WO2014038676A1 - 耐水性窒化アルミニウム粉末の製造方法 - Google Patents
耐水性窒化アルミニウム粉末の製造方法 Download PDFInfo
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- WO2014038676A1 WO2014038676A1 PCT/JP2013/074150 JP2013074150W WO2014038676A1 WO 2014038676 A1 WO2014038676 A1 WO 2014038676A1 JP 2013074150 W JP2013074150 W JP 2013074150W WO 2014038676 A1 WO2014038676 A1 WO 2014038676A1
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- 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
- C01B21/072—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 aluminium
- C01B21/0728—After-treatment, e.g. grinding, purification
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- 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
- H01L23/3733—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon having a heterogeneous or anisotropic structure, e.g. powder or fibres in a matrix, wire mesh, porous structures
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- 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
- H01L23/3737—Organic materials with or without a thermoconductive filler
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a novel method for producing water-resistant aluminum nitride powder.
- Patent Document 1 discloses a mixed powder of alumina or alumina hydrate, carbon powder, and a compound containing a rare earth metal element in a nitrogen-containing atmosphere. A method is disclosed in which reductive nitriding of alumina (or alumina hydrate) proceeds by firing at a temperature.
- Patent Document 1 it is possible to increase the particle size of the produced aluminum nitride powder by using a rare earth metal compound (co-melting agent), and the size is useful as a filler. Almost spherical aluminum nitride particles having the following are obtained.
- aluminum nitride also has the property of being easily hydrolyzed.
- the excellent characteristics of aluminum nitride are lost due to the formation of aluminum hydroxide by hydrolysis, and problems such as handling problems and corrosion occur due to the generation of ammonia.
- Patent Documents 2 and 3 various treatments such as a phosphoric acid compound treatment (Patent Documents 2 and 3) in which a phosphoric acid compound is brought into contact with the aluminum nitride powder and a silane coupling treatment (Patent Document 4) A method has been proposed.
- An object of the present invention is to provide a method for producing a water-resistant aluminum nitride powder capable of imparting good water resistance to an aluminum nitride powder having yttria on the particle surface.
- the present inventors have found that yttria present on the particle surface of the aluminum nitride powder can be effectively removed by an acid solution, and phosphoric acid after sufficiently reducing yttria present on the particle surface. It has been found that by performing a water resistance treatment with a compound, good water resistance can be imparted to the aluminum nitride powder, and the present invention has been completed.
- the present invention is a method for producing a water-resistant aluminum nitride powder by treating the particle surface of the aluminum nitride powder, (I) contacting the aluminum nitride powder having at least yttria on the particle surface with an acid solution; and (Ii) The step of bringing the aluminum nitride powder and the phosphoric acid compound into contact with each other in the order described above. After the step (i), filtration, washing, and extraction of the dried aluminum nitride powder with 1 mol / L hydrochloric acid.
- the amount of yttria extracted when the operation is performed is 1000 mg or less with respect to 100 g of the aluminum nitride powder filtered, washed, and dried. is there.
- the “amount of yttria to be extracted” is determined by sequentially performing the following steps (a) to (e).
- the ultrasonic tank used in the step (b) Branson Bransonic desktop ultrasonic cleaner (tank dimensions: width 295 ⁇ depth 150 ⁇ height 150 mm, tank capacity: 6.0 L, ultrasonic output) : 120W) can be preferably employed.
- the depth from which the distance from the bottom outer surface of a sample bottle to the water surface of an ultrasonic tank becomes 40 mm can be employ
- the sample bottle is made of glass.
- the “phosphate compound” is a concept including all acidic phosphorus compounds having a group represented by the following general formula (1) and salts thereof.
- an aluminum nitride powder having an average particle diameter of 1 to 30 ⁇ m, more preferably 3 to 30 ⁇ m can be suitably used.
- the “average particle diameter” means a sphere equivalent diameter (diameter) corresponding to an intermediate value of the particle size distribution (volume distribution) measured by the laser diffraction scattering method.
- Measurement of the particle size distribution by the laser diffraction / scattering method can be performed by a commercially available laser diffraction / scattering particle size distribution measuring apparatus (for example, MT3300 manufactured by Nikkiso Co., Ltd.).
- the solvent of the acid solution in the step (i) is water, and the pH of the acid solution is 4 or less.
- the pH of the acid solution is more preferably 3 or less.
- the phosphoric acid compound in the step (ii) is at least one compound selected from inorganic phosphoric acid, a metal salt of inorganic phosphoric acid, and organic phosphoric acid having an organic group.
- inorganic phosphoric acid or simply “phosphoric acid” means not only orthophosphoric acid H 3 PO 4 but also pyrophosphoric acid H 4 P 2 O 7 and higher condensed phosphoric acid H n + 2 P n O 3n + 1 , In addition, it is a concept including metaphosphoric acid (polyphosphoric acid) (HPO 3 ) n . Further, in the present application, “organophosphoric acid” means a phosphoric acid compound having an organic group, and is a concept including not only incomplete esters of phosphoric acid but also phosphonic acids and incomplete esters thereof.
- the adhesion amount of the phosphate compound per unit surface area of the aluminum nitride powder is 0.5 to 50 mg / m 2 in terms of orthophosphate ion (PO 4 3 ⁇ ), more preferably. Is 1 to 10 mg / m 2 .
- the adhesion amount of the phosphate compound to the aluminum nitride powder is determined based on the amount (X) of the phosphate compound used in the step (ii) and the nitridation of the phosphate compound used in the step (ii). Based on the amount (Y) of the phosphoric acid compound that has not adhered to the aluminum powder, it is calculated by the formula (XY).
- the step (ii) is performed by dispersing aluminum nitride particles in the phosphoric acid compound solution, and the mixture is evaporated after the step (ii) without passing through another solid-liquid separation process (for example, filtration, decantation, etc.).
- the step (ii) is performed by dispersing aluminum nitride particles in a phosphoric acid compound solution, and the aluminum nitride particles are filtered and dried after the step (ii), a water-resistant aluminum nitride powder is obtained.
- the amount of the phosphoric acid compound contained in the phosphoric acid compound solution is X
- the amount of the phosphoric acid compound contained in the filtrate is Y.
- “Adhesion amount of phosphate compound per unit surface area of aluminum nitride powder” is the specific surface area (S) of the raw aluminum nitride powder by the BET method, and the adhesion amount of phosphate compound converted to the amount of orthophosphate ions ( Based on Z), it is calculated by the formula (Z / S).
- the method for producing a water-resistant aluminum nitride powder of the present invention it is possible to impart good water resistance to an aluminum nitride powder in which yttrium is present in the form of an oxide on the particle surface.
- FIG. 1 is a scanning electron microscope (SEM) image of raw material aluminum nitride powder particles prepared in Example 1.
- FIG. 3 is a result of powder X-ray diffraction of the raw material aluminum nitride powder prepared in Example 1.
- FIG. 1 is a flowchart for explaining a manufacturing method S1 of water-resistant aluminum nitride powder according to an embodiment of the present invention (hereinafter, simply referred to as “manufacturing method S1”).
- the manufacturing method S1 includes a pickling step S11, a solid-liquid separation step S12, a phosphoric acid compound treatment step S13, and a post-treatment step S14 in this order.
- each process is demonstrated in order.
- the pickling step S1 (hereinafter sometimes abbreviated as “S1”) is a step of bringing an aluminum nitride powder having at least yttria on the particle surface into contact with an acid solution.
- the contact between the aluminum nitride powder and the acid solution in the pickling step S1 is, for example, a method of dispersing the aluminum nitride powder in the acid solution, a slurry in which the aluminum nitride powder is dispersed in a solvent (for example, water), and an acid. It can be performed by a method of mixing with a solution.
- the aluminum nitride powder as a raw material is not particularly limited as long as yttria is present on the particle surface.
- yttria is present on the surface of the particle includes all states in which yttria is present on the surface of the aluminum nitride powder particle. Examples of such a state include a state in which a part or all of the aluminum nitride powder particles are covered with a layer containing yttria; a state in which yttria particles are attached to the surface of the aluminum nitride powder particles; and aluminum nitride powder. These particles are formed by sintering aluminum nitride crystal particles through a grain boundary phase, and the grain boundary phase includes yttria.
- the aluminum nitride powder having yttria on the surface of the particles may be obtained by any method.
- it may be obtained by a conventionally known production method such as direct nitridation, reduction nitridation, vapor phase synthesis, or the like, or aluminum nitride powder formed and fired.
- an aluminum nitride powder suitable for the present invention as described in Patent Document 1, a mixed powder containing alumina or alumina hydrate, carbon powder, and yttria is fired in a nitrogen atmosphere.
- Examples thereof include aluminum nitride powder obtained by a method of reducing and nitriding alumina (or alumina hydrate).
- alumina or alumina hydrate 100 parts by mass of alumina or alumina hydrate, 0.5 to 30 parts by mass of yttria, and 38 to 46 parts by mass of carbon powder are mixed, and the resulting mixture is mixed with a nitrogen-containing atmosphere.
- examples thereof include aluminum nitride powder obtained by reducing and nitriding alumina or alumina hydrate by maintaining at a temperature of 1620 to 1900 ° C. for 2 hours or more.
- the aluminum nitride powder produced in this way is in a state where part or all of the particle surface is covered with a layer containing yttria.
- the particle size of the aluminum nitride powder used as a raw material is appropriately determined according to the application and is not particularly limited.
- the average particle diameter of the aluminum nitride powder used as a raw material (equivalent sphere diameter corresponding to the intermediate value of the volume distribution measured by the laser diffraction scattering method) is usually 0.1 to 500 ⁇ m, preferably 1 to 100 ⁇ m, more preferably 1 to 30 ⁇ m. More preferably, it is 3 to 30 ⁇ m.
- the shape of the powder is not particularly limited, and may be indefinite or spherical. However, it is preferably spherical.
- a known acid solution capable of dissolving yttria can be used as the acid solution brought into contact with the aluminum nitride powder, and water is preferably used as the solvent.
- the acid acids other than the phosphoric acid compounds described later are used, and specifically, strong acids such as hydrogen chloride, nitric acid, sulfuric acid, perchloric acid, hydrogen iodide, hydrogen bromide, permanganic acid, and thiocyanic acid. are preferably used.
- the concentration of the acid solution is not particularly limited, but is preferably 0.1 mol / L or more, more preferably 1 mol / L or more. If the concentration of the acid solution is too low, yttria is difficult to dissolve.
- the contact between the aluminum nitride powder and the acid solution is performed by mixing the slurry in which the aluminum nitride powder is dispersed in the solvent and the acid solution, the acid solution is diluted with the solvent contained in the slurry.
- the later concentration is preferably within the above range.
- the solvent of the acid solution is water
- the pH of the acid solution is preferably 4 or less, more preferably 3 or less.
- the temperature at which the aluminum nitride powder is brought into contact with the acid solution is not particularly limited, but is usually 5 ° C to 100 ° C, preferably 20 ° C to 40 ° C. If the temperature is too low, the solubility of yttria is lowered, so that the efficiency is poor. If the temperature is too high, hydrolysis of aluminum nitride may be promoted.
- the concentration of the aluminum nitride powder (solid content) when the aluminum nitride powder is brought into contact with the acid solution is not particularly limited, but is preferably 10 to 50% by mass, more preferably based on the total amount of the mixture of the aluminum nitride powder and the acid solution. Is 20 to 40% by mass. If the concentration of the aluminum nitride powder is too high, yttria is difficult to dissolve, and if it is too low, the productivity is lowered.
- the time for contacting the aluminum nitride powder and the acid solution varies depending on conditions such as temperature and concentration, but is usually 5 minutes to 24 hours, preferably 30 minutes to 2 hours. If the contact time is too short, yttria may not be sufficiently dissolved, and if it is too long, hydrolysis of aluminum nitride may proceed.
- the amount of yttria on the particle surface of the aluminum nitride powder after the pickling step S1 only needs to be reduced to an amount that does not interfere with the surface treatment with a phosphoric acid compound described later.
- the amount of yttria extracted when an extraction operation with 1 mol / L hydrochloric acid is performed on the aluminum nitride powder filtered and dried after the pickling step S1 is 1000 mg / 100 g (aluminum nitride powder) or less. More preferably, it is 250 mg / 100 g (aluminum nitride powder) or less.
- the “amount of yttria extracted” is a value determined by sequentially performing the following steps (a) to (e).
- the manufacturing method of the aluminum nitride powder of patent document 1 it extracts when performing the said process (a) thru
- the amount of yttria is 2000 mg / 100 g (aluminum nitride powder) or more.
- the solid-liquid separation step S12 (hereinafter sometimes abbreviated as “S12”) is a step of separating the acid solution and the aluminum nitride powder after S11. Specific examples of the separation method in S12 include filtration, decantation, centrifugation, and combinations thereof. In S12, it is preferable that the aluminum nitride powder separated from the acid solution is further washed with water or the like to remove the acid from the aluminum nitride powder.
- the aluminum nitride powder after contact with the acid solution can be subjected to subsequent treatment in a state of being dispersed in water or containing water after filtration, for example. Further, after the aluminum nitride powder is dried, it may be subjected to subsequent processing. However, it is possible to save energy necessary for the drying operation and to disperse the aluminum nitride powder in the phosphoric acid solution by subjecting it to a subsequent treatment (contact treatment with a phosphoric acid compound) in a state containing water. It is preferable because it is good.
- the phosphoric acid compound treatment step S13 (hereinafter sometimes abbreviated as “S13”) is a step of bringing the aluminum nitride powder that has undergone S12 into contact with the phosphoric acid compound.
- S13 a known method can be employed without any particular limitation.
- a method of dispersing aluminum nitride powder in a phosphoric acid compound solution a method of kneading aluminum nitride powder into a phosphoric acid compound solution, and making a paste, and the like can be mentioned.
- known devices such as a disperser, a homogenizer, and an ultrasonic disperser can be used.
- phosphoric acid compound in S13 a known phosphoric acid compound used for water resistance of the aluminum nitride powder can be used without particular limitation.
- examples of phosphoric acid compounds that can be used in S13 include inorganic phosphoric acid such as orthophosphoric acid, pyrophosphoric acid, and metaphosphoric acid; lithium phosphate, potassium phosphate, sodium phosphate, aluminum hydrogen phosphate, aluminum dihydrogen phosphate, etc.
- inorganic phosphoric acid metal salts inorganic ammonium phosphates such as ammonium phosphate, ammonium hydrogen phosphate, and ammonium dihydrogen phosphate; and organic phosphoric acid having an organic group.
- Preferable organic phosphoric acid includes organic phosphoric acid represented by the following general formula (2).
- organic phosphoric acid represented by the general formula (2) examples include methyl phosphoric acid (monomethyl phosphate, dimethyl phosphate, or a mixture thereof), ethyl phosphoric acid (monoethyl phosphate, diethyl phosphate, or a mixture thereof).
- Propyl phosphate (monopropyl phosphate or dipropyl phosphate or a mixture thereof), butyl phosphate (monobutyl phosphate or dibutyl phosphate or a mixture thereof), pentyl phosphate (monopentyl phosphate or dipentyl phosphate or a mixture thereof) Mixtures), hexyl phosphate (monohexyl phosphate or dihexyl phosphate or mixtures thereof), octyl phosphate (monooctyl phosphate or dioctyl phosphate or mixtures thereof), dodecyl phosphate (monododecyl phosphate or di (dodecyl phosphate) Or phosphoric acid incomplete esters such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, octyl
- the above phosphoric acid compounds may be used singly or in combination of two or more.
- the phosphoric acid compounds it is preferable to use one or more selected from inorganic phosphoric acid, a metal salt of inorganic phosphoric acid, and organic phosphoric acid.
- the phosphoric acid compound reacts with aluminum on the surface by contact with the aluminum nitride powder to form an aluminum phosphate bond (Al—O—P bond), and the aluminum nitride powder is coated with an aluminum phosphate layer. It is estimated that water resistance is exhibited.
- known conditions can be employed without particular limitation as the conditions for contacting the aluminum nitride powder and the phosphate compound.
- the contact time can usually be 1 to 120 minutes, and the temperature at the time of contact can usually be 0 to 90 ° C.
- the post-treatment step S14 is a step of taking out the water-resistant aluminum nitride powder from the mixture of the aluminum nitride powder and the phosphoric acid compound solution obtained in S13.
- S14 for example, (A) an embodiment in which the solvent is evaporated from the mixture to dryness; (B) an aluminum nitride powder is filtered from the mixture, and the filtered aluminum nitride powder is dried. Aspect: (C) An aluminum nitride powder is filtered from the mixture, washed with an appropriate solvent (for example, water), and then dried.
- the water-resistant aluminum nitride powder obtained above may be further subjected to a heat treatment at 100 to 1000 ° C. Such heat treatment can further improve the water resistance of the water-resistant aluminum nitride powder.
- manufacturing method S1 of the water resistant aluminum nitride powder of the form which uses the aluminum nitride powder which passed through solid-liquid separation process S12 as it is for phosphate compound processing process S13 was illustrated, this invention is limited to the said form Is not to be done.
- it is set as the manufacturing method of the water-resistant aluminum nitride powder of the form which performs the process for improving the efficiency of the phosphate compound process in S13 after passing through the solid-liquid separation process S12 and before the phosphate compound process process S13.
- a method for producing such a form of water resistant aluminum nitride powder will be described below.
- FIG. 2 is a flowchart for explaining a water-resistant aluminum nitride powder production method S2 (hereinafter also referred to as “production method S2”) according to another embodiment of the present invention.
- the manufacturing method S2 includes a pickling step S11, a solid-liquid separation step S12, an oxide film forming step S22, a phosphoric acid compound treatment step S13, and a post-treatment step S14 in this order.
- the steps other than the oxide film forming step S22 are the same as the steps of the same name in the manufacturing method S1.
- the oxide film forming step S22 (hereinafter sometimes abbreviated as “S22”) is performed on the particle surface of the aluminum nitride powder in which yttria on the particle surface has been reduced through the pickling step S11 and the solid-liquid separation step S12. This is a step of forming a film. Through S22, the reactivity with the phosphate compound can be increased.
- a known oxide film forming method can be employed as a known oxide film forming method can be employed as a known oxide film forming method can be employed.
- the amount of the oxide film formed in S22 is preferably such that 0.001 to 0.1 g / m 2 of aluminum oxide exists in terms of oxygen per surface area (BET method) of the raw aluminum nitride powder.
- the water-resistant aluminum nitride powder produced by the present invention is used as a filler for filling heat-dissipating materials such as heat-dissipating sheets, heat-dissipating greases, heat-dissipating adhesives, paints, and heat-conducting resins, in various applications utilizing the properties of aluminum nitride. Can be widely used.
- thermosetting resin such as an epoxy resin or a phenol resin
- thermoplastic resin such as polyethylene, polypropylene, polyamide, polycarbonate, polyimide, or polyphenylene sulfide
- rubber such as silicone rubber, EPR, or SBR.
- silicone oil a thermosetting resin such as an epoxy resin or a phenol resin
- thermoplastic resin such as polyethylene, polypropylene, polyamide, polycarbonate, polyimide, or polyphenylene sulfide
- rubber such as silicone rubber, EPR, or SBR.
- silicone oil silicone oil
- the matrix of the heat dissipation material for example, an epoxy resin or a silicone resin is preferable, and an addition reaction type liquid silicone rubber is preferable for a highly flexible heat dissipation member.
- the particle size distribution (volume distribution) was measured by a laser diffraction scattering type particle size distribution measuring apparatus (MT3300 manufactured by Nikkiso Co., Ltd.), and the sphere equivalent diameter (diameter) corresponding to the intermediate value was defined as the average particle diameter.
- the oxygen concentration of the aluminum nitride powder was measured using an oxygen / nitrogen analyzer (trade name: EMGA-620W, manufactured by HORIBA, Ltd.), helium gas as the inert gas, and an inert gas melting-infrared absorption detection method. Quantified. The amount of oxygen film was calculated from the obtained oxygen concentration by the following formula.
- Amount of oxide film oxygen concentration (wt%) / (specific surface area (m 2 / g) ⁇ 100)
- Example 1> Preparation of raw material aluminum nitride powder
- Al source ⁇ -alumina having an average particle diameter of 1.2 ⁇ m and a specific surface area of 10.7 m 2 / g is used, and carbon black having a specific surface area of 125 m 2 / g is used as a carbon powder.
- agent yttrium oxide having an average particle diameter of 1.0 ⁇ m and a specific surface area of 11.7 m 2 / g was used.
- FIG. 3 shows a scanning electron microscope (SEM) image (backscattered electron detection, acceleration voltage 1.0 kV, magnification 10,000 times) of the obtained raw material aluminum nitride powder. Moreover, the result of the powder X-ray diffraction of the obtained raw material aluminum nitride powder and the characterization of the peak are shown in FIG. From FIG. 3 and FIG. 4, it was confirmed that yttria was present on the particle surface.
- SEM scanning electron microscope
- Example 2 A water-resistant aluminum nitride powder was produced in the same manner as in Example 1 except that the acid solution was changed to 1 mol / L nitric acid.
- the amount of yttria extracted by hydrochloric acid extraction from the aluminum nitride powder after contact with the acid solution was 200 mg with respect to 100 g of the dry pickled aluminum nitride powder.
- Example 3> (Pickling process and solid-liquid separation process) 500 g of the raw material aluminum nitride powder prepared in Example 1 and 1200 mL of 1 mol / L hydrochloric acid were placed in a 5 L beaker, stirred at room temperature with a stirrer for 1 hour, and collected by suction filtration and water washing. The amount of yttria extracted by hydrochloric acid extraction from the aluminum nitride powder after contact with the acid solution was 200 mg with respect to 100 g of the dry pickled aluminum nitride powder.
- Example 4 A water resistant aluminum nitride powder was produced in the same manner as in Example 1 except that the stirring time in the pickling step was changed to 0.5 hour. The amount of yttria extracted by hydrochloric acid extraction from the aluminum nitride powder after contact with the acid solution was 918 mg with respect to 100 g of the dry pickled aluminum nitride powder. Table 2 shows the results of the water resistance test of the resulting water resistant aluminum nitride powder.
- the water-resistant aluminum nitride powder of Example 4 in which the amount of yttria extracted by hydrochloric acid extraction from the aluminum nitride powder after contact with the acid solution was within the specified range of the present invention was adjusted to pH before heating in the water resistance test. It was found that the pH after heating was 6.5 with respect to 6.5, and hydrolysis of aluminum nitride did not proceed.
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Abstract
Description
(i)少なくとも粒子表面にイットリアが存在する窒化アルミニウム粉末と、酸溶液とを接触させる工程;及び、
(ii)前記窒化アルミニウム粉末とリン酸化合物とを接触させる工程
を上記順に有し、前記工程(i)の後濾別、水洗、及び乾燥された窒化アルミニウム粉末に対して1mol/L塩酸による抽出操作を行った場合に抽出されるイットリアの量が、前記濾別、水洗、及び乾燥された窒化アルミニウム粉末100gに対して1000mg以下であることを特徴とする、耐水性窒化アルミニウム粉末の製造方法である。
(a)上記濾別、水洗、及び乾燥された窒化アルミニウム粉末10gを、50mLサンプル瓶中の1mol/L塩酸25mLに、25℃において加える工程;
(b)サンプル瓶を超音波槽中の水に浸漬した状態で保持し、25℃において43kHzの超音波を30分間印加する工程;
(c)サンプル瓶中の内容物を濾過することにより、濾液を得る工程;
(d)濾液中のイットリウム含有量を、ICP発光分光法により定量する工程;及び
(e)濾液中のイットリウム含有量を、イットリアとしての含有量に換算する工程。
ここで工程(b)において使用する超音波槽としては、ブランソン製ブランソニック卓上型超音波洗浄器(槽内寸法:幅295×奥行150×高さ150mm、槽容量:6.0L、超音波出力:120W)を好ましく採用できる。またサンプル瓶を超音波槽中に保持する際の深度としては、サンプル瓶の底部外表面から超音波槽の水面までの距離が40mmとなる深度を好ましく採用できる。なおサンプル瓶は本体がガラス製のものを用いるものとする。
リン酸化合物の付着量をオルトリン酸イオン(PO4 3-)の量に換算するにあたっては、リン酸化合物のリン原子1molがオルトリン酸イオン(PO4 3-)1molに対応するものとする。
「窒化アルミニウム粉末の単位表面積あたりのリン酸化合物の付着量」は、原料窒化アルミニウム粉末のBET法による比表面積(S)、及び、オルトリン酸イオンの量に換算されたリン酸化合物の付着量(Z)に基づいて、式(Z/S)により算出するものとする。
酸洗工程S1(以下において「S1」と略記することがある。)は、少なくとも粒子表面にイットリアが存在する窒化アルミニウム粉末と、酸溶液とを接触させる工程である。酸洗工程S1における窒化アルミニウム粉末と酸溶液との接触は、例えば、酸溶液中に窒化アルミニウム粉末を分散させる方法や、窒化アルミニウム粉末が溶媒(例えば水等。)中に分散されたスラリーと酸溶液とを混合する方法等により行うことができる。
本発明において、原料となる窒化アルミニウム粉末は、粒子表面にイットリアが存在する限りにおいて、特に制限されない。
酸洗工程S1において、窒化アルミニウム粉末と接触させる酸溶液は、イットリアを溶解可能な公知の酸の溶液を使用することができ、溶媒としては水が好ましく使用される。上記酸としては、後述するリン酸化合物以外の酸が用いられ、具体的には、塩化水素、硝酸、硫酸、過塩素酸、ヨウ化水素、臭化水素、過マンガン酸、チオシアン酸などの強酸が好適に使用される。
窒化アルミニウム粉末と酸溶液とを接触させる温度は特に限定されないが、通常5℃~100℃であり、好ましくは20℃~40℃である。温度が低すぎるとイットリアの溶解度が下がるため効率が悪く、温度が高すぎると窒化アルミニウムの加水分解が促進されるおそれがある。
酸洗工程S1後における窒化アルミニウム粉末の粒子表面のイットリア量は、後述のリン酸化合物による表面処理を妨害しない量まで低減されていればよい。好ましくは、酸洗工程S1の後濾別及び乾燥された窒化アルミニウム粉末に対して1mol/L塩酸による抽出操作を行った場合に抽出されるイットリアの量が、1000mg/100g(窒化アルミニウム粉末)以下、より好ましくは250mg/100g(窒化アルミニウム粉末)以下である。
(a)上記濾別及び乾燥された窒化アルミニウム粉末10gを、50mLサンプル瓶中の1mol/L塩酸25mLに、25℃において加える工程;
(b)サンプル瓶を超音波槽中の水に浸漬した状態で保持し、25℃において43kHzの超音波を30分間印加する工程;
(c)サンプル瓶中の内容物を濾過することにより、濾液を得る工程;
(d)濾液中のイットリウム含有量を、ICP発光分光法により定量する工程;及び
(e)濾液中のイットリウム含有量を、イットリアとしての含有量に換算する工程。
固液分離工程S12(以下において「S12」と略記することがある。)は、S11の後、酸溶液と窒化アルミニウム粉末とを分離する工程である。S12における分離の具体的な方法としては、濾過、デカンテーション、遠心分離、及びこれらの組み合わせ等を例示できる。S12においては、酸溶液から分離した窒化アルミニウム粉末に対して更に水等による洗浄処理を行い、窒化アルミニウム粉末から酸を除去することが好ましい。
リン酸化合物処理工程S13(以下において「S13」と略記することがある。)は、S12を経た窒化アルミニウム粉末とリン酸化合物とを接触させる工程である。S13において窒化アルミニウム粉末とリン酸化合物を接触させる方法としては、公知の方法を特に制限なく採用することができる。例えば、窒化アルミニウム粉末をリン酸化合物溶液中に分散させる方法や、窒化アルミニウム粉末をリン酸化合物溶液に練り込みペースト状にする方法等が挙げられる。窒化アルミニウム粉末をリン酸化合物溶液中に分散させるにあたっては、ディスパーザー、ホモジナイザー、超音波分散機等の公知の装置を用いることができる。
S13におけるリン酸化合物としては、窒化アルミニウム粉末の耐水化に使用する公知のリン酸化合物を特に制限なく使用可能である。S13において使用可能なリン酸化合物の例としては、オルトリン酸、ピロリン酸、メタリン酸等の無機リン酸;リン酸リチウム、リン酸カリウム、リン酸ナトリウム、リン酸水素アルミニウム、リン酸二水素アルミニウム等の無機リン酸金属塩;リン酸アンモニウム、リン酸水素アンモニウム、リン酸二水素アンモニウム等の無機リン酸アンモニウム塩;及び、有機基を有する有機リン酸を挙げることができる。好ましい有機リン酸としては、下記一般式(2)で表される有機リン酸を挙げることができる。
S13において、窒化アルミニウム粉末とリン酸化合物とを接触させる際の条件としては、公知の条件を特に制限なく採用可能である。例えば、接触時間は通常1~120分間とすることができ、また、接触時の温度は通常0~90℃とすることができる。
後処理工程S14(以下において「S14」と略記することがある。)は、S13において得られた窒化アルミニウム粉末とリン酸化合物溶液との混合物から耐水性窒化アルミニウム粉末として取り出す工程である。S14の具体的な態様としては例えば、(A)混合物から溶媒を蒸発させることにより混合物を乾固させる態様;(B)混合物から窒化アルミニウム粉末を濾別し、濾別した窒化アルミニウム粉末を乾燥する態様;及び、(C)混合物から窒化アルミニウム粉末を濾別し、適当な溶媒(例えば水等。)で洗浄した後、乾燥する態様、等を挙げることができる。
酸化膜形成工程S22(以下において「S22」と略記することがある。)は、酸洗工程S11及び固液分離工程S12を経て粒子表面のイットリアが低減された窒化アルミニウム粉末の粒子表面に、酸化膜を形成する工程である。S22を経ることにより、リン酸化合物との反応性を高めることが可能である。S22において酸化膜を形成する方法としては、公知の酸化膜形成方法を採用することができる。S22において形成する酸化膜の量は、原料窒化アルミニウム粉末の表面積(BET法)当たり酸素換算で0.001~0.1g/m2の酸化アルミニウムが存在する程度の量が好ましい。窒化アルミニウム粉末の粒子表面の酸化膜量は、窒化アルミニウム粉末の酸素濃度を、酸素・窒素分析装置(例えば商品名:EMGA-620W、堀場製作所製)を使用し、不活性ガスとしてヘリウムガスを使用して不活性ガス融解-赤外線吸収検出法にて定量することにより、該酸素濃度から以下の式によって決定できる。
酸化膜量=酸素濃度(wt%)/(BET比表面積(m2/g)×100)
本発明によって製造される耐水性窒化アルミニウム粉末は、窒化アルミニウムの性質を生かした種々の用途、特に放熱シート、放熱グリース、放熱接着剤、塗料、熱伝導性樹脂などの放熱材料に充填するフィラーとして広く用いることができる。
レーザー回折散乱式粒度分布測定装置(日機装(株)製MT3300)によって粒度分布(体積分布)を測定し、その中間値に対応する球相当径(直径)を平均粒子径とした。
BET一点法にて測定を行った。
次の工程(a)乃至(f)を順に行うことにより決定した。
(a)酸溶液との接触後、濾別、水洗、及び乾燥された窒化アルミニウム粉末10gを、50mLサンプル瓶(アズワン製スクリュー管瓶No.7、本体は硼珪酸ガラス製)中の1mol/L塩酸25mLに、25℃において加えた。
(b)サンプル瓶を超音波槽(ブランソン製ブランソニック卓上型超音波洗浄器、槽内寸法:幅295×奥行150×高さ150mm、槽容量:6.0L、超音波出力:43kHz、120W)中の水(5L)に浸漬した状態で保持し、25℃において43kHzの超音波を30分間印加した。なお超音波槽の水面からサンプル瓶の底部外側表面までの深さは40mmとした。
(c)サンプル瓶中の内容物を濾過することにより、濾液を得た。
(d)濾液中のイットリウム含有量を、ICP発光分光法により定量した。
(e)濾液中のイットリウム含有量を、イットリアとしての含有量に換算した。
(f)換算されたイットリア含有量を、上記「酸溶液との接触後、濾別、水洗、及び乾燥された窒化アルミニウム粉末」100g当たりの値に換算した。
窒化アルミニウム粉末の酸素濃度を、酸素・窒素分析装置(商品名:EMGA-620W、堀場製作所製)を使用し、不活性ガスとしてヘリウムガスを使用して不活性ガス融解-赤外線吸収検出法にて定量した。得られた酸素濃度から次の式によって酸素膜量を算出した。
リン酸処理工程を経て得られた耐水性窒化アルミニウム粉末2gを室温の純水100g中に分散させ、分散液のpHをpH試験紙にて測定した後、この分散液を圧力容器に充填し120℃まで加熱し、24時間保持した後、水冷によって室温まで冷却し、分散液のpHをpH試験紙にて再度測定し、加熱前と加熱後の2つのpH値を記録した。加熱後のpHが加熱前のpHより上昇していれば、窒化アルミニウムの加水分解が進行したことを意味する。
(原料窒化アルミニウム粉末の準備)
Al源として、平均粒子径1.2μm、比表面積10.7m2/gのα-アルミナを使用し、カーボン粉末として、比表面積125m2/gのカーボンブラックを使用し、希土類金属化合物(共融解剤)として、平均粒子径1.0μm、比表面積11.7m2/gの酸化イットリウムを使用した。
上記得られた原料窒化アルミニウム粉末500gと1mol/Lの濃度の塩酸1200mLを5Lビーカーに入れ、室温にてスターラーで1時間撹拌して、酸溶液との接触処理を行った。
次いで、吸引ろ過により、窒化アルミニウム粉末を酸溶液から濾別し、水による洗浄を行った後、窒化アルミニウム粉末を回収した。上記酸溶液との接触後の窒化アルミニウム粉末から塩酸抽出により抽出されるイットリアの量は、乾燥した酸洗済み窒化アルミニウム粉末100gに対して200mgであった。
上記酸溶液との接触後の窒化アルミニウム粉末を0.5wt%の濃度のオルトリン酸水溶液0.6Lに分散させ、30分間羽根撹拌(撹拌翼を用いて撹拌)した後、分散液を乾固させて耐水性窒化アルミニウム粉末を得た。
酸溶液を1mol/L硝酸に変更した以外は、実施例1と同様にして耐水性窒化アルミニウム粉末を製造した。
(酸洗工程及び固液分離工程)
5Lビーカーに実施例1で準備した原料窒化アルミニウム粉末500gと1mol/L塩酸1200mLを入れ、室温にてスターラーで1時間撹拌し、吸引ろ過及び水洗により粉末を回収した。酸溶液との接触後の窒化アルミニウム粉末から塩酸抽出により抽出されるイットリアの量は、乾燥した酸洗済み窒化アルミニウム粉末100gに対して200mgであった。
上記酸溶液との接触後の窒化アルミニウム粉末を、大気雰囲気中、1000℃で5時間酸化処理を行った。酸化処理後の窒化アルミニウム粉末の粒子表面の酸化膜量は0.02g/m2であった。
上記酸化処理を経た窒化アルミニウム粉末を4wt%の濃度のオルトリン酸水溶液0.6Lに分散させ、30分間羽根撹拌した後、分散液を乾固させることにより、耐水性窒化アルミニウム粉末を得た。耐水性試験の結果、加熱前のpH=6.5に対して加熱後のpH=6.5であり、窒化アルミニウム粉末の加水分解が進行しなかったことが判明した。
酸洗工程を行わなかった比較例である。5Lビーカーに、実施例1で準備した原料窒化アルミニウム粉末500g及び0.5wt%オルトリン酸水溶液0.6Lを入れ、30分間羽根撹拌した後、分散液を乾固させることにより耐水性窒化アルミニウム粉末の製造を試みた。耐水性試験の結果、加熱前のpH=6.5に対して加熱後のpH=11であり、窒化アルミニウムの加水分解が進行したことが判明した。
オルトリン酸水溶液の濃度を5wt%とした以外は比較例1と同様にして、耐水性窒化アルミニウム粉末の製造を試みた。耐水性試験の結果、加熱前のpH=6.5に対して加熱後のpH=11であり、窒化アルミニウムの加水分解が進行したことが判明した。
酸洗工程における撹拌時間を0.5時間とした以外は実施例1と同様にして、耐水性窒化アルミニウム粉末を製造した。酸溶液との接触後の窒化アルミニウム粉末から塩酸抽出により抽出されるイットリアの量は、乾燥した酸洗済み窒化アルミニウム粉末100gに対して918mgであった。得られた耐水性窒化アルミニウム粉末の耐水性試験の結果を表2に示す。
原料窒化アルミニウム粉末及び酸洗条件を変更することにより、酸洗工程後に塩酸抽出により抽出されるイットリアの量が本発明の範囲外(粉末100gあたり1000mg超)である3種類の窒化アルミニウム粉末を用意した。これら3種類の窒化アルミニウム粉末に対して実施例1と同様にリン酸化合物処理を行い、耐水性窒化アルミニウム粉末の製造を試みた。それぞれについて耐水性試験の結果を表2に示す。
一方、塩酸抽出により抽出されるイットリアの量が本発明の規定範囲を超える窒化アルミニウム粉末に対してリン酸化合物処理を施した比較例3~5の耐水性窒化アルミニウム粉末は、耐水性試験において加熱前のpH=6.5に対して加熱後のpH=11であり、窒化アルミニウムの加水分解が進行したことが判明した。
Claims (5)
- 窒化アルミニウム粉末の粒子表面を処理することによって耐水性窒化アルミニウム粉末を製造する方法であって、
(i)少なくとも粒子表面にイットリアが存在する窒化アルミニウム粉末と、酸溶液とを接触させる工程;及び、
(ii)前記窒化アルミニウム粉末とリン酸化合物とを接触させる工程
を上記順に有し、
前記工程(i)の後濾別、水洗、及び乾燥された窒化アルミニウム粉末に対して1mol/L塩酸による抽出操作を行った場合に抽出されるイットリアの量が、該濾別、水洗、及び乾燥された窒化アルミニウム粉末100gに対して1000mg以下であり、
前記抽出されるイットリアの量は、
(a)前記濾別及び乾燥された窒化アルミニウム粉末10gを、50mLサンプル瓶中の1mol/L塩酸25mLに、25℃において加える工程;
(b)前記サンプル瓶を超音波槽中に保持し、25℃において43kHzの超音波を30分間印加する工程;
(c)前記サンプル瓶中の内容物を濾過することにより、濾液を得る工程;
(d)前記濾液中のイットリウム含有量を、ICP発光分光法により定量する工程;及び
(e)前記濾液中のイットリウム含有量を、イットリアとしての含有量に換算する工程
を上記順に行うことにより決定される
ことを特徴とする、耐水性窒化アルミニウム粉末の製造方法。 - 前記窒化アルミニウム粉末の平均粒子径が1~30μmである、
請求項1に記載の耐水性窒化アルミニウム粉末の製造方法。 - 前記酸溶液の溶媒が水であり、前記酸溶液のpHが4以下である、請求項1又は2に記載の耐水性窒化アルミニウム粉末の製造方法。
- 前記リン酸化合物が、無機リン酸、無機リン酸の金属塩、及び、有機基を有する有機リン酸からなる群から選ばれる1種以上の化合物である、
請求項1~3のいずれか一項に記載の耐水性窒化アルミニウム粉末の製造方法。 - 前記工程(ii)において、前記窒化アルミニウム粉末の単位表面積あたりの前記リン酸化合物の付着量が、オルトリン酸イオン(PO4 3-)換算で0.5~50mg/m2である、
請求項1~4のいずれか一項に記載の耐水性窒化アルミニウム粉末の製造方法。
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US9399577B2 (en) | 2016-07-26 |
EP2894126B1 (en) | 2018-08-01 |
TW201418149A (zh) | 2014-05-16 |
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JPWO2014038676A1 (ja) | 2016-08-12 |
KR102051899B1 (ko) | 2019-12-04 |
US20150225238A1 (en) | 2015-08-13 |
EP2894126A1 (en) | 2015-07-15 |
JP6239518B2 (ja) | 2017-11-29 |
TWI583622B (zh) | 2017-05-21 |
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KR20150051939A (ko) | 2015-05-13 |
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