WO2013065556A1 - 窒化ホウ素粉末の連続的製造方法 - Google Patents
窒化ホウ素粉末の連続的製造方法 Download PDFInfo
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- WO2013065556A1 WO2013065556A1 PCT/JP2012/077499 JP2012077499W WO2013065556A1 WO 2013065556 A1 WO2013065556 A1 WO 2013065556A1 JP 2012077499 W JP2012077499 W JP 2012077499W WO 2013065556 A1 WO2013065556 A1 WO 2013065556A1
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- 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
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- 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
- C01B21/0645—Preparation by carboreductive nitridation
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/583—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on boron nitride
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/76—Crystal structural characteristics, e.g. symmetry
- C04B2235/767—Hexagonal symmetry, e.g. beta-Si3N4, beta-Sialon, alpha-SiC or hexa-ferrites
Definitions
- the present invention relates to a continuous production method of boron nitride powder. More specifically, after heat-treating the boron-containing material and the nitrogen-containing material to obtain crude boron nitride having a BN content of 80% by weight or more, the crude boron nitride is combined with a boron-containing flux component containing a predetermined amount of boron.
- the present invention relates to a continuous production method of crystalline hexagonal boron nitride powder, which is charged in a heat-resistant container and reheated at 1550 to 2400 ° C. in a continuous reaction furnace in a nitrogen gas atmosphere to grow crystals.
- Hexagonal boron nitride powder (hereinafter referred to as h-BN powder) has excellent properties such as heat resistance, lubricity, electrical insulation, and thermal conductivity, so it is a solid lubricant, mold release agent, and cosmetic raw material. It is used in many applications such as fillers for heat conductive resins and sintered body raw materials. Among them, it is particularly useful as a cosmetic raw material and a heat conductive filler for a resin because of its excellent concealing effect when mixed in cosmetics and high thermal conductivity.
- a boron-containing material such as boric acid, boron oxide, or borax and a nitrogen-containing material such as melamine, urea, dicyandiamide, ammonia, or nitrogen are reacted in a heated atmosphere.
- a nitrogen-containing material such as melamine, urea, dicyandiamide, ammonia, or nitrogen
- Patent Document 1 discloses that a boron-containing substance and a nitrogen-containing substance are heat-treated at a temperature of about 900 to 1300 ° C. to synthesize a crude BN powder, and then the crude BN powder is washed with water. It has been shown that crystalline h-BN powder can be efficiently produced by removing impurities and treating again at a high temperature of about 1500 to 1800 ° C.
- Patent Document 2 discloses that a mixture containing a boron-containing substance such as boric acid and a nitrogen-containing substance such as melamine is baked and crystallized at a high temperature of 1800 ° C. to 2200 ° C. after adding the Ca-containing substance. It has been shown that crystalline h-BN powder can be produced. Similarly, Patent Document 3 shows that calcium carbonate and calcium borate are suitable as Ca-containing substances when producing crystalline h-BN powder. Furthermore, Patent Document 6 discloses a method in which crude boron nitride powder is cured at 60 ° C. or lower for one week or longer and then reheated.
- a boron-containing substance such as boric acid
- a nitrogen-containing substance such as melamine
- Patent Document 4 is characterized by reducing and nitriding a carbon compound serving as a reducing agent and a boron-containing substance such as boric acid at a high temperature of 1650 ° C. to 2300 ° C. in the presence of a nitriding catalyst in a nitrogen gas atmosphere. -A continuous process for the production of BN is described. Patent Document 5 describes a high-temperature continuous reaction furnace suitable for h-BN reductive nitridation.
- JP-A-61-72604 Japanese Patent Laid-Open No. 11-29307 Japanese Patent Laid-Open No. 11-79720 JP 60-155507 A JP-A-62-102080 JP 2010-37123 A
- the present invention provides a method for producing a crystalline hexagonal boron nitride powder having a higher particle size and a higher crystallinity continuously and with less contamination of the furnace with higher efficiency and lower cost. It was raised as an issue.
- the present inventors realize the problem of producing h-BN powder having a large particle size and excellent crystallinity at a high efficiency and at a low cost continuously with less contamination of the furnace. As a result, we conducted an intensive study.
- the crude boron nitride is heat-resistant together with a boron-containing flux component containing a predetermined amount of boron. It was found that crystalline h-BN powder can be continuously produced by charging into a container and reheating at 1550 to 2400 ° C. in a continuous reaction furnace in a nitrogen gas atmosphere to grow crystals. It came.
- the crude product is obtained in the second step.
- Boron nitride is charged into a heat-resistant container together with a boron-containing flux component satisfying the following formula (1), and is reheated at 1550 to 2400 ° C. in a continuous reaction furnace in a nitrogen gas atmosphere to grow crystals. This is a continuous process for producing crystalline hexagonal boron nitride powder.
- Formula (1) Boron content in boron-containing flux component / crude boron nitride content ⁇ 1.4 wt%
- the second of the present invention is the continuous production method of the crystalline hexagonal boron nitride powder according to the first, wherein the heat treatment temperature in the first step is 800 ° C. or higher and lower than 1550 ° C.
- a third aspect of the present invention is the method for continuously producing crystalline hexagonal boron nitride powder according to the first or second aspect, wherein the heat-resistant container is made of graphite or boron nitride.
- a fourth aspect of the present invention is the continuous production method of crystalline hexagonal boron nitride powder according to any one of the first to third, wherein the heat-resistant container is a graphite container at least an inner surface of which is coated with boron nitride. is there.
- a fifth aspect of the present invention is the continuous production method of crystalline hexagonal boron nitride powder according to any one of the first to fourth aspects, wherein the continuous reaction furnace is a pusher type tunnel furnace.
- the crude boron nitride powder has a graphitization index (GI) by X-ray diffraction of 2.5 or more and a number average particle diameter of 9 ⁇ m or less, and 1550 to 2400 ° C. in a nitrogen gas atmosphere.
- the crystalline hexagonal boron nitride powder after the reheating treatment with a graphite has a graphitization index (GI) by X-ray diffraction method of 1.9 or less and a number average particle diameter of 10 ⁇ m or more. 6.
- the present invention includes an invention (Invention A) that does not have the requirement of Formula (1) in the first invention. Also in the invention A, the matters mentioned in the second to sixth inventions are preferable embodiments. Regarding all other requirements, the invention A is the same as the first invention.
- FIG. 1 is a view showing an example of a longitudinal sectional view of a pusher type tunnel furnace used in the present invention.
- FIG. 2 is a diagram showing an example of a heat-resistant container used in the pusher-type tunnel furnace of the present invention.
- the present invention provides a first step of obtaining a crude boron nitride by heat-treating a boron-containing substance and a nitrogen-containing substance, and a boron-containing flux component containing the crude boron nitride and a predetermined amount of boron in an inert gas atmosphere. It is characterized by including a second step of crystal growth by reheating treatment in a continuous reaction furnace.
- crude boron nitride for crystal growth of boron nitride is prepared.
- the crude boron nitride is reacted with a reduced amount of boron to further grow boron nitride crystals.
- boron-containing substance used in the present invention various compounds such as boric acid, boron oxide, borate salts of inorganic or organic compounds, boron halides, borazine, borosiloxane can be used.
- boron compounds such as boric acid, boron oxide, alkali metal or alkaline earth metal borate (for example, borax) can be preferably used.
- boric acid and boron oxide include orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), tetraboric acid (H 2 B 4 O 7 ), and boric anhydride (B 2 O 3 ).
- One or more of the compounds represented by 2 O 3 ) ⁇ (H 2 O) x (where x 0 to 3) are preferred.
- the nitrogen-containing substance used in the present invention may be any substance that contains a nitrogen atom in the molecule, and organic nitrogen compounds, inorganic nitrogen compounds, simple nitrogen substances, and mixtures thereof can be used.
- organic nitrogen compounds among nitrogen-containing substances.
- organic compounds having NH 2 groups such as melamine and urea, organic ammonium salts
- An amide compound, an organic compound having an N ⁇ C— group, and the like are preferable.
- melamine and urea are particularly preferably used.
- examples of inorganic nitrogen compounds include ammonia gas, ammonium salts of alkali metals or alkaline earth metals, and the like.
- nitrogen simple substance nitrogen gas, liquid nitrogen, etc. can be illustrated.
- the boron-containing substance and the nitrogen-containing substance are reacted in advance as long as a predetermined BN content is obtained as described later. It may be allowed to stand, or may be charged into a furnace without being reacted and fired as it is.
- the nitrogen-containing substance is a gas such as ammonia gas or nitrogen gas, only the boron-containing substance is charged into the furnace, and then the inside of the furnace is replaced with the gas and heated as it is.
- the atmosphere can be replaced with a gas such as ammonia gas or nitrogen gas, so that nitrogen can be introduced more efficiently. It is not limited, and it is possible even under a general inert gas atmosphere. Furthermore, a small amount of water or oxygen may be mixed.
- the above components may be mixed using a conventionally known method, for example, using a high-speed stirring device such as a Henschel mixer.
- the maximum temperature of the furnace in the first step is not particularly limited. However, in consideration of the equipment cost of the furnace and the utility cost required for heating, for example, it is less than 1550 ° C, preferably less than 1500 ° C, more preferably less than 1460 ° C, More preferably, it is less than 1400 degreeC, Most preferably, it is less than 1350 degreeC, Preferably it is 800 degreeC or more, More preferably, it is 850 degreeC or more, More preferably, it is 900 degreeC or more. If the maximum temperature of the furnace becomes too high, special heat-resistant materials and expensive heat insulating materials will be required for the furnace in the first step, which will increase the equipment cost and increase the cost of utilities required for heating.
- H-BN powders that are produced cause a cost increase.
- the crystallization of BN powder proceeds halfway, so that the tendency to make crystallization difficult to progress when heated once again after being taken out becomes stronger.
- rate of temperature increase the rate of temperature decrease, the processing time at the maximum temperature, and the like.
- the crude BN powder obtained in the first step needs to have a BN content of 80% by weight or more. If the BN content is less than 80% by weight, a large amount of volatiles and impurities are generated during continuous reheating at 1550-2400 ° C in the second step. Or the yield of the crystalline h-BN powder in the continuous reactor decreases.
- the BN content of the crude BN powder obtained in the first step is preferably 85% by weight or more, more preferably 90% by weight or more.
- the crude BN powder obtained in the first step may be once cooled and taken out into the air atmosphere and cured at a temperature of 60 ° C. or lower for one week or more, or as it is in the second step without being cooled. It may be charged into a continuous reactor. When cured, high crystallization can be promoted.
- Second Step The crude BN powder thus obtained is reheated at 1550-2400 ° C. in a nitrogen gas atmosphere to grow crystals, thereby producing h-BN powder having a large particle size and excellent crystallinity. be able to.
- the present invention is characterized in that the amount of the boron-containing flux component used is suppressed in the second step, but when the boron-containing flux component is suppressed, volatilization of the flux component during the reheating treatment causes Even if the high crystallization of boron nitride is at an excellent level, it may not reach the highest level.
- the maximum temperature at the time of reheating is in the range of 1550 to 2400 ° C, but in order to obtain a higher crystalline h-BN powder, a higher maximum temperature is preferable, and in order to reduce furnace management costs and maintenance costs It is preferable to keep the maximum temperature low.
- the maximum temperature is preferably 1600 to 2300 ° C, more preferably 1700 to 2250 ° C, still more preferably 1750 to 2200 ° C, and most preferably 1800 to 2150 ° C.
- the processing time at the maximum temperature is long, and in order to reduce productivity and utility costs, it is preferable that the processing time at the maximum temperature is short.
- the treatment time at the preferred maximum temperature is 10 minutes to 10 hours, more preferably 20 minutes to 6 hours, and most preferably 30 minutes to 5 hours.
- the atmosphere at the time of reheating needs to be carried out in a nitrogen gas atmosphere.
- the GI can be obtained by calculating the integral intensity ratio, that is, the area ratio of the (100), (101), and (102) lines of the X-ray diffraction diagram by the following formula, and the smaller this value, the higher the crystallinity.
- GI [area ⁇ (100) + (101) ⁇ ] / [area (102)]
- GI is an index of crystallinity of h-BN powder, and the higher the crystallinity, the smaller this value becomes.
- GI 1.60.
- the GI is further reduced because the powder is easily oriented.
- the crude BN powder obtained in the first step preferably has a GI value of 2.5 or more, and the crystalline h-BN powder after crystal growth in the second step has a GI of 1. It is preferable to make it 9 or less. If the GI value of the crude BN powder obtained in the first step is less than 2.5, crystal growth in the second step may be difficult.
- the GI value in the first step is more preferably 2.6 or more, further preferably 2.8 or more, and most preferably 3.0 or more. If the GI value in the second step exceeds 1.9, crystallization is often insufficient for use as a final product.
- the GI value in the second step is more preferably 1.8 or less, further preferably 1.6 or less, and most preferably 1.4 or less.
- the number average particle diameter of h-BN powder is measured with a laser scattering type particle size analyzer after throwing the h-BN powder into an aqueous solution containing a surfactant so that it does not aggregate and dispersing with an ultrasonic disperser for 1 minute. It is the value.
- the crude BN powder obtained in the first step preferably has a number average particle size of 9 ⁇ m or less, and the crystalline h-BN powder after crystal growth in the second step has a number average particle size. Is preferably 10 ⁇ m or more.
- the number average particle size in the first step is more preferably 8 ⁇ m or less, further preferably 7 ⁇ m or less, and most preferably 6 ⁇ m or less. If the number average particle size in the second step is less than 10 ⁇ m, crystallization is often insufficient for use as a final product.
- the number average particle size in the second step is preferably 12 ⁇ m or more, more preferably 14 ⁇ m or more, further preferably 16 ⁇ m or more, and most preferably 18 ⁇ m or more.
- the present invention it is necessary to add a boron-containing flux component when the crystal is grown by reheating at 1550 to 2400 ° C. in the second step.
- a boron-containing flux component it is preferable to positively add a boron-containing flux component in the second step, but by controlling the reactivity of the first step well, it is suitable for the crude BN powder produced in the first step.
- the free boron component By leaving the free boron component, the free boron component can be used as it is as the boron-containing flux component in the second step.
- the above components may be mixed using a conventionally known method, for example, using a high speed stirring device such as a Henschel mixer.
- Boron compounds other than boron nitride are used as the boron-containing flux component.
- various compounds such as boric acid, boron oxide, borate salts of inorganic or organic compounds, boron halides, borazine, borosiloxane, etc. can be used, but from the viewpoint of economy and reactivity, Boron compounds such as alkali metal or alkaline earth metal borates, boric acid, and boron oxide can be preferably used.
- an alkali metal borate such as borax, or an alkaline earth metal borate such as calcium borate or magnesium borate is preferable.
- boric acid, boron oxide, and calcium borate are particularly preferable.
- the boron-containing flux component it is preferable to use an alkali metal or alkaline earth metal borate, but it is not necessary to add borate as a raw material. That is, if an alkali metal-containing substance / alkaline earth metal-containing substance and a boron-containing substance are present, an alkali metal or alkaline earth metal borate is generated in the system by reacting at a high temperature, and h- Promotes crystallization of BN powder. Furthermore, the purity of the obtained h-BN powder can be improved by selecting a substance in which components other than alkali metal or alkaline earth metal do not remain or easily volatilize.
- alkali metal-containing substances and alkaline earth metal-containing substances lithium, sodium, potassium and the like are preferably used as the alkali metal, and beryllium, magnesium, calcium, strontium, barium and the like are preferably used as the alkaline earth metal.
- An organometallic compound such as a narate compound is preferably used.
- the alkali metal-containing material / alkaline earth metal-containing material does not need to have a particularly high purity, and those of commercially available quality for industrial use are preferably used.
- boric acid and boron oxide include orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), tetraboric acid (H 2 B 4 O 7 ), and boric anhydride (B 2 O 3 ).
- One or more of the compounds represented by 2 O 3 ) ⁇ (H 2 O) x (where x 0 to 3) are preferred.
- the boron-containing flux component added at the time of reheating treatment at 1550 to 2400 ° C. for crystal growth is added at 50 parts by weight or less with respect to 100 parts by weight of the crude BN powder.
- the amount of the additive exceeds 50 parts by weight with respect to the crude BN powder, the amount of crystalline h-BN powder that can be fired at one time when produced in the same furnace is reduced, resulting in a decrease in production efficiency.
- the inside of the furnace may be contaminated by volatilization of the flux component. Further, since the additive remains in the obtained crystalline h-BN powder, the purity of the crystalline h-BN powder is lowered.
- the amount of the boron-containing flux component added to 100 parts by weight of the crude BN powder is preferably 40 parts by weight or less, more preferably 30 parts by weight or less, further preferably 20 parts by weight or less, particularly preferably 15 parts by weight or less, and most preferably 11 parts by weight or less.
- boron contained in the boron-containing flux component satisfies the following formula.
- the value on the left side of the formula (1) is preferably 1.3% by weight or less, more preferably 1.2% by weight or less, and still more preferably 1.1% by weight or less.
- the value of the left side of Formula (1) is 0.01 weight% or more, for example, Preferably it is 0.05 weight% or more, More preferably, it is 0.1 weight% or more. If the value on the left side of equation (1) is too large, the furnace may be contaminated and the pipes may be clogged, so that crystal growth may not be promoted.
- Formula (1) Boron content in boron-containing flux component / crude boron nitride content ⁇ 1.4 wt%
- the boron-containing flux component added in the second step may remain in the h-BN powder when taken out from the continuous reaction furnace in the second step. In that case, it is preferable to wash the flux component by washing the h-BN powder with an acidic aqueous solution after taking out.
- an acidic aqueous solution a general-purpose inorganic strong acid aqueous solution such as hydrochloric acid, nitric acid or sulfuric acid is used.
- a continuous reaction furnace is used for reheating treatment at 1550 to 2400 ° C. in the second step.
- a continuous reactor is different from a method in which a sample is heat-treated by a temperature rising / falling operation of a furnace such as a general batch-type reactor, in which a sample to be processed in a furnace previously maintained at a temperature to be reheated is processed. By passing through, it shows a reactor that continuously heat-treats samples.
- the temperature increase / decrease operation of the furnace as much as 2000 ° C. becomes unnecessary, so that the energy cost required for the heat treatment can be greatly reduced.
- the raw material will continuously receive a thermal history before and after the raw material passes through the high temperature zone, so the processing time kept in the high temperature zone is the same.
- the crystallinity is high with a large particle size, and a high-quality h-BN powder can be obtained.
- reaction furnace As the continuous reaction furnace, generally used reaction furnaces can be widely applied.
- the term “continuous” as used herein does not refer only to a method in which the sample is constantly moving, but may be a method in which the sample moves a certain distance every certain time.
- the raw BN obtained in the first step and the boron-containing flux component are charged into a heat-resistant container, and then the heat-resistant container containing the raw material is moved every few minutes to several hours, so that the inside of the continuous reaction furnace A method in which the sample passes through the high temperature region maintained at 1550 to 2400 ° C. over a certain period of time is employed.
- the heat-resistant container used for the reheating treatment at 1550 to 2400 ° C. in the second step is preferably made of graphite or boron nitride.
- Other heat-resistant containers may have reactivity with crude BN powder and boron-containing flux components at high temperatures, and the cost of the containers may increase.
- a graphite or boron nitride vessel is used for the pusher furnace as a continuous reaction furnace, the frictional force generated between the vessel and the furnace inner wall in the furnace can be reduced, thereby extending the life of the continuous reaction furnace. It becomes possible.
- a container whose container surface or inner surface is coated with boron nitride in order to reduce the reactivity between the crude BN powder or boron-containing flux component and the container.
- the continuous reaction furnace used in the second step is preferably a pusher type tunnel furnace. That is, the crude BN obtained in the first step and the boron-containing flux component are charged into a heat-resistant container, and then the heat-resistant container containing the raw material is continuously supplied into a pusher-type tunnel furnace maintained at 1550 to 2400 ° C. As a result, the raw material continuously passes through the space maintained at 1550-2400 ° C without raising or lowering the temperature of the pusher tunnel, so that crystalline h-BN powder is continuously produced. Will be.
- Examples of pusher-type tunnel furnaces that can be reheated to 1550-2400 ° C include furnaces with a structure in which a tunnel made of a heat-resistant material such as graphite or boron nitride is installed in a furnace equipped with a graphite heater. (For example, FIG. 1).
- a pusher near the entrance of such a tunnel furnace and pushing the heat-resistant container filled with the raw material at intervals with the pusher, the raw material is sequentially sent to the high temperature area, and crystallization in the high temperature area is performed. proceed.
- the tunnel is made of heat-resistant materials such as graphite and boron nitride, even if a small amount of volatile matter is generated from the raw material, the volatile matter will not contaminate the heater. It becomes possible to operate continuously for a period.
- the h-BN powder having a large particle size and high crystallinity obtained by the present invention is excellent in the concealing effect by other components when mixed in cosmetics, and can be preferably used for cosmetics, for example. Moreover, since it is highly crystalline, it has a high thermal conductivity, and since it has a large particle size, the thermal resistance at the contact surface between the particles can be reduced. Therefore, it is particularly useful as a thermal conductive filler for resins, for example. As the resin when used as the thermally conductive filler, it can be effectively used for both thermosetting resins and thermoplastic resins.
- thermosetting resin epoxy resins such as glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, urethane resins, curable silicone resins, curable acrylic resins, etc.
- Thermoplastic resins include aromatic vinyl resins such as polystyrene, vinyl cyanide resins such as polyacrylonitrile, chlorine resins such as polyvinyl chloride, polymethacrylate resins such as polymethyl methacrylate, and polyacrylic acid.
- Ester resins polyolefin resins such as polyethylene, polypropylene and cyclic polyolefin resins, polyvinyl ester resins such as polyvinyl acetate, polyvinyl alcohol resins and their derivative resins, polymethacrylic acid resins and polyacrylic acid resins and these Metal salt resins, polyconjugated diene resins, polymers obtained by polymerizing maleic acid and fumaric acid and their derivatives, polymers obtained by polymerizing maleimide compounds, amorphous semi-aromatic polyesters and amorphous Fully aromatic polyester Amorphous polyester resins, crystalline polyester resins such as crystalline semi-aromatic polyesters and crystalline wholly aromatic polyesters, polyamide resins such as aliphatic polyamides, aliphatic-aromatic polyamides and wholly aromatic polyamides, Polycarbonate resin, polyurethane resin, polysulfone resin, polyalkylene oxide resin, cellulose resin, polyphenylene ether resin, polyphenylene
- GI Graphitization index
- Number average particle diameter 1 ml of a 20% by weight aqueous solution of sodium hexametaphosphate was put into a 100 ml beaker, and 20 mg of h-BN powder was put into this aqueous solution, followed by dispersion treatment for 3 minutes with an ultrasonic disperser. With the obtained dispersion, the number average particle size was measured using a laser diffraction particle size distribution analyzer MT3300EXII manufactured by Nikkiso Co., Ltd.
- Example 1 After mixing 55 kg of orthoboric acid and 45 kg of melamine with a Henschel mixer, the mixture was heated to 1100 ° C. in a batch-type tubular electric furnace under nitrogen flow, treated for 2 hours and then cooled to obtain crude BN powder. This crude BN powder was once taken out, allowed to stand for 10 days under conditions of 23 ° C. and 50% RH, and cured. Next, 18 kg of crude BN powder, 1.2 kg of calcium oxide, and 0.8 kg of orthoboric acid were mixed with a Henschel mixer, and then 3 kg of each mixture in a cubic shape with an outer dimension of 230 mm square and an inner dimension of 210 mm square.
- 50 containers filled with the raw material mixture were prepared by repeating the operation of charging into a graphite heat-resistant container whose inner surface and outer surface were both coated with boron nitride.
- the central part of a pusher type tunnel furnace having a graphite heater and a graphite muffle type tunnel was kept at 2050 ° C., and the interior was filled with high-purity nitrogen.
- a high-purity nitrogen stream is further flown inside, and a heat-resistant container filled with the raw material is sent to the furnace one by one every 30 minutes to maintain the temperature at 2050 ° C.
- the dripping zone was passed over 120 minutes to crystallize the crude BN powder to obtain crystalline h-BN powder.
- the obtained crystalline h-BN powder was dispersed in a nitric acid aqueous solution, followed by filtration, washing with pure water, and drying to obtain 2.66 kg of crystalline h-BN powder per heat-resistant container. .
- the characteristics of the obtained h-BN powder are as follows. Crude BN powder: graphitization index 4.74, number average particle size 0.95 ⁇ m. Crystalline h-BN powder: Graphitization index 1.09, number average particle size 23.5 ⁇ m.
- Example 2 After mixing 65 parts by weight of anhydrous boric acid and 35 parts by weight of calcium phosphate with a Henschel mixer, it was heated to 1000 ° C. in a tubular electric furnace under ammonia flow, treated for 6 hours, and then cooled to obtain crude BN powder. This crude BN powder was once taken out, allowed to stand for 10 days under conditions of 23 ° C. and 50% RH, and cured. Next, after 18 kg of crude BN powder and 2.0 kg of calcium borate were mixed with a Henschel mixer, 3 kg of the mixture per container was charged into a heat resistant container made of cubic graphite having an outer dimension of 230 mm square and an inner dimension of 210 mm square. By repeating the operation, 50 containers filled with the raw material mixture were prepared.
- the central part of a pusher type tunnel furnace having a graphite heater and a graphite muffle type tunnel was kept at 2050 ° C., and the interior was filled with high-purity nitrogen.
- a high-purity nitrogen stream is further flown inside, and a heat-resistant container filled with the raw material is sent to the furnace one by one every 30 minutes to maintain the temperature at 2050 ° C.
- the dripping zone was passed over 120 minutes to crystallize the crude BN powder to obtain crystalline h-BN powder.
- the obtained crystalline h-BN powder was dispersed in a nitric acid aqueous solution, followed by filtration, washing with pure water, and drying to obtain 2.66 kg of crystalline h-BN powder per heat-resistant container. .
- the characteristics of the obtained h-BN powder are as follows. Crude BN powder: graphitization index 3.58, number average particle size 1.05 ⁇ m. Crystalline h-BN powder: Graphitization index 1.06, number average particle size 26.5 ⁇ m.
- Comparative Example 1 After mixing 55 kg of orthoboric acid and 45 kg of melamine with a Henschel mixer, the mixture was heated to 1100 ° C. in a batch-type tubular electric furnace under nitrogen flow, treated for 2 hours and then cooled to obtain crude BN powder. This crude BN powder was once taken out, allowed to stand for 10 days under conditions of 23 ° C. and 50% RH, and cured. After 90 g of this crude BN powder, 6 g of calcium oxide, and 4 g of orthoboric acid were mixed in a crucible, they were charged into a boron nitride container and a batch-type electric atmosphere furnace capable of high-temperature heating. After replacing the interior with nitrogen, the mixture was heated at 2050 ° C.
- Comparative Example 2 55 kg of orthoboric acid and 45 kg of melamine were mixed with a Henschel mixer. 3 kg of this mixture was taken out per container, and 50 containers filled with the raw material mixture were prepared by repeating the work of charging into a cube-shaped graphite heat-resistant container having an outer dimension of 230 mm square and an inner dimension of 210 mm square.
- the central part of a pusher type tunnel furnace having a graphite heater and a graphite muffle type tunnel was kept at 2050 ° C., and the interior was filled with high-purity nitrogen.
- a high-purity nitrogen stream is further flown inside, and a heat-resistant container filled with the raw material is sent to the furnace one by one every 30 minutes to maintain the temperature at 2050 ° C.
- the sagging zone was passed over 120 minutes to synthesize crystalline h-BN powder.
- the muffle in the furnace was significantly contaminated by volatiles generated from the raw materials, so when 12 of the 50 containers were sent, the pusher of the continuous reaction furnace became inoperable and stopped.
- the obtained h-BN powder was dispersed in an aqueous nitric acid solution, filtered, washed with pure water, and dried to obtain crystalline h-BN powder.
- the characteristics of the obtained h-BN powder are as follows. Crystalline h-BN powder: Graphitization index 1.55, number average particle size 13.8 ⁇ m.
- Comparative Example 2 since continuous production was continuously attempted without taking out the crude BN powder, the production efficiency of h-BN powder was lower than in Example 1, and the contamination in the furnace became severe.
- the obtained crystalline h-BN powder had a small particle size and low crystallinity.
- the heat-resistant container filled with the raw material is sent to the furnace one by one every 30 minutes to maintain the temperature at 2050 ° C.
- Crystalline h-BN powder was synthesized by a method of nitriding with nitrogen gas while reducing orthoboric acid with acetylene black by passing through the drowned zone for 120 minutes. As a result, only 0.6 kg of h-BN powder was obtained per heat-resistant container, and the productivity was significantly reduced.
- tar-like filth was generated from the raw material, and the inside of the furnace was contaminated by being deposited near the downstream of the inside of the furnace.
- the obtained h-BN powder was dispersed in an aqueous nitric acid solution, filtered, washed with pure water, and dried to obtain crystalline h-BN powder.
- the characteristics of the obtained h-BN powder are as follows. Crystalline h-BN powder: Graphitization index 1.41, number average particle diameter 11.7 ⁇ m.
- Comparative Example 3 a method called a reductive nitriding method was adopted, so although continuous productivity was improved in comparison with Comparative Example 2, the production efficiency of h-BN powder was significantly decreased in comparison with Example 1, The inside of the furnace was contaminated, and the obtained crystalline h-BN powder had a small particle size and low crystallinity.
- the crystalline h-BN powder produced by the production method of the present invention has a large particle size and high crystallinity, and can be produced with high efficiency even in a small-scale facility.
- Such crystalline h-BN powder is particularly useful as a heat conductive filler for resin.
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Abstract
Description
式(1):ホウ素含有フラックス成分に含まれるホウ素量/粗製窒化ホウ素量≦1.4重量%
特に1550~2400℃の高温処理を連続炉で行えば、少ないホウ素含有フラックスが揮発することでその残存量が非常に少なくなるにも拘わらず、高結晶化をより確実に達成できる。
本発明で使用されるホウ素含有物質としては、ホウ酸、酸化ホウ素、無機又は有機化合物のホウ酸塩、ハロゲン化ホウ素、ボラジン、ボロシロキサン等の様々な化合物が使用可能であるが、経済性や反応性等の観点から、ホウ酸、酸化ホウ素、アルカリ金属またはアルカリ土類金属のホウ酸塩(例えば、ホウ砂)等のホウ素化合物を好適に用いることが可能である。ホウ酸及び酸化ホウ素としては、オルトホウ酸(H3BO3)、メタホウ酸(HBO2)、テトラホウ酸(H2B4O7)、無水ホウ酸(B2O3)など、一般式(B2O3)・(H2O)x〔但し、x=0~3〕で示される化合物の1種又は2種以上が好適である。
こうして得られた粗製BN粉末を、窒素ガス雰囲気下にて1550~2400℃で再加熱処理し結晶成長させることで、粒径が大きくかつ結晶性に優れたh-BN粉末を生産することができる。本発明は、後述する様に、本第二工程でホウ素含有フラックス成分の使用量を抑制する点に特徴を有するが、ホウ素含有フラックス成分を抑制すると、再加熱処理時のフラックス成分の揮発によって、窒化ホウ素の高結晶化が優れたレベルではあっても、最高レベルにまでは到達しない事がある。窒化ホウ素の高結晶化を最高レベルにするには、1500~2400℃での再加熱処理において加熱を連続炉で行う事が望ましい。再加熱時の最高温度は1550~2400℃の範囲であるが、より高結晶性のh-BN粉末を得るためには最高温度が高いほうが好ましく、炉の管理コストや維持費を低減させるためには最高温度を低く抑えるほうが好ましい。以上の兼ね合いから、最高温度は好ましくは1600~2300℃、より好ましくは1700~2250℃、さらに好ましくは1750~2200℃、最も好ましくは1800~2150℃である。より高結晶性のh-BN粉末を得るためには最高温度での処理時間は長いほうが好ましく、生産性やユーティリティー費用を低減させるためには最高温度での処理時間は短いほうが好ましい。好ましい最高温度での処理時間は、10分~10時間であり、より好ましくは20分~6時間であり、最も好ましくは30分~5時間である。再加熱時の雰囲気は窒素ガス雰囲気下で実施する必要がある。
GI=〔面積{(100)+(101)}〕/〔面積(102)〕
アルカリ金属・アルカリ土類金属(M)とホウ素(B)との元素モル比は適宜設定可能であるが、通常はM/B=1/4~4/1程度、好ましくはM/B=1/3~3/1程度で使用すればよい。
式(1):ホウ素含有フラックス成分に含まれるホウ素量/粗製窒化ホウ素量≦1.4重量%
GI=〔面積{(100)+(101)}〕/〔面積(102)〕
オルトホウ酸55kg、メラミン45kgをヘンシェルミキサーで混合した後、窒素フロー下でバッチ式の管状電気炉にて1100℃に加熱し2時間処理後冷却することで、粗製BN粉末を得た。この粗製BN粉末を一旦取り出し、23℃50%RH条件にて10日間静置し、養生した。次いで、粗製BN粉末18kg、酸化カルシウム1.2kg、オルトホウ酸0.8kgをヘンシェルミキサーで混合した後、容器1個につき混合物を3kgずつ、外寸230mm角四方、内寸210mm角四方の立方体形状で内面及び外面がいずれも窒化ホウ素でコーティングされているグラファイト製耐熱容器に仕込む作業を繰り返すことで、原料混合物が充填された容器を50個準備した。グラファイト製ヒーターとグラファイト製マッフル型トンネルとを有したプッシャー式トンネル炉の中心部分を2050℃に保ち、内部に高純度窒素を充満させた。この状態のプッシャー式トンネル炉にさらに内部に高純度窒素気流を流しながら、原料が充填された耐熱容器を30分に1回の頻度で容器一個分ずつ炉内へ送ることにより、2050℃に保たれたゾーンを120分間かけて通過させ、粗製BN粉末を結晶化させて結晶性h-BN粉末を得た。得られた結晶性h-BN粉末を硝酸水溶液に分散させたあと、ろ過、純水での洗浄、乾燥を経ることにより、耐熱容器1個あたり2.66kgの結晶性h-BN粉末を得た。
得られたh-BN粉末の特性は下記の通りである。
粗製BN粉末:黒鉛化指数4.74、数平均粒子径0.95μm。
結晶性h-BN粉末:黒鉛化指数1.09、数平均粒子径23.5μm。
無水ホウ酸65重量部、リン酸カルシウム35重量部をヘンシェルミキサーで混合した後、アンモニアフロー下で管状電気炉にて1000℃に加熱し6時間処理後冷却することで、粗製BN粉末を得た。この粗製BN粉末を一旦取り出し、23℃50%RH条件にて10日間静置し、養生した。次いで、粗製BN粉末18kg、ホウ酸カルシウム2.0kgをヘンシェルミキサーで混合した後、容器1個につき混合物を3kgずつ、外寸230mm角四方、内寸210mm角四方の立方体形状グラファイト製耐熱容器に仕込む作業を繰り返すことで、原料混合物が充填された容器を50個準備した。グラファイト製ヒーターとグラファイト製マッフル型トンネルとを有したプッシャー式トンネル炉の中心部分を2050℃に保ち、内部に高純度窒素を充満させた。この状態のプッシャー式トンネル炉にさらに内部に高純度窒素気流を流しながら、原料が充填された耐熱容器を30分に1回の頻度で容器一個分ずつ炉内へ送ることにより、2050℃に保たれたゾーンを120分間かけて通過させ、粗製BN粉末を結晶化させて結晶性h-BN粉末を得た。得られた結晶性h-BN粉末を硝酸水溶液に分散させたあと、ろ過、純水での洗浄、乾燥を経ることにより、耐熱容器1個あたり2.66kgの結晶性h-BN粉末を得た。
得られたh-BN粉末の特性は下記の通りである。
粗製BN粉末:黒鉛化指数3.58、数平均粒子径1.05μm。
結晶性h-BN粉末:黒鉛化指数1.06、数平均粒子径26.5μm。
オルトホウ酸55kg、メラミン45kgをヘンシェルミキサーで混合した後、窒素フロー下でバッチ式の管状電気炉にて1100℃に加熱し2時間処理後冷却することで、粗製BN粉末を得た。この粗製BN粉末を一旦取り出し、23℃50%RH条件にて10日間静置し、養生した。この粗製BN粉末90g、酸化カルシウム6g、オルトホウ酸4gをるつぼにて混合した後、窒化ホウ素製容器仕込み、高温加熱が可能なバッチ式電気雰囲気炉に仕込んだ。内部を窒素置換した後、2050℃にて2時間加熱し、粗製BN粉末を結晶化させた。こうして得られた結晶性h-BN粉末を硝酸水溶液に分散させたあと、ろ過、純水での洗浄、乾燥を経て、結晶性h-BN粉末を得た。
粗製BN粉末:黒鉛化指数4.74、数平均粒子径0.95μm。
結晶性h-BN粉末:黒鉛化指数1.68、数平均粒子径12.3μm。
比較例1では連続反応炉による連続的生産方式を採用しなかったため、実施例1よりも得られた結晶性h-BN粉末の粒径が小さく、かつ結晶性が低くなった。
オルトホウ酸55kg、メラミン45kgをヘンシェルミキサーで混合した。容器1個につきこの混合物3kgを取り出し、外寸230mm角四方、内寸210mm角四方の立方体形状グラファイト製耐熱容器に仕込む作業を繰り返すことで、原料混合物が充填された容器を50個準備した。グラファイト製ヒーターとグラファイト製マッフル型トンネルとを有したプッシャー式トンネル炉の中心部分を2050℃に保ち、内部に高純度窒素を充満させた。この状態のプッシャー式トンネル炉にさらに内部に高純度窒素気流を流しながら、原料が充填された耐熱容器を30分に1回の頻度で容器一個分ずつ炉内へ送ることにより、2050℃に保たれたゾーンを120分間かけて通過させ、結晶性h-BN粉末を合成した。結果、耐熱容器1個につき0.5kgしかh-BN粉末が得られず、生産性が著しく低下した。また原料から発生した揮発物等により炉内のマッフルが著しく汚染されたため、容器50個中12個を送った時点で連続反応炉のプッシャーが動作不可能となり、停止してしまった。得られたh-BN粉末を硝酸水溶液に分散させたあと、ろ過、純水での洗浄、乾燥を経て、結晶性h-BN粉末を得た。
得られたh-BN粉末の特性は下記の通りである。
結晶性h-BN粉末:黒鉛化指数1.55、数平均粒子径13.8μm。
比較例2では一旦粗製BN粉末を取り出すことなく、一貫して連続反応炉による製造を試みたため、実施例1よりもh-BN粉末の生産効率が低下し、炉内の汚染も激しくなったうえ、得られた結晶性h-BN粉末は粒径が小さく結晶性の低いものであった。
オルトホウ酸50kg、アセチレンブラック11kg、酸化カルシウム5kgをヘンシェルミキサーで混合した。容器1個につきこの混合物3kgを取り出し、外寸230mm角四方、内寸210mm角四方の立方体形状グラファイト製耐熱容器に仕込む作業を繰り返すことで、原料混合物が充填された容器を50個準備した。グラファイト製ヒーターとグラファイト製マッフル型トンネルとを有したプッシャー式トンネル炉の中心部分を2050℃に保ち、内部に高純度窒素を充満させた。この状態のプッシャー式トンネル炉にさらに内部に高純度窒素気流を流しながら、原料が充填された耐熱容器を30分に1回の頻度で容器一個分ずつ炉内へ送ることにより、2050℃に保たれたゾーンを120分間かけて通過させることで、オルトホウ酸をアセチレンブラックで還元しながら窒素ガスで窒化させる方法により、結晶性h-BN粉末を合成した。結果、耐熱容器1個につき0.6kgしかh-BN粉末が得られず、生産性が著しく低下した。また原料からタール状の汚物が発生し、炉内下流付近に析出することで炉内が汚染された。得られたh-BN粉末硝酸水溶液に分散させたあと、ろ過、純水での洗浄、乾燥を経て、結晶性h-BN粉末を得た。
得られたh-BN粉末の特性は下記の通りである。
結晶性h-BN粉末:黒鉛化指数1.41、数平均粒子径11.7μm。
比較例3では還元窒化法と呼ばれる方法を採用したため、比較例2との比較では連続生産性は改善されたものの、やはり実施例1との比較ではh-BN粉末の生産効率が著しく低下し、炉内も汚染されたうえ、得られた結晶性h-BN粉末は粒径が小さく結晶性の低いものであった。
2.ガス排出口、
3.カーボンヒーター、
4.ガス導入口、
5.トンネル型マッフル、
6.耐熱容器
Claims (6)
- 第一工程にてホウ素含有物質と窒素含有物質とを加熱処理してBN含有率が80重量%以上の粗製窒化ホウ素を得た後、第二工程にて該粗製窒化ホウ素を、下記式(1)を満足するホウ素含有フラックス成分とともに耐熱容器に仕込み、窒素ガス雰囲気下連続反応炉で1550~2400℃にて再加熱処理して結晶成長させることを特徴とする、結晶性六方晶窒化ホウ素粉末の連続的製造方法。
式(1):ホウ素含有フラックス成分に含まれるホウ素量/粗製窒化ホウ素量≦1.4重量% - 前記第一工程の加熱処理温度が800℃以上、1550℃未満である請求項1に記載の結晶性六方晶窒化ホウ素粉末の連続的製造方法。
- 前記耐熱容器が、グラファイト製または窒化ホウ素製であることを特徴とする、請求項1又は2に記載の結晶性六方晶窒化ホウ素粉末の連続的製造方法。
- 前記耐熱容器が、少なくとも内面が窒化ホウ素でコーティングされているグラファイト製容器である請求項1~3のいずれかに記載の結晶性六方晶窒化ホウ素粉末の連続的製造方法。
- 前記連続反応炉がプッシャー式トンネル炉であることを特徴とする、請求項1~4のいずれかに記載の結晶性六方晶窒化ホウ素粉末の連続的製造方法。
- 前記粗製窒化ホウ素粉末のX線回折法による黒鉛化指数(GI)が2.5以上かつ数平均粒子径が9μm以下であり、窒素ガス雰囲気中にて1550~2400℃で再加熱処理した後の結晶性六方晶窒化ホウ素粉末のX線回折法による黒鉛化指数(GI)が1.9以下かつ数平均粒子径が10μm以上であることを特徴とする、請求項1~5のいずれかに記載の結晶性六方晶窒化ホウ素粉末の連続的製造方法。
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WO2014109134A1 (ja) * | 2013-01-10 | 2014-07-17 | 株式会社カネカ | 六方晶窒化ホウ素及びそれを用いた高熱伝導性樹脂成形体 |
JP2017160086A (ja) * | 2016-03-09 | 2017-09-14 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法並びに化粧料 |
JP2017222522A (ja) * | 2016-06-13 | 2017-12-21 | 株式会社トクヤマ | 六方晶窒化ホウ素粉末及びその製造方法 |
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WO2021039586A1 (ja) * | 2019-08-28 | 2021-03-04 | 株式会社トクヤマ | 改質窒化ホウ素粉末 |
JP2021102542A (ja) * | 2019-12-25 | 2021-07-15 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法、並びに化粧料及びその製造方法 |
JP2021102540A (ja) * | 2019-12-25 | 2021-07-15 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法、並びに化粧料及びその製造方法 |
JP2021123508A (ja) * | 2020-02-03 | 2021-08-30 | 株式会社トクヤマ | 窒化アルミニウム粉末の製造方法および製造装置 |
JP7161638B1 (ja) | 2022-03-30 | 2022-10-26 | 株式会社ノリタケカンパニーリミテド | マッフル炉 |
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KR20160073435A (ko) * | 2014-12-15 | 2016-06-27 | 오씨아이 주식회사 | 질화붕소 분말의 제조방법 |
CN106241753A (zh) * | 2015-05-19 | 2016-12-21 | 常州新墨能源科技有限公司 | 一种白色石墨烯纳米粒子的制备方法 |
WO2017034003A1 (ja) * | 2015-08-26 | 2017-03-02 | デンカ株式会社 | 熱伝導性樹脂組成物 |
EP3490929A1 (en) * | 2016-07-26 | 2019-06-05 | Arconic Inc. | Methods for making boron nitride ceramic powder |
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WO2014109134A1 (ja) * | 2013-01-10 | 2014-07-17 | 株式会社カネカ | 六方晶窒化ホウ素及びそれを用いた高熱伝導性樹脂成形体 |
JP2017160086A (ja) * | 2016-03-09 | 2017-09-14 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法並びに化粧料 |
JP2017222522A (ja) * | 2016-06-13 | 2017-12-21 | 株式会社トクヤマ | 六方晶窒化ホウ素粉末及びその製造方法 |
WO2020031913A1 (ja) | 2018-08-07 | 2020-02-13 | 水島合金鉄株式会社 | 六方晶窒化ホウ素粉末 |
KR20210028712A (ko) | 2018-08-07 | 2021-03-12 | 미즈시마 페로알로이 가부시키가이샤 | 육방정 질화붕소 분말 |
WO2021039586A1 (ja) * | 2019-08-28 | 2021-03-04 | 株式会社トクヤマ | 改質窒化ホウ素粉末 |
JP2021102542A (ja) * | 2019-12-25 | 2021-07-15 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法、並びに化粧料及びその製造方法 |
JP2021102540A (ja) * | 2019-12-25 | 2021-07-15 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法、並びに化粧料及びその製造方法 |
JP7372142B2 (ja) | 2019-12-25 | 2023-10-31 | デンカ株式会社 | 六方晶窒化ホウ素粉末及びその製造方法、並びに化粧料及びその製造方法 |
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JP2021123508A (ja) * | 2020-02-03 | 2021-08-30 | 株式会社トクヤマ | 窒化アルミニウム粉末の製造方法および製造装置 |
JP7401330B2 (ja) | 2020-02-03 | 2023-12-19 | 株式会社トクヤマ | 窒化アルミニウム粉末の製造方法および製造装置 |
JP7161638B1 (ja) | 2022-03-30 | 2022-10-26 | 株式会社ノリタケカンパニーリミテド | マッフル炉 |
JP2023148905A (ja) * | 2022-03-30 | 2023-10-13 | 株式会社ノリタケカンパニーリミテド | マッフル炉 |
Also Published As
Publication number | Publication date |
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KR20140095049A (ko) | 2014-07-31 |
JPWO2013065556A1 (ja) | 2015-04-02 |
EP2774893A4 (en) | 2015-11-25 |
CN104024153A (zh) | 2014-09-03 |
JP5923106B2 (ja) | 2016-05-24 |
TW201323320A (zh) | 2013-06-16 |
EP2774893A1 (en) | 2014-09-10 |
US20140314652A1 (en) | 2014-10-23 |
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