CN110325303A - Copper particle and its manufacturing method - Google Patents
Copper particle and its manufacturing method Download PDFInfo
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- CN110325303A CN110325303A CN201880012738.6A CN201880012738A CN110325303A CN 110325303 A CN110325303 A CN 110325303A CN 201880012738 A CN201880012738 A CN 201880012738A CN 110325303 A CN110325303 A CN 110325303A
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- copper particle
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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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
Copper particle of the invention has the core comprising copper and that be formed in the surface of the core includes CuO and Cu2The copper oxide of O.When the content ratio (quality %) of oxygen included in copper particle is set as X, by Cu included in copper oxide2When the crystallite dimension (nm) of O is set as Y, meet the condition of Y >=36X-18.The crystallite dimension D of metallic copper included in coreCVolume-cumulative partial size D when (μm) and the cumulative volume based on Measurement of particle size distribution by laser diffraction are 50 capacity %50Ratio, that is, the D of (μm)C/D50Value be also preferably 0.10~0.40.In addition, the content ratio of oxygen is also preferably 0.80 mass of mass %~1.80 %.
Description
Technical field
The present invention relates to copper particle and its manufacturing methods.
Background technique
Copper has the resistivity value with silver-colored same degree, and fee of material is lower than silver, therefore is suitable for matching for printing
The raw materials such as the conductive paste of the formation of line substrate, circuit, electrode.In recent years, the fields such as circuit promoting fine-pitch and
Electrode it is thin layer, accompanying this require take into account conductive paste copper particle micronized and good agglutinating property.On the other hand, micro-
Copper after granulation is since surface area is very big, and when manufacturing conductive paste, the surface oxidation of particle becomes significant, sometimes
Lead to poorly conductive.
Patent document 1 in order to ensure copper powder micronized and electric conductivity and propose based on having used direct current hot plasma
Physical vaporous deposition (PVD method) copper powder manufacturing method.
Existing technical literature
Patent document
Patent document 1: No. 2015/122251 pamphlet of International Publication No.
Summary of the invention
The surface area of the copper particle of the particle as made from PVD method etc. is very big, and particle is easy to happen cohesion each other.Therefore,
In as the wet type dispersion step of commercialization process etc. after the manufacture of copper particle, usually carry out the tables such as copper particle and fatty acid
Surface treatment agent mixes and making particle each other becomes the surface treatment for being not susceptible to cohesion.But for this copper particle, even if
It is to be surface-treated, primary particle can also be agglomerated again and (hereinafter also referred to as be re-united) sometimes each other.
In addition, the coarse grain of copper particle as made from PVD method etc. is also more other than particle is easy cohesion each other.Exist as a result,
Conductive paste is made using this copper particle and the muddle is distributed in substrate come in the case where being burnt into, by what is be fired into
Conductive film is difficult to obtain good surface smoothness.Therefore, using by the systems such as PVD method to copper particle make conduction as raw material
Property paste in the case where, need to use filter by flocculated particle, coarse grain removing in advance, but existing copper particle is due to flocculated particle
It is more with coarse grain, therefore increased by the particle that filter removes, sometimes result in yield decline.
Therefore, the present invention is copper particle and the improvement of its manufacturing method, relates in particular to manufacture as copper particle
Particle in the case where surface treating agent has been used to be not susceptible to re-unite each other in the wet type dispersion step of commercialization process afterwards
Copper particle and its manufacturing method.
Inventor hereins have made intensive studies to solve the above-mentioned problems, as a result, it has been found that: oxygen contains
Ratio and Cu2The crystallite dimension of O, which meets the copper particle of particular kind of relationship particle is mutual after surface treatment, re-unites degree reduction.
The present invention is completed based on the discovery.
That is, the present invention provides a kind of copper particle, there is the core comprising copper and be formed in the surface of the core includes
CuO and Cu2The copper oxide of O meets the relationship of following formula (1).
Y≥36X-18 (1)
In formula, X is the content ratio (quality %) of oxygen included in copper particle, and Y is included in copper oxide
Cu2The crystallite dimension (nm) of O.
In addition, the present invention provides a kind of manufacturing method of copper particle as the preferable production process of above-mentioned copper particle, packet
Include following processes:
Raw material powder comprising copper is imported to the copper in plasma flame and forming gas phase state,
Copper particle is generated by the cooling of the above-mentioned copper of gas phase state, while the copper particle generated being exposed to and is contained
Oxygen atmosphere,
Make the surface oxidation for being exposed to the above-mentioned copper particle after oxygen-containing atmosphere and generates comprising CuO and Cu2The copper oxide of O
Layer.
Detailed description of the invention
Fig. 1 is the figure for indicating to manufacture an embodiment of the device of copper particle of the present invention.
Fig. 2 is the Cu in the copper particle for indicating to be obtained by embodiment and comparative example2The crystallite dimension of O and the content ratio of oxygen
Between relationship curve graph.
Specific embodiment
Hereinafter, to the present invention is based on its preferred embodiments to be illustrated.Copper particle of the invention has the core comprising copper
Portion includes CuO and Cu with the surface for being formed in core2The copper oxide of O.Core is located at the center in copper particle of the invention
Region is a greater part of position of the quality accounted in copper particle of the invention.On the other hand, copper oxide is located at of the invention
Surface region in copper particle, which constitute the most surfaces of copper particle of the invention.Copper oxide preferably covers the whole of core
A surface, but as long as lossless effect of the invention, then copper oxide can also be exposed to outer according to a part on the surface of core
The mode on boundary covers the surface of core.For copper particle of the invention, it is not present more outward compared with copper oxide
Layer comprising metallic element.But allow to there is the layer being made of organic compound more outward compared with copper oxide.
Its shape is not particularly limited in copper particle of the invention, can use various shape according to particular use.For example,
The copper particle of various shapes such as spherical, laminar, plate and resin-like can be used.
Copper particle of the invention is based on laser diffraction and scattering formula granularity in the case where its shape is any one of above-mentioned
Volume-cumulative partial size D when the cumulative volume of distribution analysis is 50 capacity %50Both preferably 0.2 μm~0.6 μm, more preferably
0.2 μm~0.5 μm.By making the partial size of copper particle within the scope of this, by conductions such as the copper particle preparation such as conductive pastes
Property composition and in the case where forming conductive film using the conductive composition, which becomes fine and close and electric conductivity is high.For
The copper particle that partial size is the range is obtained, as long as such as manufacturing using wet-type reduction method, PVD method etc. copper particle.Separately
Outside, volume-cumulative partial size D50Measurement can be carried out by method described in aftermentioned embodiment.
Core in copper particle of the invention is constituted comprising copper.Core include copper-clad include (i) core substantially by
The case where the case where copper is constituted and (ii) core are made of copper and other elements.In the case where (i), shared copper in core
Ratio is preferably 99 mass % or more, more preferably 99.5 mass % or more, and further preferred core is only by copper and inevitable
Impurity constitute.
Under any case in the case where above-mentioned (i) and (ii), as described above, core is to account for copper of the invention
A greater part of position of quality in grain.The thickness of copper oxide is preferably 1nm~100nm, more preferably 1nm~55nm.It is logical
Crossing makes copper oxide with thickness range presence, can sufficiently improve the electric conductivity of copper particle of the invention.Copper of the invention
The ratio of shared core for example can be by STEM-EDS (Scanning Transmission Electron in grain
Microscope-Energy-Dispersive X-ray Spectroscopy, scanning transmission electron microscope-energy dispersion X
Ray spectrum) carry out copper particle surface portion line analysis, the thickness of copper oxide is measured by the line profile of oxygen (O-K line).
As described above, the copper oxide for being located at the surface of core includes CuO and Cu2O.Copper oxide (iii) only by comprising
CuO and Cu2The oxide of the copper of O is constituted, or (iv) containing including CuO and Cu2The oxide of the copper of O, also contains in addition to this
Other substances.In the case where (iii), copper oxide is preferably only by including CuO and Cu2The oxide of the copper of O and inevitable
Impurity constitute.
CuO and Cu in any one of above-mentioned (iii) and (iv), in copper oxide2The existence of O does not have
There is special limitation.For example, CuO and Cu2O can be any mixed state, or the position that is made of CuO and by Cu2O is constituted
Position can individually exist respectively.At the position being made of CuO and by Cu2The position that O is constituted is individually existing respectively
In the case of, such as can enumerate by Cu2The position that O is constituted is present in the surface of core, the position being made of CuO is present in this
The form on the surface at position.
As the particularly preferred embodiment of copper particle of the invention, such as core can be enumerated only by copper and can not
The impurity avoided is constituted, copper oxide is only by comprising CuO and Cu2The reality that the oxide of the copper of O and inevitable impurity are constituted
Apply mode.
It is that inventor hereins study as a result, it has been found that: when the content ratio and copper of the oxygen in copper particle of the invention
Cu in the copper oxide of particle2The copper after surface treatment when the crystallite dimension of O is in particular kind of relationship, in commercialization process
The dispersibility of grain improves.Specifically, it was found that: it is set as when by the content ratio (unit: quality %) of the oxygen in copper particle
X, by the Cu in copper oxide2When the crystallite dimension (unit: nm) of O is set as Y, the case where meeting the relationship of following formula (1)
Under, the copper particle after the surface treatment in commercialization process is not susceptible to re-unite, and dispersibility especially improves.
Y≥36X-18 (1)
What the dispersibility of the copper particle after surface treatment when meeting the relationship of formula (1) in commercialization process especially improved
Reason is not yet clear, but inventor hereins are presumed as follows.Just by the copper particle of the generations such as wet-type reduction method, PVD method Lai
It says, the Cu at particle surface2The exposing degree of O increases.When to such copper particle in the commercialization process such as wet type dispersion step
In when being mixed with surface treating agents such as fatty acid, pass through fatty acid and Cu2The reaction of O and make Cu2O dissolves, in the core of copper particle
The metallic copper for being included is exposed to the external world.The copper particle that metallic copper is exposed to extraneous state is easy and the copper in same state
Particle combines, thus is easy to happen that particle is mutual to be re-united.In contrast, meet the copper particle of formula (1) due to copper oxide
Included in Cu2The crystallinity of O is high, it is thus regarded that the most surface in copper particle equably generates CuO.CuO is due to than Cu2O is steady
It is fixed, therefore be not easy to react with surface treating agents such as fatty acid, with Cu2O is compared and is not readily dissolved.Therefore, included in core
Metallic copper become the external world for being not easy to be exposed to copper particle.As a result, copper particle is not susceptible to re-unite each other.
To meet the relationship of above-mentioned formula (1) as condition, the content ratio of the oxygen in copper particle of the invention is preferably 0.8 matter
Measure the mass % of %~1.80, the more preferably 0.8 mass % of mass %~1.6, further preferably 0.8 matter of mass %~1.5
Measure %.By making the content ratio of the oxygen range, after the surface treatment in commercialization process, copper particle becomes to be not easy each other
It re-unites.The content ratio of oxygen in copper particle of the invention for example can by method described in aftermentioned embodiment come into
Row measurement.
Similarly, to meet the relationship of above-mentioned formula (1) as condition, copper particle of the invention is included in copper oxide
Cu2The crystallite dimension of O is preferably 15nm~60nm, more preferably 20nm~60nm, further preferably 20nm~55nm.Pass through
Make Cu2The crystallite dimension of O is the range, and copper particle becomes to be not susceptible to coagulate again each other after the surface treatment in commercialization process
It is poly-.Cu2The crystallite dimension of O is calculated by the diffraction maximum obtained by powder x-ray diffraction according to Scherrer (Scherrer) formula.Base
It can be carried out by method described in aftermentioned embodiment in the measurement of powder x-ray diffraction.
In order to make copper particle of the invention meet the condition of formula (1), as long as manufacturing copper particle for example, by aftermentioned method
Row.
Above description refers to the Cu in copper particle of the invention2The crystallite dimension of O, but other than the crystallite dimension,
For copper particle of the invention, the crystallite dimension D of metallic copper included in coreCPreferably 0.060 μm~0.090 μm,
More preferably 0.065 μm~0.085 μm, further preferably 0.070 μm~0.085 μm.By the crystallite dimension for making metallic copper
DCFor the range, it is also capable of increasing Cu2The crystallite dimension of O, and then CuO can be made equably to be created on the most surface of copper oxide.
The crystallite dimension of metallic copper is calculated by the diffraction maximum obtained by powder x-ray diffraction according to Scherrer (Scherrer) formula.Base
It can be carried out by method described in aftermentioned embodiment in the measurement of powder x-ray diffraction.
From more efficiently preventing from from the viewpoint of copper particle re-unites each other, for copper particle of the invention, in core
Metallic copper crystallite dimension DC(μm) and the cumulative volume based on Measurement of particle size distribution by laser diffraction are 50 appearances
Measure volume-cumulative partial size D when %50Ratio, that is, the D of (μm)C/D50Value be preferably 0.10~0.40, more preferably 0.10~
0.30, further preferably 0.20~0.30.In order to make DC/D50Value meet the range, as long as such as by aftermentioned method come
Manufacture copper particle just.
As described above, copper particle of the invention includes as the metallic copper of 0 valence copper, as cupprous Cu2O and as two
The CuO of valence copper.This three at the surface of copper particle there are ratio can be used x-ray photoelectron spectroscopy (XPS) come into
Row measurement.Measured by XPS, the x-ray photoelectron spectroscopy of various elements can be obtained, can surface to copper particle to about ten
The elemental composition of depth carries out quantitative analysis until nanometer.With regard to being surveyed by surface state of the XPS to copper particle of the invention
For x-ray photoelectron spectroscopy obtained from fixed, as the peak area P2 of cupric Cu (II) and as cupprous Cu (I)
Peak area P1 and the value of ratio, that is, P2/ (P1+P0) of peak area P0 of the Cu (0) as 0 valence copper be preferably 0.30~2.50,
More preferably 0.40~2.50.By making copper particle of the invention meet the proportional region, it can suitably set and be present in copper
The total amount of the Cu (0) and Cu (I) of particle surface and the amount of Cu (II) are to inhibit copper particle to re-unite each other.The survey of XPS is used
Surely it can be carried out by method described in aftermentioned embodiment.
Hereinafter, being illustrated to the preferable production process of copper particle of the invention.
<synthesis of 1. bronze medal particle of process>
As the manufacturing method of hitherto known copper particle, wet-type reduction method, atomization and physics can be usually enumerated
Vapour deposition process (PVD method) etc..Among these manufacturing methods, in order to make content ratio, the Cu of the oxygen in copper particle2O and metal
The crystallite dimension of copper and the D of copper particle50Etc. readily satisfying above range, it is preferred to use PVD method manufactures copper particle.Then,
The manufacturing method for the copper particle for having used PVD method is illustrated below.
Fig. 1, which is shown, is suitable for the hot plasma generation device 1 based on PVD method manufacture copper particle.Hot plasma produces
Generating apparatus 1 includes raw material powder feedway 2, raw material powder feed path 3, plasma flame generating unit 4, plasma gas supply
Device 5, chamber 6, recycling can 7, oxygen supply device 8, pressure regulation device 9 and exhaust apparatus 10 and constitute.
Raw material powder (being hereinafter also referred to as raw material powder) comprising copper is supplied via raw material powder feed path 3 by raw material powder
It is imported into plasma flame generating unit 4 to device 2.In plasma flame generating unit 4, by being supplied by plasma gas
Device 5 supplies plasma gas, generates plasma flame.The raw material powder being imported into plasma flame is evaporated and becomes
For the copper of gas phase state, then released into the chamber 6 for the terminal part side for being present in plasma flame.The copper of gas phase state with
It is cooled far from plasma flame, is grown by karyogenesis, grain and generates copper particle.Copper particle generated is exposed to chamber
Atmosphere in room 6.Copper particle after the atmosphere being exposed in chamber 6 is attached to the wall surface inside chamber 6 or accumulates in recycling can 7
It is interior.Negative pressure is kept at opposite compared with raw material powder feed path 3 by pressure regulation device 9 and the control of exhaust apparatus 10 in chamber 6, at
For raw material powder can be imported to the structure in plasma flame generating unit 4 while steadily generating plasma flame.Chamber 6
The details of interior atmosphere is as described later.
Partial size for manufacturing the raw material powder of copper particle of the present invention is not particularly limited.From to hot plasma generation device
The efficiency of supply from the viewpoint of, the volume-cumulative partial size D of raw material powder50Preferably 3 μm~30 μm.In addition, the particle of raw material powder
Shape be not particularly limited, the particle of various shapes such as spherical, laminar, plate, dendroid can be used.The copper of raw material powder
The state of oxidation of element is not particularly limited, and copper powder, cupric oxide powder (such as CuO or Cu can be used for example2O) or they
Mixture etc..The manufacturing method of raw material powder is also not particularly limited.
It is former from the viewpoint of the copper particle big from the crystallite dimension for steadily manufacturing metallic copper for this manufacturing method
The supply amount of feed powder is preferably 0.1g/ minutes~100g/ minutes.
It is preferable to use the mixed gas of argon and nitrogen for the plasma gas of generation plasma flame.By using the gaseous mixture
Body can provide raw material powder bigger energy, preferred in terms of playing effect of the present invention thus, it is possible to obtain having
Partial size and crystallite dimension (Cu2O and metallic copper) copper particle.In particular, from the sight for obtaining spherical or approximate sphericity copper particle
Point considers, preferably in addition to use the mixed gas of argon and nitrogen as plasma gas other than be adjusted to plasma flame also as layer
Stream mode and thicker, elongated." approximate sphericity " refers to shape that is not complete spherical but can identifying as ball.With regard to it is equal from
Daughter flame whether be for laminar condition, can be by carrying out being observed to most thick side from the width of plasma flame
The ratio between width of the length of plasma flame and plasma flame is judged when observation.Plasma flame length with etc.
The ratio between width of gas ions flame may determine that in the case where being 3 or more as laminar condition, plasma flame length and it is equal from
The ratio between width of daughter flame less than 3 in the case where may determine that as turbulent condition.
From the viewpoint of the laminar condition for stably keeping plasma flame, the gas flow of plasma gas is in room
Temperature lower preferably 1L/ minutes~35L/ minutes, more preferably 5L/ minutes~30L/ minutes.By using the gas stream of the range
Amount, particle generated contact in the state of maintaining proper temperature with the oxygen-containing atmosphere in aftermentioned chamber 6.As a result,
Can successfully be formed on the surface of core as target includes CuO and Cu2The copper oxide of O.Hot plasma generates dress
The plasma output power set is preferably 2kW~50kW, more preferably 5kW~35kW.From the same viewpoint, plasma
Flow (L/ minutes) of argon and nitrogen in body gas than being preferably argon: nitrogen=99:1~10:90, more preferably 95:5 at room temperature
~70:30.
For this manufacturing method, the atmosphere in chamber 6 is preferably oxygen-containing atmosphere.This is because by making gas phase state
Copper cooled and generate copper particle during is exposed to oxygen-containing atmosphere, the content ratio of the oxygen in copper particle can be protected
It holds as above range, while the Cu high comprising crystallinity can be formed on the surface of core2The copper oxide of O.At this point, pass through by
Core generated is set as temperature appropriate, is able to easily form the Cu high comprising crystallinity2The copper oxide of O.With regard to temperature
For the setting of degree, for example, as described above can by adjusting plasma gas gas flow, adjust and supplied into chamber 6
The flow (this point as described later) of oxygen controlled.As oxygen-containing atmosphere, oxygen itself, oxygen and other gas can be used
The mixed gas etc. of body.Using mixed gas, the various non-active gas headed by argon, nitrogen can be used for example
As other gases.In addition, for embodiment shown in FIG. 1, oxygen supply device 8 connect with the side of chamber and to chamber
It is interior for oxygen supply, the link position of oxygen supply device is as long as the position that oxygen can be stably supplied into chamber 6 without special
It limits.
From the viewpoint of the copper generated by the copper of gas phase state is exposed to oxygen-containing atmosphere particle stabilizedly, to chamber 6
The flow of the oxygen of interior supply is preferably 0.002L/ minutes~0.75L/ minutes, and more preferably 0.004L/ minutes~0.70L/ points
Clock.In addition, from the Cu high comprising crystallinity is formed2From the viewpoint of the copper oxide of O, the indoor oxygen concentration of chamber is preferably
100ppm~2000ppm, more preferably 200ppm~1000ppm.
<2. oxidation processes of process>
Oxidation processes are preferably further carried out by the copper particle that above-mentioned<process 1>generates.By carrying out this process, can make
The Cu of unreacted copper particle surface in<process 1>2O is slowly oxidized to CuO, can it is thicker and whole surface continuously
It includes Cu that unoccupied place, which generates,2The copper oxide of O and CuO can be less susceptible to the copper particle re-united after surface treatment.
Oxidation in this process carries out as follows.Stop the supply of raw material powder and the generation of plasma flame and makes in chamber 6
Restore normal pressure, then recycles the copper particle generated by above-mentioned<process 1>accumulation after recycling can 7, by the copper particle
It is placed under air atmosphere, makes the Cu of copper particle surface2O is oxidized to CuO and generates copper oxide.
For this process, when copper particle being placed in air atmosphere getting off to carry out, copper particle can not occur sharply
Oxidation reaction and generate copper oxide.But from the viewpoint of industrial productivity, for copper particle generated it is preferable to use
Sieve etc. is placed under air atmosphere while the particle being crushed after cohesion.
From the viewpoint of the uniformity of the oxidation processes of copper particle, copper particle is preferably placed in relative humidity and is by this process
30%~60% and temperature be under 15 DEG C~30 DEG C of air atmosphere.Oxidation reaction is carried out under this condition, and thus, it is possible to logical
Moisture included in air atmosphere is crossed by the Cu of copper oxide2O is slowly oxidized to CuO, can be formed on surface stable
Copper oxide.
In addition, for the processing time of this process, from the viewpoint for preventing abrupt oxidization of the copper particle in recycling from reacting
Consider, using the condition of air atmosphere as above range in for condition, preferably 5 minutes~60 minutes, more preferably 5 minutes~30
Minute.
By the above-mentioned manufacture method, copper particle of the invention can successfully be manufactured.For the obtained copper particle,
For the purpose of the state of oxidation for maintaining copper particle surface, it is preferably sealed in the container of non-moisture permeable material and is stored in room temperature
At (25 DEG C) temperature below.
In addition, for copper particle of the invention as made from above-mentioned manufacturing method, as the production after the manufacture of copper particle
In the case where having used surface treating agent in the wet type dispersion step of product chemical industry sequence, become to be not easy to send out compared with existing copper particle
Life re-unites.In addition, by using copper particle of the invention, can agglutinating property under lossless low temperature and manufacture conductive paste etc. and lead
Conductive composition.
Embodiment
In the following, the present invention is described in more detail by embodiment.But the scope of the present invention is not limited to the implementation
Example.As long as not special declaration, " % " refers to " quality % ".
[embodiment 1]
It is carried out with following manufacturing conditions above-mentioned<process 1>and<process 2>, manufactures copper particle.
<process 1>
By copper particle (the partial size D as made from atomization as raw material powder50: 12 μm, grain shape: spherical) with 5g/ points
The supply amount of clock imports in the plasma flame of hot plasma generation device shown in FIG. 1, forms the copper of gas phase state.Make
For the condition that plasma flame generates, use the mixed gas of argon and nitrogen as plasma gas, by plasma gas
Flow set is 19.0L/ minutes, flow (L/ minutes) ratio of the argon in plasma gas and nitrogen is set as 82:18, plasma
Body output power is set as 19kW.
So that the copper of gas phase state is generated copper particle by cooling in chamber, while copper particle being made to be exposed to oxygen-containing atmosphere,
Thus form the copper particle with core and copper oxide.To the indoor oxygen-nitrogen mixture gas of chamber (oxygen comprising 5 volume %)
Flow set be 0.20L/ minutes (flow of oxygen is 0.01L/ minutes), the indoor oxygen concentration of chamber is set as 440ppm.Later,
In the state that copper particle is present in chamber stop plasma flame generation, with 30L/ minute flows to as negative pressure (-
Nitrogen is supplied in chamber 0.05MPa), reverts to normal pressure from negative pressure with 15 minutes.
<process 2>
After having carried out<process 1>, copper particle is recycled.Under the air atmosphere that relative humidity is 50%, temperature is 25 DEG C,
The broken of particle based on sieve is carried out to the copper particle, while in the Surface Creation copper oxide of copper particle.It is placed in atmosphere gas
Time under atmosphere is set as 30 minutes.
2- propyl alcohol is added in such a way that obtained copper particle is 30 mass %, then adds 5 matter relative to copper particle
The lauric acid as dispersing agent for measuring %, prepares slurry.By the slurry with NanomizermarkII (wet type crushing device, Ji
The mechanical industrial Co. Ltd. system in field, ProductName: NM2-2000AR) broken (broken condition: 50MPa, five passages).After this is crushed
Slurry mesh be 1 μm filter (ROKI TECHNO Co., LTD., ProductName: SBP010) filter, then by filtrate
Supernatant remove, remaining solid component is dried with vacuum drier (ADVANTEC system) in 40 DEG C.Later, in nitrogen
Under atmosphere, is sieved by the sieve that mesh is 150 μm, obtained copper particle.
[embodiment 2]
In addition to will be in embodiment 1 the 0.29L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.0145L/ minutes), the indoor oxygen concentration of chamber is set as other than 640ppm, carry out operation similarly to Example 1 and
Manufacture copper particle.
[embodiment 3]
In addition to that will be in embodiment 1 the 0.11L/ minutes (flows of oxygen to the indoor oxygen of chamber-nitrogen mixture gas flow set
Be 0.0055L/ minutes), the indoor oxygen concentration of chamber is set as other than 240ppm, carry out operation similarly to Example 1 and make
Produce copper particle.
[embodiment 4]
In addition to will be in embodiment 1 the 0.34L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.017L/ minutes), the indoor oxygen concentration of chamber is set as other than 750ppm, carry out operation similarly to Example 1 and make
Produce copper particle.
[embodiment 5]
In addition to will be in embodiment 1 the 0.09L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.0045L/ minutes), the indoor oxygen concentration of chamber is set as other than 200ppm, carry out operation similarly to Example 1 and
Manufacture copper particle.
[embodiment 6]
In addition to will be in embodiment 1 the 0.39L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.0195L/ minutes), the indoor oxygen concentration of chamber is set as other than 850ppm, carry out operation similarly to Example 1 and
Manufacture copper particle.
[embodiment 7]
In addition to will be in embodiment 1 the 0.33L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.0165L/ minutes), the indoor oxygen concentration of chamber is set as other than 730ppm, carry out operation similarly to Example 1 and
Manufacture copper particle.
[embodiment 8]
In addition to will be in embodiment 1 the 0.18L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.009L/ minutes), the indoor oxygen concentration of chamber is set as other than 400ppm, carry out operation similarly to Example 1 and make
Produce copper particle.
[embodiment 9]
In addition to will be in embodiment 1 the 0.26L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.013L/ minutes), the indoor oxygen concentration of chamber is set as other than 570ppm, carry out operation similarly to Example 1 and make
Produce copper particle.
[embodiment 10]
In addition to will be in embodiment 1 the 0.24L/ minutes (stream of oxygen to the flow set of the indoor oxygen-nitrogen mixture gas of chamber
Amount is 0.012L/ minutes), the indoor oxygen concentration of chamber is set as other than 540ppm, carry out operation similarly to Example 1 and make
Produce copper particle.
[comparative example 1]
In addition in embodiment 1 by the flow set of plasma gas be 36L/ minutes, will be mixed to the indoor oxygen-nitrogen of chamber
The flow set for closing gas is 0.74L/ minutes (flow of oxygen is 0.037L/ minutes), is set as the indoor oxygen concentration of chamber
Other than 860ppm, carries out operation similarly to Example 1 and manufacture copper particle.
[comparative example 2]
In addition in embodiment 1 by the flow set of plasma gas be 36L/ minutes, will be mixed to the indoor oxygen-nitrogen of chamber
The flow set for closing gas is 0.35L/ minutes (flow of oxygen is 0.0175L/ minutes), is set as the indoor oxygen concentration of chamber
Other than 410ppm, carries out operation similarly to Example 1 and manufacture copper particle.
[comparative example 3]
In addition in embodiment 1 by the flow set of plasma gas be 36L/ minutes, will be mixed to the indoor oxygen-nitrogen of chamber
The flow set for closing gas is 0.79L/ minutes (flow of oxygen is 0.0395L/ minutes), is set as the indoor oxygen concentration of chamber
Other than 910ppm, carries out operation similarly to Example 1 and manufacture copper particle.
[comparative example 4]
In addition in embodiment 1 by the flow set of plasma gas be 36L/ minute, not into chamber importing oxygen-nitrogen
Other than mixed gas, carries out operation similarly to Example 1 and manufacture copper particle.
[comparative example 5]
In addition in embodiment 1 by the flow set of plasma gas be 36L/ minutes, will be mixed to the indoor oxygen-nitrogen of chamber
The flow set for closing gas is 0.44L/ minutes (flow of oxygen is 0.022L/ minutes), is set as the indoor oxygen concentration of chamber
510ppm, without<process 2>other than, carry out operation similarly to Example 1 and manufacture copper particle.
[evaluation]
The copper particle just obtained by embodiment and comparative example, by following methods to the content ratio and Cu of oxygen2The crystallite of O
Size is determined.In addition, when the content ratio (unit: quality %) of the oxygen in copper particle is set as X, by copper oxide
Included in Cu2When the crystallite dimension (unit: nm) of O is set as Y, it is thus identified that whether meet in each embodiment and comparative example
The relationship of above-mentioned formula (1).It the results are shown in table 1.In addition, curve graph is made in the relationship of X and Y and is shown in Fig. 2.
In turn, the copper particle just obtained by embodiment and comparative example, by following methods to volume-cumulative partial size D50And gold
Belong to the crystallite dimension D of copperCIt is determined.Also, by the crystallite dimension D of metallic copperCDivided by the volume-cumulative partial size of copper particle
D50, thus calculate DC/D50Value.It the results are shown in table 1.
In turn, the copper particle just obtained by embodiment and comparative example, by following methods with XPS depositing to the copper of each valence mumber
It is determined in ratio.It the results are shown in table 1.
In addition, passing through following sides in order to which the cohesion degree to the copper particle obtained by embodiment and comparative example is evaluated
Method carries out the surface roughness of the rate of recovery of the copper particle filtered based on filter and the film of the composition comprising copper particle
Measurement.It the results are shown in table 1.
[measuring method of the content ratio of oxygen]
The oxygen nitrogen analysis device TC-500 for having used contract commercial firm, LECO Japan to manufacture.It weighs 0.05g measurement sample and fills
Enter nickel capsule, is then heated in graphite crucible.When heating, detect that oxygen in sample and crucible are anti-by infrared absorption
The carbon monoxide and carbon dioxide answered and generated calculate the content ratio (quality %) of oxygen.
[Cu2The measurement of the crystallite dimension of O]
Cu included in the copper oxide of copper particle2The crystallite dimension of O calculates as follows: being manufactured by Co., Ltd. Neo-Confucianism
SmartLab the use of 1 ray of CuK α is that 2 θ=20 °~100 ° carry out the X-ray diffraction intensity of copper particle with measurement range
Measurement, by Cu at this time2The integral breadth at the X-ray diffraction peak at the crystal face (111) of O is calculated according to following Scherrer formula.
Scherrer formula: D=K λ/β cos θ
D: crystallite dimension
K: Scherrer constant (1.333)
λ: the wavelength of X-ray
β: integral breadth [rad]
θ: the angle of diffraction
[the volume-cumulative partial size D of copper particle50Measurement]
Polyoxyethylene (10) octyl phenyl ether that a few drop concentration are 0.1% is added to the measurement sample of 0.1g by syringe
(Wako Pure Chemical Industries, Ltd.'s system) aqueous solution simultaneously is allowed to merge, later with (Sheng Nuopuke plants of anionic surfactant
Formula commercial firm system, ProductName: SN-DISPERSANT 5468) 0.1% aqueous solution 80ml mixing, with ultrasonic homogenizer (Japan
Smart mechanism makees made US-300T) disperse 5 minutes.Later, using laser diffraction and scattering formula particle size distribution device Mai Qike
Baeyer Co. Ltd. system Microtrac HRA is to volume-cumulative partial size D50It is determined.
[measurement of the crystallite dimension of metallic copper]
The crystallite dimension of metallic copper included in the core of copper particle calculates as follows: being manufactured by Co., Ltd. Neo-Confucianism
SmartLab is that 2 θ=20 °~100 ° carry out the X-ray diffraction intensity of copper particle with measurement range using 1 ray of CuK α
Measurement, is calculated by the integral breadth at the X-ray diffraction peak of the crystal face (200) of metallic copper at this time according to following Scherrer formula.
Scherrer formula: D=K λ/β cos θ
D: crystallite dimension
K: Scherrer constant (1.333)
λ: the wavelength of X-ray
β: integral breadth [rad]
θ: the angle of diffraction
[copper of each valence mumber based on XPS there are the measurements of ratio]
The VersaProbeII for having used ULVAC-PHI Co., Ltd. to manufacture.Determination condition is as described below.
X-ray source: Mg-K alpha ray (1253.6eV)
The condition of x-ray source: 400W
Logical energy: 23eV
Energy step-length: 0.1eV
The angle of detector and sample table: 90 °
Band charge neutrality: low speed ion and electronics are used
The analysis software for the MultiPak9.0 that analysis has used ULVAC-PHI Co., Ltd. to manufacture.Peak separation uses
The main peak of Curve Fit, the Cu 2p3/2 of MultiPak9.0 refers to the peak for appearing in 930eV~940eV.Use background mode
For Shirley.The combination of C1s can be set as 234.8eV by electrification correction.
For above-mentioned peak area P0, P1 and P2, with regard to Cu, (range of the Cu (I) in 930.0eV~933.0eV carries out Cu 2p3/
The waveform at 2 peaks separates, and is calculated by its peak area ratio.
[rate of recovery of the copper particle based on filter filtering]
In the copper particle that manufacture is obtained by each embodiment and comparative example, with vacuum drier (ADVANTEC system) in 40 DEG C
The filter for being 1 μm to the mesh after the slurry of bag filter cupric particle is dried, to the copper remained on filter
The quality of grain and filter is determined.The quality of the filter before filtering is subtracted by the quality measurement, thus calculates remaining
In the quality of the copper particle on filter.In addition, to the quality of copper particle made from the method as each embodiment and comparative example into
Measurement is gone.Gone out by these Mass Calculations the quality of manufactured copper particle and the quality of the copper particle remained on filter and
The ratio between manufactured total amount of quality of copper particle (quality of manufactured copper particle/(remain in the copper particle on filter
The quality of the copper particle of quality+manufactured) × 100), using the value as the rate of recovery (%).The rate of recovery is denoted as when being 60% or more
"○" is denoted as "×" when the rate of recovery is less than 60%.
[surface roughness of the film of the composition comprising copper particle]
Weigh the copper particle 10g obtained by the copper particle obtained by each embodiment and comparative example and containing 10 mass %'s
The terpinol of thermoplastic cellulose ester (Dow Chemical's system, ProductName: ETHOCEL STD100) (pacifies former Chemical Co., Ltd.
System) carrier 1.5g, pre- mixing has been carried out with scraper, has then used the rotation-revolution vacuum mixer ARE- of Thinky Corp.
500 follow to carry out two circulations with stirring mode (1000rpm × 1 minute) and deaeration mode (2000rpm × 30 second) for one
The processing of ring, is gelatinized.In turn, total five processing are carried out to the paste using three-roll mill, thus further progress point
Mixing is dissipated, paste is prepared.Using scraper, gap is set as 35 μm, the muddle so prepared is distributed on glass slide substrate.It
Afterwards, using nitrogen furnace, the heat drying 10 minutes at 150 DEG C and produce film.For the film, surface roughness meter is used
(Tokyo precision system SURFCOM480B-12) is determined surface roughness.
Known to result as shown in Table 1: the filter rate of recovery of the copper particle of each embodiment increases, and the copper of comparative example
The filter rate of recovery of grain reduces.The reason for this is that because the copper particle of embodiment inhibits particle to re-unite each other.
In addition, knowing: for the surface roughness of the film obtained by the copper particle of the high each embodiment of the rate of recovery, though
The right filter rate of recovery increases, but same with the surface roughness of the film obtained by the copper particle of comparative example.Its reason is also
Because the copper particle of embodiment inhibits particle to aggregate with one another.
Industrial availability
According to the present invention, a kind of copper particle is provided, in the wet type dispersion as the commercialization process after the manufacture of copper particle
Particle in the case where surface treating agent has been used to be not susceptible to re-unite each other in process.
Claims (6)
1. a kind of copper particle, has the core comprising copper and that be formed in the surface of the core includes CuO and Cu2The copper oxide of O
Layer, meets the relationship of following formula (1),
Y≥36X-18 (1)
In formula, X is the content ratio in terms of quality % of oxygen included in copper particle, and Y is Cu included in copper oxide2O
The crystallite dimension in terms of nm.
2. copper particle according to claim 1, wherein the crystallite dimension D of metallic copper included in the coreCWith base
Volume-cumulative partial size D when the cumulative volume of Measurement of particle size distribution by laser diffraction is 50 capacity %50Ratio be
DC/D50Value be 0.10~0.40, D50And DCUnit be μm.
3. copper particle according to claim 1 or 2, wherein the content ratio of oxygen is 0.80 mass of mass %~1.80 %.
4. copper particle according to any one of claim 1 to 3, wherein be measured on the surface to the copper particle
Obtained from x-ray photoelectron spectroscopy, the peak area P0 of the peak area P1 and Cu (0) of the peak area P2 and Cu (I) of Cu (II)
Ratio, that is, P2/ (P1+P0) value be 0.30~2.50.
5. a kind of manufacturing method of copper particle comprising following processes:
Raw material powder comprising copper is imported to the copper in plasma flame and forming gas phase state,
Copper particle is generated by the cooling of the copper of the gas phase state, while the copper particle generated being exposed to oxygenous
Atmosphere,
Make the surface oxidation for being exposed to the copper particle after oxygen-containing atmosphere and generates comprising CuO and Cu2The copper oxide of O.
6. the manufacturing method of copper particle according to claim 5, wherein the copper particle after oxygen-containing atmosphere will be exposed to
It is placed 5 minutes~60 minutes in the case where relative humidity is 30%~60% and 15 DEG C~30 DEG C of air atmosphere, makes the copper particle
Surface oxidation and generate the copper oxide.
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| PCT/JP2018/012780 WO2018181482A1 (en) | 2017-03-31 | 2018-03-28 | Copper particles and manufacturing method therefor |
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| KR (1) | KR102403998B1 (en) |
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| JP6956765B2 (en) * | 2019-08-07 | 2021-11-02 | Ｊｘ金属株式会社 | Joining method using copper powder paste |
| JP6956766B2 (en) * | 2019-08-07 | 2021-11-02 | Ｊｘ金属株式会社 | Joining method using copper powder paste |
| JP6704083B1 (en) * | 2019-11-22 | 2020-06-03 | 東邦チタニウム株式会社 | Copper powder and its manufacturing method |
| CN113019468A (en) * | 2021-03-05 | 2021-06-25 | 昆明理工大学 | Copper-based Cu-Cu2Preparation method of O-CuO ternary composite core-shell material |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002169273A (en) * | 2000-11-30 | 2002-06-14 | Murata Mfg Co Ltd | Photosensitive copper paste and circuit board using the same |
| CN1422510A (en) * | 2000-04-10 | 2003-06-04 | 特乔尼科斯有限公司 | Twin plasma torch apparatus |
| CN102350499A (en) * | 2011-09-28 | 2012-02-15 | 河北工业大学 | Cu/Cu2O core-shell composite microsphere and preparation method thereof |
| CN102784643A (en) * | 2011-05-19 | 2012-11-21 | 中国科学院过程工程研究所 | Ternary copper catalyst prepared from copper powder recovered from waste organic silicon contacts and preparation method thereof |
| CN103182504A (en) * | 2011-12-27 | 2013-07-03 | 三星电机株式会社 | Copper powder, copper paste and method for preparing copper powder |
| TW201619401A (en) * | 2014-10-03 | 2016-06-01 | Mitsui Mining & Smelting Co | Copper powder |
| CN105705276A (en) * | 2014-02-14 | 2016-06-22 | 三井金属矿业株式会社 | Copper powder |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6280641B1 (en) * | 1998-06-02 | 2001-08-28 | Mitsubishi Gas Chemical Company, Inc. | Printed wiring board having highly reliably via hole and process for forming via hole |
| TWI359708B (en) * | 2007-03-14 | 2012-03-11 | Phibro Tech Inc | Method of producing fine particle copper powders |
| CN203495238U (en) * | 2013-10-08 | 2014-03-26 | 江苏泰禾金属工业有限公司 | Copper powder smashing device |
-
2018
- 2018-03-28 KR KR1020197024034A patent/KR102403998B1/en active IP Right Grant
- 2018-03-28 WO PCT/JP2018/012780 patent/WO2018181482A1/en active Application Filing
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- 2018-03-28 JP JP2019509979A patent/JP7050756B2/en active Active
- 2018-03-29 TW TW107110963A patent/TWI803486B/en active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422510A (en) * | 2000-04-10 | 2003-06-04 | 特乔尼科斯有限公司 | Twin plasma torch apparatus |
| JP2002169273A (en) * | 2000-11-30 | 2002-06-14 | Murata Mfg Co Ltd | Photosensitive copper paste and circuit board using the same |
| CN102784643A (en) * | 2011-05-19 | 2012-11-21 | 中国科学院过程工程研究所 | Ternary copper catalyst prepared from copper powder recovered from waste organic silicon contacts and preparation method thereof |
| CN102350499A (en) * | 2011-09-28 | 2012-02-15 | 河北工业大学 | Cu/Cu2O core-shell composite microsphere and preparation method thereof |
| CN103182504A (en) * | 2011-12-27 | 2013-07-03 | 三星电机株式会社 | Copper powder, copper paste and method for preparing copper powder |
| CN105705276A (en) * | 2014-02-14 | 2016-06-22 | 三井金属矿业株式会社 | Copper powder |
| TW201619401A (en) * | 2014-10-03 | 2016-06-01 | Mitsui Mining & Smelting Co | Copper powder |
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| KR102403998B1 (en) | 2022-05-31 |
| WO2018181482A1 (en) | 2018-10-04 |
| TW201841702A (en) | 2018-12-01 |
| JPWO2018181482A1 (en) | 2020-02-06 |
| CN110325303B (en) | 2022-01-11 |
| JP7050756B2 (en) | 2022-04-08 |
| KR20190132351A (en) | 2019-11-27 |
| TWI803486B (en) | 2023-06-01 |
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