JP5034796B2 - Oxide-coated nickel fine particles and method for producing the same - Google Patents

Description

  The present invention relates to oxide-coated nickel fine particles and a method for producing the same, and more particularly, as a material for conductive paste, while relaxing the property of being easily oxidized of the metal, the properties of the metal, such as high electrical conductivity and metallic luster The present invention relates to oxide-coated nickel fine particles having excellent oxidation resistance and electrical conductivity, and a low-cost and efficient production method. The oxide-coated nickel fine particles obtained here are used for forming a conductive film such as an electronic material wiring excellent in oxidation resistance.

In recent years, fine particles such as copper, nickel, silver, and silver-palladium alloys have been used as conductive metal powders used in conductive pastes for electronic components such as circuit formation. Among these metal fine particles, nickel fine particles, in particular, are attracting attention as materials that are inexpensive and less susceptible to electromigration compared to noble metal fine particles such as silver and silver-palladium alloys. However, nickel fine particles tend to oxidize at a relatively low temperature in the atmosphere, and therefore have a drawback that the conductivity is lowered, and the range of use thereof is limited.
By the way, as the conductive paste containing fine metal particles as a filler, it is roughly divided into a sintered paste used to sinter the metal powder in the paste and used for wiring and electrodes, and a polymer paste solidified with a curable polymer. In any case, it is indispensable that the heat treatment is performed at a temperature of 150 to 350 ° C., so that there is a problem in oxidation resistance in this temperature region. In particular, in the polymer paste, since oxidation proceeds gradually even at room temperature, a means for improving the oxidation resistance has been demanded.

  As means for this purpose, oxide-coated metal fine particles can be considered. For example, as a method of supplying a raw material mixture to thermal plasma and obtaining oxide-coated metal fine particles in which various oxides are coated on various metal fine particles, an oxide coating layer having an average thickness of 1 to 10 nm is firmly formed. It is disclosed that oxide-coated metal fine particles that are completely coated on the entire surface can be obtained (see, for example, Patent Document 1). However, in this method, since there is no description about oxidation resistance, metallic luster and electrical resistance, it is not clear how much the original characteristics of the metal fine particles are maintained. In general, in a hot plasma atmosphere, particles obtained by melting, evaporation, and condensation are often spherical particles, and even if not, they are determined by the crystal habit of the substance, and oxide-coated particles of any shape are used. It is difficult to get. Moreover, according to the TEM image, the coating layers are integrated due to aggregation of particles, and it is difficult to control the particle size distribution. Furthermore, since the apparatus is expensive and the amount of oxide attached to the inner wall of the apparatus is large, it is difficult to manufacture at low cost.

  In addition, a method is disclosed in which noble metal, copper, or the like is included in the oxide coating layer and the oxidation resistance is imparted while lowering the specific resistance (see, for example, Patent Document 2). However, this method has a problem that it is difficult to manufacture at a low cost because the manufacturing method is complicated.

  Further, a copper powder having a first inorganic coat layer made of copper oxide or cuprous oxide on the surface of the copper powder and having various inorganic coat layers such as silicon oxide on the outer shell has been proposed (for example, patents) Reference 3). According to this, oxide-coated copper powder is produced at a relatively low cost, but the second oxide layer is coated by a mechanochemical reaction using a hybridizer, so that an extremely thin film can be uniformly coated. Because it is difficult, it seems difficult to obtain a good specific resistance. For example, it is assumed that it is used for low-temperature fired paste, and the oxidation resistance, volume resistivity, etc. of the powder have not been investigated, and the manufactured oxide-coated metal fine particles maintain the excellent properties of metal fine particles It is unclear whether the oxidation resistance will be improved as it is.

  In view of the above situation, there is a demand for oxide-coated metal fine particles that are excellent in oxidation resistance by using, as a main raw material, a metal that is inexpensive, excellent in electrical conductivity, and has less electromigration as a material for a conductive paste.

JP 2000-219901 A (first page, second page) JP 2004-179139 A (first page, second page) JP 2005-154861 A (first page, second page)

  In view of the above-mentioned problems of the prior art, the object of the present invention is to relieve the property of nickel being easily oxidized as a material for a conductive paste, while at the same time exhibiting properties such as nickel's high electrical conductivity and metallic luster. An object of the present invention is to provide an oxide-coated nickel fine particle excellent in oxidation resistance and electrical conductivity, and a low-cost and efficient production method.

  In order to achieve the above object, the present inventors have conducted extensive research on oxide-coated nickel fine particles, and as a result, oxide-coated nickel composed of core particles made of specific metal fine particles and a specific coating layer. When the fine particles are used as a material for a conductive paste, oxide-coated nickel fine particles that can relieve the property of nickel being easily oxidized while exhibiting properties such as nickel's high electrical conductivity and metallic luster are obtained. In addition, as a manufacturing method, a step (A) of forming nickel fine particles having a coating layer made of an aluminum hydroxide under specific conditions, and then solid-liquid separating the nickel fine particles having the coating layer, Step (B) of performing a drying process, and finally. When the method including the step (C) of thermally decomposing aluminum hydroxide under specific conditions was used, it was found that the oxide-coated nickel fine particles were obtained, and the present invention was completed.

That is, according to the first invention of the present invention, the core particle (a) made of nickel fine particles and the oxide containing as a main component aluminum made of a continuous film formed on the surface of the core particle (a) are formed. A method for producing oxide-coated nickel fine particles comprising a coating layer (b), wherein the aluminum content is 0.07 to 0.4% by weight based on the total amount of oxide-coated nickel fine particles, An aqueous solution containing an aluminum salt and urea in an amount sufficient for the aluminum content to be 0.07 to 0.4% by weight based on the total amount of the oxide-coated nickel fine particles Step (A) of supplying nickel particles having a coating layer made of aluminum hydroxide by supplying a material heated at -100 ° C., and solid-liquid separation of the nickel particles having the coating layer The step (B) of performing the drying treatment, and the step of thermally decomposing the aluminum hydroxide by heating the nickel fine particles having the coating layer after the drying treatment at 200 to 800 ° C. in a reducing atmosphere (C ), And a method for producing oxide-coated nickel fine particles.

According to a second aspect of the present invention, there is provided the method for producing oxide-coated nickel fine particles according to the first aspect , wherein the aluminum salt is aluminum sulfate or aluminum nitrate.

According to a third aspect of the present invention, there is provided the method for producing oxide-coated nickel fine particles according to the first or second aspect , wherein sodium hexametaphosphate is added to the suspension. The

  The oxide-coated nickel fine particles of the present invention are metal fine particles that can relieve the property of nickel being easily oxidized as a conductive paste material, while at the same time exhibiting properties such as nickel's high electrical conductivity and metallic luster. In addition, a continuous film having an oxidation start temperature higher than that of the core particle, a volume resistivity and a metallic luster equivalent to the core particle, and a uniform thickness of the oxide coating layer is formed, and its industrial value is extremely high. large. Furthermore, in the production method of the present invention, the oxide-coated nickel fine particles can be produced efficiently at a low cost, so that the industrial value is extremely large.

Hereinafter, the oxide-coated nickel fine particles of the present invention and the production method thereof will be described in detail.
1. Oxide-coated nickel fine particles The oxide-coated nickel fine particles of the present invention are oxides containing, as main components, core particles (a) composed of nickel fine particles and aluminum composed of a continuous film formed on the surfaces of the core particles (a). An oxide-coated nickel fine particle comprising a coating layer (b) comprising:
The aluminum content is 0.07 to 0.4% by weight based on the total amount of the oxide-coated nickel fine particles.

  In the oxide-coated nickel fine particles of the present invention, nickel fine particles are used as the core particles (a). Thereby, high electrical conductivity and metallic luster are imparted by an inexpensive material compared with noble metals. Furthermore, the coating layer (b) made of an oxide containing aluminum as a main component formed on the surface of the core particle (a) relaxes the property of being easily oxidized of nickel as a conductive paste material. The original properties such as high electrical conductivity and metallic luster can be exhibited, that is, characteristics excellent in oxidation resistance and electrical conductivity are achieved.

  The nickel fine particles used for the core particles (a) are not particularly limited, and those having a purity produced industrially are used. Moreover, the average particle diameter is not specifically limited, 0.1-25 micrometers is preferable. The average particle size was measured by SEM observation. Here, the average particle size means a value obtained by observing from the direction in which the projected area is maximized to obtain the maximum particle size of individual particles and averaging the values.

  The shape of the nickel fine particle is not particularly limited, but is preferably a plate-like particle having an [average particle diameter / average thickness] ratio of 10 or more. As a result, a conductive paste material excellent in electrical conductivity and metallic luster can be obtained. That is, for example, when metal fine particles are used in the polymer paste, plate-shaped metal fine particles are often used in order to increase the contact point and obtain desired electrical conductivity with a small metal content. In addition, the metallic luster required as an excellent characteristic of metals other than electrical conductivity is more emphasized by the plate-like metal fine particles, although light is repelled by free electrons.

  In the oxide-coated nickel fine particles, the content ratio of aluminum in the particles is 0.07 to 0.4% by weight, and preferably 0.07 to 0.2% by weight. That is, when the aluminum content is less than 0.07% by weight, the coating layer becomes too thin, and the oxidation start temperature obtained from TG (thermogravimetric change) measurement is less than 350 ° C. It is insufficient. On the other hand, if the aluminum content exceeds 0.4% by weight, the oxidation start temperature obtained from TG measurement exceeds 410 ° C., and the effect of improving oxidation resistance increases, but the volume resistivity becomes too high. . When the aluminum content is 0.2% by weight or less, a volume resistivity equivalent to that of nickel fine particles that are not coated is obtained.

  The thickness of the coating layer (b) is not particularly limited, and is adjusted so as to obtain desired oxidation resistance and electrical conductivity, but is preferably 1 to 20 nm, and more preferably 1 to 10 nm. .

  The volume resistivity in the measurement of dust resistance of the oxide-coated nickel fine particles is not particularly limited, but is preferably 100 to 10,000 μΩcm when the relative packing density of the particles is 50%. That is, the volume resistivity, which is an index of electrical conductivity, is preferably low, but there are many uncoated nickel fine particles of 200 μΩcm or more, and the lower limit is 100 μΩcm. On the other hand, when the volume resistivity exceeds 10,000 μΩcm, the use of the conductive powder as an application is remarkably limited.

  The oxide-coated nickel fine particles are not particularly limited, but the difference in median diameter D50 measured with a laser light diffraction / scattering particle size analyzer from the core particles used is preferably 10% or less. An example of the laser light diffraction / scattering particle size analyzer is Microtrack HRA MODEL 9320-X100 (manufactured by Microtrack), and a 0.2% by weight aqueous hexametaphosphate solution is preferably used as the solvent. As a result, a continuous film having a uniform coating layer thickness is formed, and fine particles desirable as a conductive paste material can be obtained. That is, although it depends on the required characteristics of each use of the conductive paste, basically, it is desirable to coat each of the metal fine particles as the raw material so that the particles are dispersed.

2. Method for producing oxide-coated nickel fine particles The method for producing oxide-coated nickel fine particles of the present invention is not particularly limited. For example, in an aqueous suspension containing nickel fine particles, the aluminum content is oxidized. Supplied with an aqueous solution containing an aluminum salt and urea in an amount sufficient to be 0.07 to 0.4% by weight based on the total amount of the object-coated nickel fine particles, and heated at 30 to 100 ° C. A step (A) of forming nickel fine particles having a coating layer made of an oxide, a step (B) of solid-liquid separating the nickel fine particles having the coating layer and performing a drying treatment, and a coating layer after the drying treatment A step (C) of heating the nickel fine particles having 200 to 200 to 800 ° C. in a reducing atmosphere to thermally decompose the aluminum hydroxide. As a result, oxide-coated nickel fine particles having characteristics excellent in oxidation resistance and electrical conductivity can be obtained efficiently.

  Step (A) of the above production method is an amount sufficient for the aluminum content ratio to be 0.07 to 0.4% by weight based on the total amount of the oxide-coated nickel fine particles in the aqueous suspension containing the nickel fine particles. This is a step of forming nickel fine particles having a coating layer made of an aluminum hydroxide by supplying an aqueous solution containing an aluminum salt and urea heated at 30 to 100 ° C.

  In the step (A), first, an aqueous solution containing an aluminum salt and urea in an amount sufficient for the aluminum content to be 0.07 to 0.4% by weight based on the total amount of the oxide-coated nickel fine particles is 30 to 100. A coating solution is prepared by heat treatment at a temperature of ° C. Aluminum salt is used as a coating agent, and urea is used as a base. Here, hydroxylation of the aluminum salt in the aqueous solution can be promoted by addition of urea and heating at the above temperature. The coating solution after heating is transparent and no crystallization of fine particles is observed. Here, the concentration of the aluminum salt and urea in the aqueous solution containing the aluminum salt and urea is not particularly limited, but for example, 0.007 to 0.14 mol / L and 0.9 to 18 g / L, respectively. preferable.

  Next, when the obtained coating liquid is supplied into the suspension, a coating layer of aluminum hydroxide is formed on the nickel fine particles. Here, as a supply ratio to the suspension of the coating liquid, an amount sufficient to be 0.07 to 0.4% by weight with respect to the total amount of the oxide-coated nickel fine particles is selected. In addition, the hydroxyl group for forming aluminum hydroxide is supplied from water. At this time, the weight ratio of the nickel fine particles to water is not particularly limited, but sufficient water is required to supply the hydroxyl group.

  Further, in the above method, since the coating speed is slow, aggregation of the nickel fine particles hardly occurs. Thereby, the difference of the median diameter D50 measured with the laser beam diffraction scattering type particle size analyzer with a core particle becomes small. That is, the aluminum hydroxide coating is performed while stirring the suspension, but if the coating is performed too rapidly, the amount of hydroxide deposited at the contact points between the nickel fine particles increases, resulting in a high strength at the contact points. As a result, the nickel fine particles are aggregated.

  As the nickel fine particles used in the step (A), when obtaining plate-like oxide-coated nickel fine particles, it is preferable to use plate-like particles having an [average particle diameter / average thickness] ratio of 10 or more. That is, the shape of the resulting oxide-coated nickel fine particles mainly depends on the shape of the core particles. Here, the average thickness is obtained by embedding plate powder in a resin, polishing the cross section, selecting particles embedded vertically, and observing the cross section with an SEM. The average particle diameter of the nickel fine particles is not particularly limited, but is preferably 0.1 to 25 μm. On the other hand, considering the average particle size, it is not preferable to use plate-like particles having an [average particle size / average thickness] ratio of more than 50 because the strength of the plate-like particles is low and the particles may be deformed.

  Although it does not specifically limit as an aluminum salt used at the said process (A), Aluminum sulfate or aluminum nitrate is mentioned.

  In the step (A), in order to improve the dispersibility of the particles in the aqueous suspension containing the nickel fine particles, although not particularly limited, it is preferable to add sodium hexametaphosphate. Thereby, since the adhesion of aluminum hydroxide to the inner wall of the reaction vessel such as a beaker is also reduced, it is preferable from the viewpoint of operation. Note that. The addition amount of sodium hexametaphosphate is preferably 0.01 to 0.2% by weight with respect to water. That is, when the amount is less than 0.01% by weight, the effect of improving the dispersibility of the particles is insufficient. On the other hand, when the amount exceeds 0.2% by weight, no further improvement in the effect is observed.

  Step (B) of the above production method is a step of subjecting the nickel fine particles having the coating layer to solid-liquid separation and performing a drying treatment. Here, the solid-liquid separation method is not particularly limited, and a normal filtration method is used. Further, the method for the drying treatment is not particularly limited, but in particular, when metallic luster is required, a method of removing moisture at a temperature of 100 ° C. or less in a non-oxidized state by a normal vacuum dryer or the like. Is preferably used.

  Step (C) of the production method is a step of thermally decomposing the aluminum hydroxide by heating the nickel fine particles having the coating layer after the drying treatment at 200 to 800 ° C. in a reducing atmosphere. Thereby, oxide-coated nickel fine particles composed of core particles made of nickel fine particles and a coating layer made of an oxide containing aluminum as a main component covering the core particles are obtained.

  Here, heat treatment is preferably performed in a reducing atmosphere. That is, when heat treatment is performed in the atmosphere or in an inert gas atmosphere, it is oxidized by oxygen in the atmosphere and oxygen in water vapor generated from aluminum hydroxide. Moreover, as heating temperature, it is preferable to carry out at the temperature of 200-800 degreeC. That is, when the temperature is less than 200 ° C., the decomposition and dehydration reaction of the aluminum hydroxide is insufficient, and there is a possibility that it may have an adverse effect when used as a conductive paste. On the other hand, when the temperature exceeds 800 ° C., sintering between the oxide-coated nickel fine particles cannot be ignored, depending on the ratio of the coating layer.

  By the manufacturing method described above, a coating layer made of an oxide containing aluminum as a main component and made of a continuous film having a uniform layer thickness and oxide-coated nickel fine particles made of nickel fine particles can be obtained at low cost. In addition, when the thickness of the oxide coating layer is appropriately reduced, fine particles having high electrical conductivity while having oxidation resistance can be obtained.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples of the present invention, but the present invention is not limited to these examples. In addition, the analysis methods of aluminum (Al) and urea used in Examples and Comparative Examples, and the volume resistivity by the dust resistance measurement, the average particle diameter and average thickness of the core particles, and the evaluation method of the oxidation start temperature are as follows: It is as follows.
(1) Analysis of Al: The analysis was performed by ICP emission analysis.
(2) Measurement of volume resistivity by dust resistance measurement: It was carried out with a dust resistance measuring machine (PD-51 manufactured by Mitsubishi Chemical Corporation).
(3) Measurement of average particle diameter of core particles: It was determined by observing with FE-SEM (manufactured by Hitachi, Ltd., FE-SEM S-4700).
(4) Measurement of oxidation start temperature: TG measurement was performed in an air stream, and the temperature when the weight began to increase and increased by 0.1% was defined as the oxidation start temperature, and the temperature was determined. It can be said that the higher the temperature, the better the oxidation resistance.

Example 1
First, a coating solution composed of an aqueous solution having an Al ₂ (SO ₄ ) ₃ concentration of 0.028 mol / L and a urea concentration of 3.6 g / L was produced, and suction filtered through a 0.4 μm membrane filter to remove dust. The aqueous solution was then kept in an oven at 100 ° C. for 2 hours, and then taken out to room temperature and rapidly cooled.
Next, a suspension composed of 1.71 g of nickel fine particles having an average particle diameter of 20 μm (manufactured by INCO, 225), 180 mL of pure water, and 0.02% by weight of sodium hexametaphosphate with pure water was prepared.
While the suspension was stirred at 200 rpm with a stirrer, 11.25 mL of the coating solution was supplied at a rate of 0.6 mL / min. After maintaining the supply for 50 minutes, the solution was suction filtered and dried at 60 ° C. with a vacuum dryer.
After the nickel fine particles coated with the obtained aluminum hydroxide were heated to 700 ° C. at a rate of 10 ° C./min in a mixed atmosphere of hydrogen 0.2 L / min and nitrogen 9.8 L / min, It cooled in the furnace to 0 degreeC, and the oxide covering nickel fine particle was obtained.
Thereafter, the Al quality of the obtained aluminum oxide-coated nickel fine particles and the oxidation start temperature were determined. Moreover, TEM observation of the cross section was performed. As a result, the Al quality was 0.34% by weight. Moreover, the oxidation start temperature was 384 degreeC. FIG. 1 shows a TEM image of a cross section. From FIG. 1, it can be seen that the film is uniformly coated with a thickness of about 10 to 20 nm.

(Example 2)
The same procedure as in Example 1 was conducted except that the nickel fine particles in the suspension were 10.28 g, the pure water was 1080 mL, and the coating liquid 67.5 mL was supplied at a rate of 3.6 mL / min. The Al quality of the obtained aluminum oxide-coated nickel fine particles, the oxidation start temperature, and the volume resistivity measured by dust resistance measurement were obtained. As a result, the Al quality was 0.28% by weight. The oxidation start temperature was 382 ° C. Further, the volume resistivity at a relative packing density of 50% of the particles was about 560 μΩcm.

(Example 3)
The same procedure as in Example 1 was performed except that the nickel fine particles in the suspension were 200 g, the pure water was 8000 mL, and the coating solution 1300 mL was supplied at a rate of 69 mL / min. The volume resistivity was determined by measuring the Al quality of the fine particles, the oxidation start temperature, and the dust resistance measurement. As a result, the Al quality was 0.17% by weight. The oxidation start temperature was 408 ° C. The volume resistivity at a relative packing density of 50% was about 260 μΩcm.

(Example 4)
The same procedure as in Example 1 was carried out except that the nickel fine particles in the suspension were 200 g, the pure water was 8000 mL, and the coating liquid 650 mL was supplied at a rate of 69 mL / min, and then the aluminum oxide-coated nickel obtained The volume resistivity was determined by measuring the Al quality of the fine particles, the oxidation start temperature, and the dust resistance measurement. As a result, the Al quality was 0.09% by weight. The oxidation start temperature was 382 ° C. The volume resistivity at a relative packing density of 50% was about 190 μΩcm.

(Comparative Example 1)
Using the nickel fine particles used in Examples 1 to 4, the oxidation resistivity was measured and the volume resistivity at a relative packing density of 50% was measured without performing the coating treatment. As a result, the oxidation start temperature was 341 ° C. The volume resistivity at a relative packing density of 50% was about 260 μΩcm.

(Comparative Example 2)
The same procedure as in Example 1 was performed except that the nickel fine particles in the suspension were 200 g, the pure water was 8000 mL, and the coating solution 2600 mL was supplied at a rate of 69 mL / min. Thereafter, the obtained aluminum oxide-coated nickel The volume resistivity was determined by measuring the Al quality of the fine particles, the oxidation start temperature, and the dust resistance measurement. As a result, the Al quality was 0.05% by weight. The oxidation start temperature was 303 ° C. Further, the volume resistivity at a relative packing density of 50% of the particles was about 160 μΩcm.

  As described above, in Examples 1 to 4, the coating treatment is performed according to the method of the present invention using a predetermined coating liquid and a predetermined suspension with a sufficient amount of aluminum in oxidation resistance and electrical conductivity. Therefore, it can be seen that a desired aluminum content ratio is obtained, and oxide-coated nickel fine particles having electric conductivity equivalent to that of the used nickel fine particles and high oxidation resistance can be obtained. In contrast, in Comparative Example 1, no coating treatment was performed, and in Comparative Example 2, since the coating treatment did not meet these conditions, the desired aluminum content ratio was not obtained in the obtained nickel fine particles, and oxidation was not performed. It can be seen that satisfactory results are not obtained in the starting temperature or electrical conductivity.

  As is clear from the above, the oxide-coated nickel fine particles and the method for producing the same of the present invention are used particularly in the field of conductive pastes for electronic parts such as circuit formation using metal fine particles, and metal glossy pigments.

It is a figure showing the cross-sectional TEM image of the aluminum oxide coating nickel fine particle obtained in Example 1 (imaging magnification of 100,000 times).

Claims (3)

A core particle (a) made of nickel fine particles, and a coating layer (b) made of an oxide containing as a main component aluminum made of a continuous film formed on the surface of the core particle (a). A method for producing oxide-coated nickel fine particles having a content ratio of 0.07 to 0.4% by weight based on the total amount of oxide-coated nickel fine particles,
In an aqueous suspension containing nickel fine particles, an aqueous solution containing an aluminum salt and urea in an amount sufficient for the aluminum content to be 0.07 to 0.4% by weight based on the total amount of the oxide-coated nickel fine particles. Supplying the heat-treated one at 30 to 100 ° C. to form nickel fine particles having a coating layer made of aluminum hydroxide (A),
A step (B) of solid-liquid separating the nickel fine particles having the coating layer and performing a drying treatment; and
Heating the nickel fine particles having the coating layer after the drying treatment in a reducing atmosphere at 200 to 800 ° C. to thermally decompose the aluminum hydroxide (C),
A method for producing oxide-coated nickel fine particles, comprising: 2. The method for producing oxide-coated nickel fine particles according to claim 1 , wherein the aluminum salt is aluminum sulfate or aluminum nitrate. The method for producing oxide-coated nickel fine particles according to claim 1 or 2 , wherein sodium hexametaphosphate is added to the suspension.

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