WO2018181482A1 - 銅粒子及びその製造方法 - Google Patents
銅粒子及びその製造方法 Download PDFInfo
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- WO2018181482A1 WO2018181482A1 PCT/JP2018/012780 JP2018012780W WO2018181482A1 WO 2018181482 A1 WO2018181482 A1 WO 2018181482A1 JP 2018012780 W JP2018012780 W JP 2018012780W WO 2018181482 A1 WO2018181482 A1 WO 2018181482A1
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- copper
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- oxygen
- oxide layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2201/00—Treatment under specific atmosphere
- B22F2201/03—Oxygen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
- B22F2302/25—Oxide
Definitions
- the present invention relates to copper particles and a method for producing the same.
- copper has a specific resistance value comparable to that of silver, it has a lower material cost than silver. Therefore, copper is a raw material for conductive pastes used in the formation of printed wiring boards, electrical circuits, and electrodes. Is preferably used. In recent years, as fine pitches and thinning of electrodes have been promoted in fields such as electric circuits, it has been required to achieve both fineness of copper particles for conductive paste and good sinterability. On the other hand, since the microparticulated copper has a very large surface area, the surface oxidation of the particles becomes remarkable during the production of the conductive paste, and the conductivity may be inferior.
- Patent Document 1 proposes a method for producing copper powder by physical vapor deposition (PVD method) using direct current thermal plasma for the purpose of making copper powder fine particles and ensuring conductivity.
- PVD method physical vapor deposition
- the fine copper particles produced by the PVD method have a very large surface area, and the particles tend to aggregate. Therefore, in a wet dispersion process or the like, which is a commercialization process after the manufacture of copper particles, a surface treatment is generally performed in which the copper particles are mixed with a surface treatment agent such as a fatty acid so that the particles are less likely to aggregate. However, even if such a copper particle is subjected to a surface treatment, the primary particles may aggregate again (hereinafter also referred to as reaggregation).
- the copper particles produced by the PVD method have many coarse particles in addition to the fact that the particles tend to aggregate. Therefore, when a conductive paste is prepared using such copper particles, and the paste is applied to a base material and fired, the conductive film obtained by firing is difficult to obtain good surface smoothness. Therefore, when producing conductive paste using copper particles produced by PVD method or the like as raw materials, it is necessary to remove aggregated particles and coarse particles using a filter in advance, but conventional copper particles are aggregated particles. In addition, due to the large number of coarse particles, the number of particles removed by the filter may increase and the yield may decrease.
- the present invention resides in the improvement of the copper particles and the production method thereof. Specifically, when the surface treatment agent is used in the wet dispersion process, which is a commercialization process after the copper particles are produced, the particles are re-agglomerated.
- the present invention relates to hard copper particles and a method for producing the same.
- the present inventors have found that the copper particles satisfying a specific relationship between the oxygen content ratio and the Cu 2 O crystallite size have been re-established after the surface treatment. It has been found that the degree of aggregation is reduced. The present invention has been completed based on this finding.
- the present invention has a core portion comprising copper, and a copper oxide layer comprising CuO and Cu 2 O formed on the surface of the core portion, to provide a copper particles satisfy the relation of the following formula (1) Is. Y ⁇ 36X-18 (1)
- X is the content ratio (% by mass) of oxygen contained in the copper particles
- Y is the crystallite size (nm) of Cu 2 O contained in the copper oxide layer.
- the present invention provides a suitable method for producing the copper particles,
- the raw material powder containing copper element is introduced into the plasma flame to form vapor phase copper, While generating copper particles by cooling the copper in the gas phase, the generated copper particles are exposed to an oxygen-containing atmosphere,
- the present invention provides a method for producing copper particles, which includes a step of oxidizing the surface of the copper particles after being exposed to an oxygen-containing atmosphere to form a copper oxide layer containing CuO and Cu 2 O.
- FIG. 1 is a view showing an embodiment of an apparatus for producing copper particles of the present invention.
- FIG. 2 is a graph showing the relationship between the crystallite size of Cu 2 O and the content ratio of oxygen in the copper particles obtained in Examples and Comparative Examples.
- the copper particles of the present invention have a core part containing copper and a copper oxide layer containing CuO and Cu 2 O formed on the surface of the core part.
- a core part is located in the center area
- the copper oxide layer is located in the surface area of the copper particles of the present invention and constitutes the outermost surface of the copper particles of the present invention.
- the copper oxide layer preferably covers the entire surface of the core part. However, as long as the effect of the present invention is not impaired, the copper oxide layer is formed so that a part of the surface of the core part is exposed to the outside. The surface of the part may be covered. In the copper particles of the present invention, no layer containing a metal element exists outside the copper oxide layer. However, it is allowed that a layer made of an organic compound exists outside the copper oxide layer.
- the shape of the copper particles of the present invention is not particularly limited, and various shapes can be adopted according to specific applications.
- copper particles having various shapes such as a spherical shape, a flake shape, a plate shape, and a dendritic shape can be used.
- the copper particles of the present invention have a volume cumulative particle size D 50 of 0.2 ⁇ m or more and 0.6 ⁇ m or less at a cumulative volume of 50 vol% according to the laser diffraction scattering type particle size distribution measurement method, regardless of the shape of the copper particles described above. It is preferable that it is 0.2 ⁇ m or more and 0.5 ⁇ m or less.
- a conductive composition such as a conductive paste is prepared from the copper particles, and the conductive film is formed using the conductive composition.
- the film is dense and highly conductive.
- a wet reduction method, a PVD method, or the like may be employed to manufacture the copper particles.
- measurement of the volume cumulative particle diameter D 50 may be carried out by the method described in the examples below.
- the core part in the copper particles of the present invention is configured to contain copper. That the core part contains copper includes (a) the case where the core part is substantially made of copper and (b) the case where the core part is made of copper and other elements.
- the proportion of copper in the core part is preferably 99% by mass or more, more preferably 99.5% by mass or more, and the core part consists of copper and inevitable impurities only. Is more preferable.
- the core portion is a portion that occupies most of the mass of the copper particles of the present invention.
- the thickness of the copper oxide layer is preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 55 nm or less. When the copper oxide layer exists in this thickness range, the conductivity of the copper particles of the present invention can be sufficiently increased.
- the ratio of the core portion in the copper particles of the present invention is determined by performing line analysis of the surface portion of the copper particles using, for example, STEM-EDS (Scanning Transmission Electron Microscope-Energy-Dispersive X-ray Spectroscopy), and oxygen (OK line). The thickness of the copper oxide layer can be measured from the line profile.
- the copper oxide layer located on the surface of the core part contains CuO and Cu 2 O as described above.
- the copper oxide layer is composed of only (c) a copper oxide containing CuO and Cu 2 O, or (d) a copper oxide containing CuO and Cu 2 O, in addition to other materials Is included.
- the copper oxide layer is preferably composed only of copper oxide containing CuO and Cu 2 O and inevitable impurities.
- the copper particles of the present invention for example, an embodiment in which the core portion is composed only of copper and inevitable impurities, and the copper oxide layer is composed only of copper oxide containing CuO and Cu 2 O and inevitable impurities. Is mentioned.
- the copper particles in a state where the metallic copper is exposed to the outside are easily bonded to the copper particles in the same state, reaggregation of the particles easily occurs.
- CuO is uniformly formed on the outermost surface of the copper particles due to the high crystallinity of Cu 2 O contained in the copper oxide layer. I believe that. Since CuO is more stable than Cu 2 O, it hardly reacts with a surface treatment agent such as a fatty acid and is less soluble than Cu 2 O. Therefore, the copper metal contained in the core portion is difficult to be exposed to the outside of the copper particles. As a result, the copper particles are difficult to reaggregate.
- the content ratio of oxygen in the copper particles of the present invention is preferably 0.8% by mass or more and 1.80% by mass or less, and 0.8% by mass or more and 1% or less. More preferably, it is 6 mass% or less, and it is still more preferable that it is 0.8 mass% or more and 1.5 mass% or less.
- the content ratio of oxygen in the copper particles of the present invention can be measured, for example, by the method described in Examples described later.
- the copper particles of the present invention preferably have a crystallite size of Cu 2 O contained in the copper oxide layer of 15 nm or more and 60 nm or less, and 20 nm or more and 60 nm, provided that the relationship of the formula (1) is satisfied. More preferably, it is more preferably 20 nm or more and 55 nm or less.
- the crystallite size of Cu 2 O is calculated from the diffraction peak obtained by powder X-ray diffraction according to Scherrer's equation. Measurement by powder X-ray diffraction can be carried out by the method described in the examples described later.
- the copper particles of the present invention may be manufactured by a method described later.
- the crystallite size of Cu 2 O in the copper particles of the present invention has been described.
- the copper particles of the present invention have a metal copper crystallite contained in the core portion.
- size D C is less than 0.090 ⁇ m or more 0.060Myuemu, more preferably less than 0.065 .mu.m 0.085 .mu.m, and still more preferably not less than 0.070 ⁇ m 0.085 ⁇ m.
- crystallite size D C of the metallic copper is in this range, the crystallite size of the Cu 2 O can also be increased, it is possible to uniformly generate more CuO on the outermost surface of the copper oxide layer.
- the crystallite size of metallic copper is calculated from the diffraction peak obtained by powder X-ray diffraction according to the Scherrer equation. Measurement by powder X-ray diffraction can be carried out by the method described in the examples described later.
- the copper particles of the present invention have a core portion with respect to a volume cumulative particle diameter D 50 ( ⁇ m) at a cumulative volume of 50 vol% by a laser diffraction scattering particle size distribution measurement method.
- the value of D C / D 50 which is the ratio of the crystallite size D C ( ⁇ m) of the metallic copper, is preferably 0.10 or more and 0.40 or less, and is 0.10 or more and 0.30 or less. Is more preferably 0.20 or more and 0.30 or less.
- copper particles may be produced by a method described later.
- the copper particles of the present invention include metal copper that is zero-valent copper, Cu 2 O that is monovalent copper, and CuO that is divalent copper.
- the abundance ratio of these three elements on the surface of the copper particles can be measured using an X-ray photoelectron spectrometer (XPS). According to XPS measurement, X-ray photoelectron spectroscopy spectra of various elements can be obtained, and quantitative analysis can be performed on elemental components at a depth of about 10 nm from the surface of the copper particles.
- the peak area P1 of Cu (I) which is monovalent copper and Cu (0) which is zero-valent copper is preferably 0.30 or more and 2.50 or less, and 0.40 More preferably, it is 2.50 or less.
- the copper particles of the present invention satisfy this ratio range, the total amount of Cu (0) and Cu (I) present on the surface of the copper particles and the amount of Cu (II) are reaggregated between the copper particles. It can set appropriately so as to suppress.
- the measurement using XPS can be performed by the method described in Examples described later.
- Step 1 Synthesis of copper particles> Conventionally known methods for producing copper particles include a wet reduction method, an atomization method, a physical vapor deposition method (PVD method), and the like. Among these production methods, in order to make the oxygen content ratio in the copper particles, the crystallite size of Cu 2 O and copper metal, and the D 50 of the copper particles easily satisfy the above range, the PVD method is used. It is preferable to employ and produce copper particles. Therefore, a method for producing copper particles using the PVD method will be described below.
- FIG. 1 shows a thermal plasma generator 1 that is suitably used for the production of copper particles by the PVD method.
- the thermal plasma generator 1 includes a raw material powder supply device 2, a raw material powder supply path 3, a plasma flame generator 4, a plasma gas supply device 5, a chamber 6, a recovery pot 7, an oxygen supply device 8, a pressure adjustment device 9, and an exhaust device. 10 is comprised.
- Raw material powder containing copper element (hereinafter also simply referred to as raw material powder) is introduced into the plasma flame generating section 4 from the raw material powder supply device 2 through the raw material powder supply path 3.
- a plasma flame is generated when the plasma gas is supplied from the plasma gas supply device 5.
- the raw material powder introduced into the plasma flame is evaporated and converted into vapor phase copper, and then released into the chamber 6 existing on the end side of the plasma flame.
- the copper in the vapor phase is cooled as it moves away from the plasma flame, and copper particles are generated through nucleation and grain growth.
- the produced copper particles are exposed to the atmosphere in the chamber 6.
- the copper particles after being exposed to the atmosphere in the chamber 6 adhere to the wall surface inside the chamber 6 or accumulate in the collection pot 7.
- the inside of the chamber 6 is controlled by the pressure adjusting device 9 and the exhaust device 10 so that the negative pressure is relatively maintained as compared with the raw material powder supply path 3, stably generating a plasma flame and plasma the raw material powder.
- the structure can be introduced into the flame generating part 4. Details of the atmosphere in the chamber 6 will be described later.
- the particle size of the raw material powder used for manufacture of the copper particle of this invention there is no restriction
- the shape of the raw material powder particles is not particularly limited, and various shapes such as a spherical shape, a flake shape, a plate shape, and a dendritic shape can be used.
- the oxidation state of the copper element in the raw material powder is not particularly limited, and for example, metal copper powder, copper oxide powder (for example, CuO or Cu 2 O), or a mixture thereof can be used. There are no particular restrictions on the method for producing the raw material powder.
- the supply amount of the raw material powder is preferably 0.1 g / min or more and 100 g / min or less.
- the plasma gas that generates the plasma flame is preferably a mixed gas of argon and nitrogen.
- this mixed gas it is possible to give a larger energy to the raw material powder, and due to this, suitable particle diameter and crystallite size (Cu 2 O and metallic copper) for achieving the effects of the present invention.
- the plasma flame in addition to using a mixed gas of argon and nitrogen as the plasma gas, the plasma flame can be adjusted to be thick and long in a laminar flow state. preferable.
- the “substantially spherical shape” refers to a shape that is not a perfect spherical shape but can be recognized as a sphere.
- Whether or not the plasma flame is in a laminar flow state can be determined by the ratio of the length of the plasma flame to the width of the plasma flame when observed from the side surface where the width of the plasma flame is observed to be the thickest.
- the ratio of the length of the plasma flame to the width of the plasma flame is 3 or more, it is judged as a laminar flow state, and when the ratio of the length of the plasma flame to the width of the plasma flame is less than 3, it is judged as a turbulent flow state. Can do.
- the gas flow rate of the plasma gas is preferably 1 L / min to 35 L / min at room temperature, more preferably 5 L / min to 30 L / min. .
- the plasma output of the thermal plasma generator is preferably 2 kW to 50 kW, more preferably 5 kW to 35 kW.
- the atmosphere in the chamber 6 is an oxygen-containing atmosphere. Highly crystalline on the surface of the core part while maintaining the oxygen content in the copper particles in the above-mentioned range by being exposed to an oxygen-containing atmosphere during the process of cooling the vapor phase copper and producing copper particles This is because a copper oxide layer containing Cu 2 O can be formed.
- the resulting core part by setting an appropriate temperature, it is possible to easily form the copper oxide layer comprising a high Cu 2 O crystallinity.
- the temperature can be controlled by adjusting the gas flow rate of the plasma gas or by adjusting the flow rate of oxygen supplied into the chamber 6 (which will be described later).
- oxygen gas itself or a mixed gas of oxygen gas and another gas can be used.
- various inert gases such as argon and nitrogen can be used.
- the oxygen supply device 8 is connected to the side surface of the chamber and oxygen is supplied into the chamber.
- oxygen can be stably supplied into the chamber 6 at the connection position of the oxygen supply device. If it is a position, it will not specifically limit.
- the flow rate of oxygen supplied into the chamber 6 is preferably 0.002 L / min or more and 0.75 L / min or less. 0.004 L / min or more and 0.70 L / min or less is more preferable.
- the oxygen concentration in the chamber is preferably 100 ppm or more and 2000 ppm or less, and more preferably 200 ppm or more and 1000 ppm or less.
- the oxidation in this step is performed as follows. After the supply of the raw material powder and the generation of the plasma flame are stopped and the inside of the chamber 6 is returned to normal pressure, the copper particles generated in the ⁇ Step 1> are accumulated in the recovery pot 7 and then recovered, and the copper particles are collected in the atmosphere. Under an atmosphere, Cu 2 O on the surface of the copper particles is oxidized to CuO to form a copper oxide layer.
- a copper oxide layer can be generated without causing a rapid oxidation reaction of the copper particles.
- the copper particles in this step, it is preferable to place the copper particles in an air atmosphere having a relative humidity of 30% to 60% and a temperature of 15 ° C to 30 ° C.
- an air atmosphere having a relative humidity of 30% to 60% and a temperature of 15 ° C to 30 ° C.
- the processing time of this process is 5 minutes or more and 60 minutes or less on condition that the conditions of an atmospheric condition are in the above-mentioned range from a viewpoint of preventing the rapid oxidation reaction at the time of collection
- the copper particles of the present invention can be successfully manufactured.
- the copper particles obtained in this manner are preferably sealed in a non-moisture permeable material container and stored at a temperature of room temperature (25 ° C.) or lower for the purpose of maintaining the oxidized state of the copper particle surface. .
- the copper particles of the present invention produced by the above-described production method are re-combined with conventional copper particles when a surface treatment agent is used in a wet dispersion process, which is a production process after the production of copper particles. It becomes difficult to agglomerate.
- a conductive composition such as a conductive paste can be produced without impairing the sinterability at low temperatures.
- Example 1 The above-mentioned ⁇ Step 1> and ⁇ Step 2> were performed under the following production conditions to produce copper particles.
- Step 1 Copper particles (particle diameter D 50 : 12 ⁇ m, particle shape: spherical) as raw material powder produced by the atomization method are introduced into the plasma flame of the thermal plasma generator shown in FIG. 1 at a supply rate of 5 g / min, Vapor phase copper.
- a mixed gas of argon and nitrogen is used as the plasma gas, the flow rate of the plasma gas is 19.0 L / min, and the flow rate (L / min) ratio of argon to nitrogen in the plasma gas is 82:18.
- the plasma output was 19 kW.
- Copper particles having a core part and a copper oxide layer were formed so that copper particles were exposed to an oxygen-containing atmosphere while copper in a gas phase was generated by cooling in a chamber.
- the flow rate of the oxygen-nitrogen mixed gas (containing 5% by volume of oxygen) into the chamber was 0.20 L / min (the flow rate of oxygen was 0.01 L / min), and the oxygen concentration in the chamber was 440 ppm.
- the generation of the plasma flame is stopped in a state where the copper particles are present in the chamber, and nitrogen gas is supplied into the chamber at a negative pressure ( ⁇ 0.05 MPa) at a flow rate of 30 L / min. The pressure was returned to normal pressure over 15 minutes.
- ⁇ Process 2> After performing ⁇ Step 1>, copper particles were recovered. A copper oxide layer was formed on the surface of the copper particles while crushing the particles with a sieve in an air atmosphere having a relative humidity of 50% and a temperature of 25 ° C. The time for placing in the atmosphere was 30 minutes.
- Example 1 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.29 L / min (the flow rate of oxygen is 0.0145 L / min) and the oxygen concentration in the chamber is 640 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 3 Example 1 was the same as Example 1 except that the oxygen-nitrogen mixed gas flow rate into the chamber was 0.11 L / min (oxygen flow rate was 0.0055 L / min) and the oxygen concentration in the chamber was 240 ppm. The operation was performed to produce copper particles.
- Example 4 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.34 L / min (the flow rate of oxygen is 0.017 L / min) and the oxygen concentration in the chamber is 750 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 5 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.09 L / min (the flow rate of oxygen is 0.0045 L / min) and the oxygen concentration in the chamber is 200 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 6 Example 1 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.39 L / min (the flow rate of oxygen is 0.0195 L / min) and the oxygen concentration in the chamber is 850 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 7 Example 1 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.33 L / min (the flow rate of oxygen is 0.0165 L / min) and the oxygen concentration in the chamber is 730 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 8 Example 1 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.18 L / min (the flow rate of oxygen is 0.009 L / min) and the oxygen concentration in the chamber is 400 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 9 Example 1 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.26 L / min (the flow rate of oxygen is 0.013 L / min) and the oxygen concentration in the chamber is 570 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 10 is the same as Example 1 except that the flow rate of the oxygen-nitrogen mixed gas into the chamber is 0.24 L / min (the flow rate of oxygen is 0.012 L / min) and the oxygen concentration in the chamber is 540 ppm.
- the copper particles were manufactured by performing the above operations.
- Example 1 the flow rate of plasma gas is 36 L / min, the flow rate of oxygen-nitrogen mixed gas into the chamber is 0.74 L / min (the flow rate of oxygen is 0.037 L / min), and the oxygen concentration in the chamber is 860 ppm. Except for the above, copper particles were produced in the same manner as in Example 1.
- Example 2 In Example 1, the flow rate of plasma gas is 36 L / min, the flow rate of oxygen-nitrogen mixed gas into the chamber is 0.35 L / min (the flow rate of oxygen is 0.0175 L / min), and the oxygen concentration in the chamber is 410 ppm. Except for the above, copper particles were produced in the same manner as in Example 1.
- Example 3 In Example 1, the flow rate of plasma gas is 36 L / min, the flow rate of oxygen-nitrogen mixed gas into the chamber is 0.79 L / min (the flow rate of oxygen is 0.0395 L / min), and the oxygen concentration in the chamber is 910 ppm. Except for the above, copper particles were produced in the same manner as in Example 1.
- Example 5 In Example 1, the flow rate of plasma gas is 36 L / min, the flow rate of oxygen-nitrogen mixed gas into the chamber is 0.44 L / min (the flow rate of oxygen is 0.022 L / min), and the oxygen concentration in the chamber is 510 ppm. Then, except that ⁇ Step 2> was not performed, the same operations as in Example 1 were performed to produce copper particles.
- the crystallite size D C of the cumulative volume particle diameter D 50 and metallic copper was measured by the following method. Then, the crystallite size D C of the metallic copper was calculated value of D C / D 50 is divided by a volume cumulative particle diameter D 50 of the copper particles. The results are shown in Table 1.
- the recovery rate of the copper particles by filter filtration and the surface roughness of the coating film of the composition containing the copper particles are as follows. Measured with The results are shown in Table 1.
- Scherrer's formula: D K ⁇ / ⁇ cos ⁇ D: Crystallite size K: Scherrer constant (1.333)
- ⁇ wavelength of X-ray ⁇ : integral width [rad]
- ⁇ Diffraction angle
- the background mode used is Shirley.
- the binding energy of C1s was set to 234.8 eV.
- the above-described peak areas P0, P1, and P2 were calculated from the peak area ratio after Cu 2p3 / 2 peak separation was performed in the range of 930.0 eV or more and 933.0 eV or less for Cu (Cu (I)).
- the ratio of the mass of the produced copper particles to the total mass of the mass of the copper particles remaining on the filter and the mass of the produced copper particles (the mass of the produced copper particles / (on the filter The mass of the remaining copper particles + the mass of the produced copper particles) ⁇ 100) was calculated, and this value was defined as the recovery rate (%).
- This paste was further processed 5 times in total using a 3 roll mill to further disperse and mix to prepare a paste.
- the paste thus prepared was applied onto a slide glass substrate with a doctor blade and a gap of 35 ⁇ m. Then, using a nitrogen oven, it was heated and dried at 150 ° C. for 10 minutes to prepare a coating film.
- the surface roughness of this coating film was measured using a surface roughness meter (SURFCOM 480B-12 manufactured by TOKYO SEIMITSU).
- the copper particles of each example have a high filter recovery rate, whereas the copper particles of the comparative example have a low filter recovery rate.
- the reason for this is that the reaggregation of the particles of the copper particles of the examples is suppressed.
- the surface roughness of the coating film obtained from the copper particles of each Example having a high recovery rate was the same as the surface roughness of the coating film obtained from the copper particles of the comparative example, although the filter recovery rate was increased. It turns out that it is equivalent. This is also because the copper particles of the examples are suppressed from agglomerating particles.
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Abstract
Description
Y≧36X-18 ・・・(1)
式中、Xは銅粒子中に含まれる酸素の含有割合(質量%)であり、Yは酸化銅層中に含まれるCu2Oの結晶子サイズ(nm)である。
銅元素を含む原料粉をプラズマ炎中に導入して気相状態の銅となし、
気相状態の前記銅の冷却によって銅粒子を生成させつつ、生成した該銅粒子を酸素含有雰囲気に曝し、
酸素含有雰囲気に曝された後の前記銅粒子の表面を酸化させてCuO及びCu2Oを含む酸化銅層を生成させる工程を有する、銅粒子の製造方法を提供するものである。
Y≧36X-18 ・・・(1)
<工程1.銅粒子の合成>
これまで知られている銅粒子の製造方法としては、一般に湿式還元法、アトマイズ法及び物理気相成長法(PVD法)などが挙げられる。これらの製造方法のうち、銅粒子における酸素の含有割合、Cu2O及び金属銅の結晶子サイズ、並びに銅粒子のD50などが上述の範囲を容易に満たすようにするために、PVD法を採用して銅粒子を製造することが好ましい。そこで以下にPVD法を用いた銅粒子の製造方法を説明する。
前記<工程1>で生成した銅粒子は、更に酸化処理されることが好ましい。本工程を行うことによって、<工程1>で未反応であった銅粒子表面のCu2OをCuOに緩やかに酸化させ、Cu2O及びCuOを含む酸化銅層をより厚く且つ表面全体に隙間なく生成させることができ、表面処理後において、一層再凝集しづらい銅粒子を得ることができる。
以下の製造条件で、上述の<工程1>及び<工程2>を行い、銅粒子を製造した。
アトマイズ法によって製造された原料粉となる銅粒子(粒径D50:12μm、粒子形状:球状)を、5g/minの供給量で図1に示す熱プラズマ発生装置のプラズマ炎中に導入し、気相状態の銅とした。プラズマ炎発生の条件として、アルゴンと窒素との混合ガスをプラズマガスとして用い、プラズマガスの流量を19.0L/min、プラズマガスにおけるアルゴンと窒素との流量(L/min)比を82:18、プラズマ出力を19kWとした。
気相状態の銅をチャンバー内で冷却によって銅粒子を生成させつつ、銅粒子が酸素含有雰囲気に曝されるようにして、コア部と酸化銅層を有する銅粒子を形成した。チャンバー内への酸素-窒素混合ガス(酸素を5体積%含む)の流量は0.20L/min(酸素の流量は0.01L/min)、チャンバー内の酸素濃度は440ppmとした。その後、銅粒子がチャンバー内に存在している状態でプラズマ炎の発生を停止させ、陰圧(-0.05MPa)となっているチャンバー内に窒素ガスを30L/minの流量で供給し、陰圧から15分かけて常圧に戻した。
<工程1>を行った後、銅粒子を回収した。その銅粒子を、相対湿度が50%で、温度が25℃の大気雰囲気下で、篩による粒子の解砕を行いつつ銅粒子の表面に酸化銅層を生成させた。大気雰囲気下に置く時間は、30分とした。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.29L/min(酸素の流量は0.0145L/min)、チャンバー内の酸素濃度を640ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガス流量を0.11L/min(酸素の流量は0.0055L/min)、チャンバー内の酸素濃度を240ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.34L/min(酸素の流量は0.017L/min)、チャンバー内の酸素濃度を750ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.09L/min(酸素の流量は0.0045L/min)、チャンバー内の酸素濃度を200ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.39L/min(酸素の流量は0.0195L/min)、チャンバー内の酸素濃度を850ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.33L/min(酸素の流量は0.0165L/min)、チャンバー内の酸素濃度を730ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.18L/min(酸素の流量は0.009L/min)、チャンバー内の酸素濃度を400ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.26L/min(酸素の流量は0.013L/min)、チャンバー内の酸素濃度を570ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてチャンバー内への酸素-窒素混合ガスの流量を0.24L/min(酸素の流量は0.012L/min)、チャンバー内の酸素濃度を540ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてプラズマガスの流量を36L/minとし、チャンバー内への酸素-窒素混合ガスの流量を0.74L/min(酸素の流量は0.037L/min)、チャンバー内の酸素濃度を860ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてプラズマガスの流量を36L/minとし、チャンバー内への酸素-窒素混合ガスの流量を0.35L/min(酸素の流量は0.0175L/min)、チャンバー内の酸素濃度を410ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてプラズマガスの流量を36L/minとし、チャンバー内への酸素-窒素混合ガスの流量を0.79L/min(酸素の流量は0.0395L/min)、チャンバー内の酸素濃度を910ppmとした以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてプラズマガスの流量を36L/minとし、チャンバー内に酸素-窒素混合ガスを導入しなかった以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例1においてプラズマガスの流量を36L/minとし、チャンバー内への酸素-窒素混合ガスの流量を0.44L/min(酸素の流量は0.022L/min)、チャンバー内の酸素濃度を510ppmとし、<工程2>を行わなかった以外は、実施例1と同様の操作を行い銅粒子を製造した。
実施例及び比較例で得られた銅粒子について、酸素の含有割合及びCu2Oの結晶子サイズを以下の方法で測定した。そして、銅粒子中の酸素の含有割合(単位:質量%)をXとし、酸化銅層に含まれるCu2Oの結晶子サイズ(単位:nm)をYとしたときに、各実施例及び比較例において前記式(1)の関係を満たしているか否かを確認した。その結果を表1に示した。また、XとYとの関係をグラフ化したものを図2に示した。
LECOジャパン合同会社製の酸素・窒素分析装置TC-500を用いた。測定試料0.05gを秤量し、ニッケルカプセルに入れた後、黒鉛坩堝内で加熱する。加熱の際に、試料中の酸素と坩堝とが反応して生成した一酸化炭素及び二酸化炭素を、赤外線吸収法で検出し、酸素の含有割合(質量%)を算出した。
銅粒子の酸化銅層中に含まれるCu2Oの結晶子サイズは、株式会社リガク製のSmartLabにて、CuKα1線を使用して、測定範囲2θ=20°~100°で銅粒子のX線回折強度を測定したときのCu2Oの結晶面(111)におけるX線回折ピークの積分幅から、下記のシェラーの式により算出した。
シェラーの式:D=Kλ/βcosθ
D:結晶子サイズ
K:シェラー定数(1.333)
λ:X線の波長
β:積分幅[rad]
θ:回折角
0.1gの測定試料に、0.1%濃度のポリオキシエチレン(10)オクチルフェニルエーテル(和光純薬工業株式会社製)水溶液をスポイトで数滴添加してなじませた後、アニオン系界面活性剤(サンノプコ株式会社製 品名:SNディスパーサント5468)の0.1%水溶液80mlと混合し、超音波ホモジナイザ(日本精機製作所製 US-300T)で5分間分散させた。その後、レーザー回折散乱式粒度分布測定装置、マイクロトラック・ベル株式会社製マイクロトラックHRAを用いて、体積累積粒径D50を測定した。
銅粒子のコア部中に含まれる金属銅の結晶子サイズは、株式会社リガク製のSmartLabにて、CuKα1線を使用して、測定範囲2θ=20°~100°で銅粒子のX線回折強度を測定したときの金属銅の結晶面(200)におけるX線回折ピークの積分幅から、下記のシェラーの式により算出した。
シェラーの式:D=Kλ/βcosθ
D:結晶子サイズ
K:シェラー定数(1.333)
λ:X線の波長
β:積分幅[rad]
θ:回折角
アルバック・ファイ株式会社製のVersaProbeIIを用いた。測定条件は以下のとおりである。
X線源:Mg-Kα線(1253.6eV)
X線源の条件:400W
Pass Energy:23eV
エネルギーステップ:0.1eV
検出器と試料台の角度:90°
帯電中和:低速イオン及び電子を使用
解析は、アルバック・ファイ株式会社製MultiPak9.0の解析ソフトを用いた。ピーク分離はMultiPak9.0のCurve Fitを用い、Cu 2p3/2のメインピークとは、930eV以上940eV以下に現れるピークのことである。使用バックグラウンドモードはShirleyである。帯電補正はC1sの結合エネルギーを234.8eVとした。
上述のピーク面積P0、P1及びP2は、Cu(Cu(I)については930.0eV以上933.0eV以下の範囲でCu 2p3/2ピークの波形分離を行い、そのピーク面積比から算出した。
各実施例及び比較例で得られた銅粒子の製造時において、銅粒子を含むスラリーをろ過した後の目開き1μmのフィルターを真空乾燥機(ADVANTEC製)で40℃にて乾燥し、フィルター上に残存した銅粒子とフィルターとの質量を測定した。この測定質量からろ過前のフィルターの質量を差し引くことにより、フィルター上に残存した銅粒子の質量を算出した。また、各実施例及び比較例の方法で製造された銅粒子の質量を測定した。これらの質量から、フィルター上に残存した銅粒子の質量と製造された銅粒子の質量との合計量に対する、製造された銅粒子の質量の比(製造された銅粒子の質量/(フィルター上に残存した銅粒子の質量+製造された銅粒子の質量)×100)を算出し、この値を回収率(%)とした。回収率が60%以上であった場合を「○」とし、回収率が60%未満であった場合を「×」とした。
各実施例及び比較例で得られた銅粒子で得られた銅粒子10gと、10質量%の熱可塑性セルロースエーテル(The Dow Chemical Company製 品名:ETHOCEL STD100)を含有したターピネオール(ヤスハラケミカル株式会社製)ビヒクル1.5gとを秤量し、ヘラで予備混練した後、株式会社シンキー製の自転・公転真空ミキサーARE-500を用いて、攪拌モード(1000rpm×1分間)と脱泡モード(2000rpm×30秒間)とを1サイクルとした処理を2サイクル行い、ペースト化した。このペーストを、更に3本ロールミルを用いて合計5回処理することで更に分散混合を行い、ペーストを調製した。このように調製したペーストを、ドクターブレードを用い、ギャップを35μmに設定してスライドガラス基板上に塗布した。その後、窒素オーブンを用い、150℃で10分間加熱乾燥し塗膜を作製した。この塗膜について、表面粗さ計(TOKYO SEIMITSU製SURFCOM 480B-12)を用いて表面粗さを測定した。
また、回収率が高い各実施例の銅粒子から得られた塗膜の表面粗さは、フィルター回収率が増大したにもかかわらず、比較例の銅粒子から得られた塗膜の表面粗さと同等となっていることが判る。この理由も、実施例の銅粒子は、粒子どうしの凝集が抑制されていることによる。
Claims (6)
- 銅を含むコア部と、該コア部の表面に形成されたCuO及びCu2Oを含む酸化銅層とを有し、下記式(1)の関係を満たす銅粒子。
Y≧36X-18 ・・・(1)
式中、Xは銅粒子中に含まれる酸素の含有割合(質量%)であり、Yは酸化銅層中に含まれるCu2Oの結晶子サイズ(nm)である。 - レーザー回折散乱式粒度分布測定法による累積体積50容量%における体積累積粒径D50(μm)に対する、前記コア部中に含まれる金属銅の結晶子サイズDC(μm)の比率であるDC/D50の値が0.10以上0.40以下である請求項1に記載の銅粒子。
- 酸素の含有割合が0.80質量%以上1.80質量%以下である請求項1又は2に記載の銅粒子。
- 前記銅粒子の表面を測定して得られるX線光電子分光スペクトルにおいて、Cu(I)のピーク面積P1及びCu(0)のピーク面積P0に対する、Cu(II)のピーク面積P2の比率であるP2/(P1+P0)の値が0.30以上2.50以下である請求項1ないし3のいずれか一項に記載の銅粒子。
- 銅元素を含む原料粉をプラズマ炎中に導入して気相状態の銅となし、
前記気相状態の銅の冷却によって銅粒子を生成させつつ、生成した該銅粒子を酸素含有雰囲気に曝し、
酸素含有雰囲気に曝された後の前記銅粒子の表面を酸化させてCuO及びCu2Oを含む酸化銅層を生成させる工程を有する、銅粒子の製造方法。 - 酸素含有雰囲気に曝された後の前記銅粒子を、相対湿度が30%以上60%以下で、且つ15℃以上30℃以下の大気雰囲気下に5分以上60分以下置き、該銅粒子の表面を酸化させて前記酸化銅層を生成させる請求項5に記載の銅粒子の製造方法。
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KR20190132351A (ko) | 2019-11-27 |
CN110325303B (zh) | 2022-01-11 |
JPWO2018181482A1 (ja) | 2020-02-06 |
TW201841702A (zh) | 2018-12-01 |
CN110325303A (zh) | 2019-10-11 |
KR102403998B1 (ko) | 2022-05-31 |
JP7050756B2 (ja) | 2022-04-08 |
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