis is changed to 5 hours, and “boron carbide having an average particle diameter of 2 ⁇ m” is synthesized to synthesize agglomerated boron nitride. A powder was produced. Since the average particle diameter of the obtained boron nitride powder was too small, the particle strength could not be measured.
- Comparative Example 2 is the same as Example 1, except that the grinding time at the time of boron carbide synthesis is changed to 45 minutes, and “boron carbide with an average particle diameter of 25 ⁇ m (carbon amount 20.1%)” is synthesized, Boron nitride powder was produced.
- Comparative Example 3 changes the grinding time at the time of boron carbide synthesis to 45 minutes, synthesizes "boron carbide (carbon amount 20.0%) having an average particle diameter of 25 ⁇ m", and sets the jet mill grinding pressure to 0.5 MPa.
- a boron nitride powder was produced under the same conditions as in Example 1 except that the powder was ground until the powder disappeared.
- Comparative Example 4 The boron nitride powder was manufactured on the conditions of Example 1 except the comparative example 4 having made the temperature increase rate from 1000 degreeC into 10 degrees C / min.
- Comparative Example 5 was produced under the same conditions as in Example 2 except that the firing was carried out in an atmosphere containing 50 vol% ammonia gas up to a temperature of 1000 ° C., and the primary particles were scaly Thus, boron nitride fine particles having spherical primary particles were obtained instead of agglomerated boron nitride. Since the average particle diameter of the obtained boron nitride powder was too small, the particle strength could not be measured.
- the present invention particularly preferably relates to a boron nitride powder excellent in thermal conductivity, a method for producing the same, and a method for producing the same, which is filled in a resin composition particularly for applications with a film thickness of 100 ⁇ m or less.
- a heat conductive resin composition using the present invention can be provided, and can be suitably used as a raw material of a heat radiating member of a heat generating electronic component such as a power device.
- the heat conductive resin composition can be widely used for a heat radiating member.
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Abstract
Description
以下の(A)~(C)の特徴を有する、一次粒子が鱗片状の六方晶窒化ホウ素が凝集して塊状粒子になった塊状窒化ホウ素を含む窒化ホウ素粉末。
(A)前記塊状粒子における累積破壊率63.2%時の粒子強度が5.0MPa以上であること。
(B)前記窒化ホウ素粉末の平均粒径が2μm以上20μm以下であること。
(C)前記窒化ホウ素粉末のX線回折から求められる配向性指数が20以下であること。
[1]に記載の窒化ホウ素粉末を含み、膜厚が100μm以下である放熱部材。
[1]に記載の窒化ホウ素粉末の製造方法であって、
炭素量18%以上21%以下かつ平均粒径5μm以上15μm以下である炭化ホウ素を、1800℃以上かつ0.6MPa以上の窒素加圧雰囲気にて焼成する、加圧窒化焼成工程と、
前記加圧窒化焼成工程により得られた焼成物をホウ素源と混合し、脱炭開始可能な温度に上昇させた後に昇温速度5℃/min以下で1800℃以上である保持温度になるまで昇温を行い、前記保持温度の窒素雰囲気にて保持することで、塊状窒化ホウ素を得る、脱炭結晶化工程と、
前記脱炭結晶化工程により得られた塊状窒化ホウ素を粉砕し、平均粒径が2μm以上20μm以下である窒化ホウ素粉末を得る粉砕工程と
を含む、製造方法。
[1]に記載の窒化ホウ素粉末の製造方法であって、
ホウ酸アルコキシドガスおよびアンモニアガスを、750℃以上で気相反応させる気相反応工程と、
前記気相反応工程により得られた中間体を、1000℃までは20体積%以下のアンモニア雰囲気で、1000℃以上では50体積%以上の割合のアンモニア雰囲気の条件にて1500℃以上である焼成温度に至るまで昇温し、前記焼成温度にて焼成を行い、塊状窒化ホウ素を得る結晶化工程と、
前記結晶化工程により得られた塊状窒化ホウ素を粉砕し、平均粒径が2μm以上20μm以下である窒化ホウ素粉末を得る粉砕工程と
を含む、製造方法。
本発明の実施形態に係る窒化ホウ素粉末は、以下の特徴を有する、鱗片状の六方晶窒化ホウ素一次粒子が凝集して塊状になった塊状窒化ホウ素を含む。
本明細書において、従来技術によるものでは無い「塊状窒化ホウ素粒子」または「塊状粒子」とは、鱗片状の六方晶窒化ホウ素一次粒子が凝集して塊状になった窒化ホウ素の粒子のことを言う。当該塊状窒化ホウ素粒子は、JIS R1639-5:2007に準拠して求められる粒子強度(単一顆粒圧壊強さ)が、累積破壊率63.2%時に5.0MPa以上である。粒子強度が5.0MPa未満では、樹脂との混練時やプレス時などに応力で凝集粒子が崩れてしまい、熱伝導率が低下する問題が発生する。なお「63.2%」とは、上記JIS R1639-5:2007が引用するJIS R1625:2010にて教示されている、ワイブル(Weibull)分布関数における lnln{1/(1-F(t))} = 0 を満たす値として知られているものであり、粒子の個数基準の値である。
本発明の実施形態に係る「窒化ホウ素粉末」は、その平均粒径が2μm以上であり、より好ましくは4μm以上、さらに好ましくは5μm以上であってよい。また、窒化ホウ素粉末の平均粒径は20μm以下であり、より好ましくは19μm以下、さらに好ましくは18μm以下であってよい。窒化ホウ素粉末の平均粒径の範囲は、2μm以上20μm以下とすることができ、より好ましくは4μm以上18μm以下としてもよい。
本発明の実施形態に係る窒化ホウ素粉末の配向性指数は、X線回折から求めることができ、その値は20以下であり、好ましくは19以下、より好ましくは18以下とすることもできる。
本発明の実施形態に係る窒化ホウ素粉末は、下記の二種類の手法のいずれかによって製造可能である。
手法(a)は、加圧窒化焼成工程、脱炭結晶化工程、および粉砕工程を含む。
手法(a)における加圧窒化焼成工程では、炭素量18%以上21%以下かつ平均粒径が5μm以上15μm以下の炭化ホウ素を原料として使用する。この炭化ホウ素原料を、後述する特定の焼成温度及び加圧条件の雰囲気にて、加圧窒化焼成を行うことで、炭窒化ホウ素を得ることができる。
炭化ホウ素原料の平均粒径は、最終的に得られる塊状窒化ホウ素の平均粒径に影響するため、平均粒径5μm以上15μm以下である。炭化ホウ素原料には、不純物のホウ酸や遊離炭素が、不可避的なものを除いて含まれないか、または含まれるとしても少量であることが望ましい。
加圧窒化焼成工程における焼成温度は1800℃以上であり、好ましくは1900℃以上とすることができる。また、焼成温度の上限値は、好ましくは2400℃以下、より好ましくは2200℃以下とすることができる。好ましい実施形態における当該焼成温度の範囲は、1800~2200℃とすることができる。
手法(a)における脱炭結晶化工程は、加圧窒化焼成工程にて得られた炭窒化ホウ素を、常圧以上の雰囲気にて、後述する特定の昇温速度で保持温度になるまで昇温を行い、特定の温度範囲で一定時間保持する熱処理を行うことにより、鱗片状の六方晶窒化ホウ素である一次粒子が凝集して塊状になった塊状窒化ホウ素粒子を得ることができる。すなわちこの脱炭結晶化工程においては、炭窒化ホウ素を脱炭化させるとともに、所定の大きさの鱗片状にさせつつ、これらを凝集させて塊状の窒化ホウ素粒子とする。
前記加圧窒化焼成工程及び前記脱炭結晶化工程を経て、鱗片状窒化ホウ素粒子(一次粒子)が凝集した塊状粒子を得ることができる。本実施形態により得られるこの塊状粒子は粒子強度が高いため、粉砕後の平均粒径が2μm以上20μm以下となるように粉砕しても、その塊状形態および低い配向性指数を維持できるという効果を奏する。
手法(b)は、気相反応工程、結晶化工程、および粉砕工程を含む。
気相反応工程では、ホウ酸アルコキシドガスとアンモニアガスとを原料とし、反応温度750℃以上において気相合成を行うことにより、中間体を得ることができる。気相反応工程では、管状炉(炉温度すなわち気相反応温度としては750~1,600℃とすることができる)を用いることができ、キャリアガスとして不活性ガス気流を使い、当該不活性ガス気流中でホウ酸アルコキシドを揮発させることによってアンモニアガスとの気相反応を起こさせることができる。
結晶化工程では、気相反応工程で得られた中間体を鱗片状窒化ホウ素にする。結晶化工程の温度条件では、昇温を開始してから1000℃まではアンモニアガス20体積%以下、より好ましくは15体積%以下を含むアンモニア雰囲気下で昇温する。当該アンモニア雰囲気にはその他のガスとして不活性ガスが含まれ、好ましくは窒素またはアルゴンを含めることができる。
上記の気相合成工程及び結晶化工程を経て得られた鱗片状窒化ホウ素粉末は、高い粒子強度を有しているため、上述した平均粒径を有するようにして二次粒子(凝集粒子)を粉砕しても、依然として塊状形態および低い配向性指数を維持することが可能である。したがって手法(a)と同様に粉砕工程を行うことができる。
本発明の或る実施形態によれば、上述した窒化ホウ素粉末を含めるようにして用い、熱伝導樹脂組成物を製造することもできる。この熱伝導樹脂組成物の製造方法は、公知の製造方法を用いることができる。得られた熱伝導樹脂組成物は、放熱部材等に幅広く使用することができる。
熱伝導樹脂組成物に使用する樹脂としては、例えばエポキシ樹脂、シリコーン樹脂、シリコーンゴム、アクリル樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル、フッ素樹脂、ポリアミド(例えば、ポリイミド、ポリアミドイミド、ポリエーテルイミド等)、ポリエステル(例えば、ポリブチレンテレフタレート、ポリエチレンテレフタレート等)、ポリフェニレンエーテル、ポリフェニレンスルフィド、全芳香族ポリエステル、ポリスルホン、液晶ポリマー、ポリエーテルスルホン、ポリカーボネート、マレイミド変性樹脂、ABS樹脂、AAS(アクリロニトリル-アクリルゴム・スチレン)樹脂、AES(アクリロニトリル・エチレン・プロピレン・ジエンゴム-スチレン)樹脂等を用いることができる。特にエポキシ樹脂(好適にはナフタレン型エポキシ樹脂)は、耐熱性と銅箔回路への接着強度が優れていることから、プリント配線板の絶縁層として好適である。また、シリコーン樹脂は耐熱性、柔軟性及びヒートシンク等への密着性が優れていることから熱インターフェース材として好適である。
平均粒径は、ベックマンコールター社製レーザー回折散乱法粒度分布測定装置(LS-13 320)を用いて、測定処理の前に試料にホモジナイザーをかけずに測定した。また、得られた平均粒径は体積統計値による平均粒径である。
JIS R1639-5:2007に準じて測定を実施した。測定装置としては、微小圧縮試験器(島津製作所社製「MCT-W500」)を用いた。粒子強度(σ:単位MPa)は、粒子内の位置によって変化する無次元数(α=2.48)と圧壊試験力(P:単位N)と粒子径(d:単位μm)からσ=α×P/(π×d2)の式を用いて20粒子以上に対して測定を行い、累積破壊率63.2%時点の値を算出した。なお、平均粒径が2μm未満では、粒子強度の算出が不可であった。
配向度の測定にはX線回折装置(リガク社製ULTIMA-IV)を用いた。窒化ホウ素粉末を固めて試料を作成し、試料にX線を照射して、(002)面と(100)面のピーク強度比(002)/(100)を算出して評価した。
熱伝導率は、窒化ホウ素粉末を含んだ熱伝導樹脂組成物から作成したシートを測定用試料として、測定を行った。熱伝導率(H:単位W/(m・K))は、熱拡散率(A:単位m2/sec)と密度(B:単位kg/m3)、比熱容量(C:単位J/(kg・K))から、H=A×B×Cとして、算出した。熱拡散率は、測定用試料としてのシートを幅10mm×10mm×厚み0.05mmに加工し、レーザーフラッシュ法により求めた。測定装置はキセノンフラッシュアナライザ(NETZSCH社製「LFA447NanoFlash」)を用いた。密度はアルキメデス法を用いて求めた。比熱容量は、DSC(リガク社製「ThermoPlus Evo DSC8230」)を用いて求めた。熱伝導率の合格値は5W/(m・K)以上と設定した。
上記(4)の熱伝導率評価法において作成した厚み0.05mm(膜厚50μm)のシートに対し、目視で凹凸なく製膜できていることを確認できたものを○(合格)と評価し、一方作製中にレベリングしてしまい、凹凸ができ製膜できなかったものを×(失格)と評価した。
炭化ホウ素の炭素量は炭素分析装置「IR-412型」(LECO社製)にて測定した。
実施例1は、手法(a)に従って窒化ホウ素粉末を作成した。また作成した窒化ホウ素粉末を樹脂に充填し、評価を行った。
日本電工製オルトホウ酸(以下「ホウ酸」と略記する)100部と、デンカ株式会社製アセチレンブラック(商品名HS100)35部とをヘンシェルミキサーを用いて混合したのち、黒鉛製のルツボ中に充填し、アーク炉にて、アルゴン雰囲気で、2200℃にて5時間加熱し炭化ホウ素(B4C)を合成した。合成した炭化ホウ素塊をボールミルで1時間40分粉砕し、篩網を用いて粒径75μm以下に篩分け、更に硝酸水溶液で洗浄して鉄分等不純物を除去後、濾過・乾燥して平均粒径10μmの炭化ホウ素粉末を作製した。得られた炭化ホウ素粉末の炭素量は19.9%であった。
合成した炭化ホウ素を窒化ホウ素製のルツボに充填した後、抵抗加熱炉を用い、窒素ガス雰囲気下で、2000℃、9気圧(0.8MPa)の条件で10時間加熱することにより炭窒化ホウ素(B4CN4)を得た。
合成した炭窒化ホウ素100部と、ホウ酸100部とをヘンシェルミキサーを用いて混合したのち、窒化ホウ素製のルツボに充填し、抵抗加熱炉を用い0.3MPaの圧力条件で、窒素ガス雰囲気下で、室温から1000℃までの昇温速度を10℃/min、1000℃からの昇温速度を2℃/minとして保持温度2000℃まで昇温した。当該保持温度2000℃にて、保持時間5時間で加熱することにより、一次粒子が凝集して塊状になった塊状窒化ホウ素を合成した。
合成した塊状窒化ホウ素をヘンシェルミキサーにより解砕をおこなった後、篩網を用いて、篩目850μmのナイロン篩にて分級を行った。その後、ジェットミル(第一実業社製「PJM-80」)にて0.3MPaの粉砕条件にて粉砕を行い、平均粒径8μmの窒化ホウ素粉末を得た。
得られた窒化ホウ素粉末の樹脂への充填材としての特性の評価を行った。ナフタレン型エポキシ樹脂(DIC社製、商品名HP4032)100部と硬化剤としてイミダゾール類(四国化成社製、商品名2E4MZ-CN)10部の混合物を100体積%として、窒化ホウ素粉末が50体積%となるように混合し、PET製シートの上に厚みが0.3mmになるように塗布した後、500Paの減圧脱泡を10分間行った。その後、温度150℃、圧力160kg/cm2の条件で60分間のプレス加熱加圧を行って0.05mmのシートとした。
実施例2は手法(b)に従って窒化ホウ素粉末を合成し、その後樹脂に充填した。
炉心管を抵抗加熱炉に設置し温度1000℃に加熱した。ホウ酸トリメチル(多摩化学株式会社製「TMB-R」)を窒素バブリングにより導入管を通して炉心管に導入し、一方、アンモニアガス(純度99.9%以上)も、導入管を経由して炉心管に導入した。導入されたホウ酸トリメチルとアンモニアはモル比1:1.2で、炉内で気相反応し、反応時間10秒で合成することにより白色粉末を生成した。生成した白色粉末を回収した。
回収した白色粉末を窒化ホウ素製ルツボに充填し、誘導加熱炉にセットした後、窒素とアンモニア混合雰囲気で、温度1000℃までは10体積%アンモニアガスを含んだ雰囲気下にて昇温し、1000℃以上では50体積%アンモニアガスを含んだ雰囲気下にて、保持温度である1800℃まで昇温した。当該保持温度で5時間加熱し、焼成終了後、冷却し、焼成物を回収した。
合成した塊状窒化ホウ素をヘンシェルミキサーにより解砕をおこなった後、篩網を用いて、篩目850μmのナイロン篩にて分級を行った。その後、ジェットミル(第一実業社製PJM-80)にて0.3MPaの粉砕条件にて粉砕を行い、平均粒径5μmの窒化ホウ素粉末を得た。
実施例3は炭化ホウ素合成時の粉砕を1時間20分に変更し、「平均粒径14μmの炭化ホウ素」を合成したこと以外は実施例1と同様の条件で、凝集窒化ホウ素粉末を製造した。
実施例4はジェットミル粉砕圧を0.5MPaにしたこと以外は実施例1と同様の条件で、窒化ホウ素粉末を製造した。
実施例5は炭化ホウ素合成時の粉砕を1時間20分に変更し、「平均粒径14μmの炭化ホウ素(炭素量19.8%)」を合成し、凝集窒化ホウ素をジェットミル粉砕圧を0.5MPaにて粉砕したこと以外は実施例1と同様の条件で、窒化ホウ素粉末を製造した。
実施例6は1000℃からの昇温速度を0.5℃/minにしたこと以外は実施例1と同様の条件で、窒化ホウ素粉末を製造した。
実施例7は1000℃からの昇温速度を5℃/minにしたこと以外は実施例1と同様の条件で、窒化ホウ素粉末を製造した。
比較例1は炭化ホウ素合成時の粉砕を5時間に変更し、「平均粒径2μmの炭化ホウ素」を合成し凝集窒化ホウ素を合成したこと以外は実施例1と同様の条件にて、窒化ホウ素粉末を製造した。得られた窒化ホウ素粉末の平均粒径が小さすぎたため、粒子強度は測定不能であった。
比較例2は炭化ホウ素合成時の粉砕時間を45分に変更し、「平均粒径25μmの炭化ホウ素(炭素量20.1%)」を合成したこと以外は実施例1と同様の条件で、窒化ホウ素粉末を製造した。
比較例3は炭化ホウ素合成時の粉砕時間を45分に変更し、「平均粒径25μmの炭化ホウ素(炭素量20.0%)」を合成し、ジェットミル粉砕圧を0.5MPaにし、粗粉がなくなるまで粉砕したこと以外は実施例1と同様の条件で、窒化ホウ素粉末を製造した。
比較例4は1000℃からの昇温速度を10℃/minにした以外は実施例1の条件で、窒化ホウ素粉末を製造した。
比較例5は温度1000℃まで、50体積%アンモニアガスを含んだ雰囲気下にて焼成を行った以外は実施例2と同様の条件で、窒化ホウ素粉末を製造したところ、一次粒子が鱗片状からなる凝集窒化ホウ素ではなく、一次粒子が球状の窒化ホウ素微粒子が得られた。得られた窒化ホウ素粉末の平均粒径は小さすぎたため、粒子強度は測定不能であった。
Claims (4)
- 以下の(A)~(C)の特徴を有する、一次粒子が鱗片状の六方晶窒化ホウ素が凝集して塊状粒子になった塊状窒化ホウ素を含む窒化ホウ素粉末。
(A)前記塊状粒子における累積破壊率63.2%時の粒子強度が5.0MPa以上であること。
(B)前記窒化ホウ素粉末の平均粒径が2μm以上20μm以下であること。
(C)前記窒化ホウ素粉末のX線回折から求められる配向性指数が20以下であること。 - 請求項1に記載の窒化ホウ素粉末を含み、膜厚が100μm以下である放熱部材。
- 請求項1に記載の窒化ホウ素粉末の製造方法であって、
炭素量18%以上21%以下かつ平均粒径5μm以上15μm以下である炭化ホウ素を、1800℃以上かつ0.6MPa以上の窒素加圧雰囲気にて焼成する、加圧窒化焼成工程と、
前記加圧窒化焼成工程により得られた焼成物をホウ素源と混合し、脱炭開始可能な温度に上昇させた後に昇温速度5℃/min以下で1800℃以上である保持温度になるまで昇温を行い、前記保持温度の窒素雰囲気にて保持することで塊状窒化ホウ素を得る、脱炭結晶化工程と、
前記脱炭結晶化工程により得られた塊状窒化ホウ素を粉砕し、平均粒径が2μm以上20μm以下である窒化ホウ素粉末を得る粉砕工程と
を含む、製造方法。 - 請求項1に記載の窒化ホウ素粉末の製造方法であって、
ホウ酸アルコキシドガスおよびアンモニアガスを、750℃以上で気相反応させる気相反応工程と、
前記気相反応工程により得られた中間体を、1000℃までは20体積%以下のアンモニア雰囲気で、1000℃以上では50体積%以上の割合のアンモニア雰囲気の条件にて1500℃以上である焼成温度に至るまで昇温し、前記焼成温度にて焼成を行い、塊状窒化ホウ素を得る結晶化工程と、
前記結晶化工程により得られた塊状窒化ホウ素を粉砕し、平均粒径が2μm以上20μm以下である窒化ホウ素粉末を得る粉砕工程と
を含む、製造方法。
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CN115298151A (zh) * | 2020-03-31 | 2022-11-04 | 电化株式会社 | 复合体的制造方法 |
WO2021251494A1 (ja) * | 2020-06-12 | 2021-12-16 | デンカ株式会社 | 熱伝導性樹脂組成物及び放熱シート |
WO2022039235A1 (ja) * | 2020-08-20 | 2022-02-24 | デンカ株式会社 | 中空部を有する窒化ホウ素粒子を含有するシート |
JP7158634B2 (ja) | 2020-08-20 | 2022-10-21 | デンカ株式会社 | 中空部を有する窒化ホウ素粒子を含有するシート |
JPWO2022039235A1 (ja) * | 2020-08-20 | 2022-02-24 | ||
WO2022071246A1 (ja) * | 2020-09-30 | 2022-04-07 | デンカ株式会社 | 窒化ホウ素粉末、及び窒化ホウ素粉末の製造方法 |
JP7140939B2 (ja) | 2020-09-30 | 2022-09-21 | デンカ株式会社 | 窒化ホウ素粉末、及び窒化ホウ素粉末の製造方法 |
JPWO2022071227A1 (ja) * | 2020-09-30 | 2022-04-07 | ||
WO2022071225A1 (ja) * | 2020-09-30 | 2022-04-07 | デンカ株式会社 | 窒化ホウ素粉末、及び窒化ホウ素粉末の製造方法 |
JPWO2022071225A1 (ja) * | 2020-09-30 | 2022-04-07 | ||
JP7458523B2 (ja) | 2020-09-30 | 2024-03-29 | デンカ株式会社 | 窒化ホウ素粉末 |
WO2022071227A1 (ja) * | 2020-09-30 | 2022-04-07 | デンカ株式会社 | 窒化ホウ素粉末、及び窒化ホウ素粉末の製造方法 |
WO2023162598A1 (ja) * | 2022-02-22 | 2023-08-31 | デンカ株式会社 | 窒化ホウ素粉末の製造方法、窒化ホウ素粉末及び樹脂封止材 |
WO2023204139A1 (ja) * | 2022-04-21 | 2023-10-26 | デンカ株式会社 | 窒化ホウ素粉末、及び、放熱シート、並びに、窒化ホウ素粉末の製造方法 |
WO2023204140A1 (ja) * | 2022-04-21 | 2023-10-26 | デンカ株式会社 | 窒化ホウ素粉末、及び、その製造方法、並びに、放熱シート |
JP7505139B2 (ja) | 2022-04-21 | 2024-06-24 | デンカ株式会社 | 窒化ホウ素粉末、及び、放熱シート、並びに、窒化ホウ素粉末の製造方法 |
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CN111212811B (zh) | 2023-03-21 |
KR20200068673A (ko) | 2020-06-15 |
PH12020550416A1 (en) | 2021-04-12 |
US20200247672A1 (en) | 2020-08-06 |
KR102619752B1 (ko) | 2023-12-29 |
EP3696140A4 (en) | 2020-12-09 |
EP3696140B1 (en) | 2021-07-21 |
EP3696140A1 (en) | 2020-08-19 |
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