CN105451914A - Composite copper particles and production method therefor - Google Patents

Composite copper particles and production method therefor Download PDF

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Publication number
CN105451914A
CN105451914A CN201480043903.6A CN201480043903A CN105451914A CN 105451914 A CN105451914 A CN 105451914A CN 201480043903 A CN201480043903 A CN 201480043903A CN 105451914 A CN105451914 A CN 105451914A
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China
Prior art keywords
particle
copper
inorganic oxide
powder
copper particle
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儿平寿博
佐佐木宣宏
箕轮光
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/068—Flake-like particles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/01—Alloys based on copper with aluminium as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Powder Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

These composite copper particles are obtained by combining flat copper particles and a plurality of inorganic oxide particles being more minute than the flat copper particles. The inorganic oxide particles are unevenly distributed on the surface of the flat copper particles. Ideally, the volume cumulative particle diameter (D50) at the cumulative volume of 50% by volume, as determined by the laser diffraction/scattering particle size distribution measurement method, is 0.1-10 [mu]m. In addition, ideally the aspect ratio indicated by d/t, being the ratio between the major axis (d) of the plate surface and the thickness (t), is 5-30. The inorganic oxide also ideally has a higher hardness than copper.

Description

Composite copper particle and manufacture method thereof
Technical field
The present invention relates to composite copper particle and manufacture method thereof.
Background technology
It is large that laminar copper particle results from its flat shape and specific area, and particle contact area is each other large, therefore, has the following advantages: electric conductivity can be made to improve by adding in conductive composition, and can adjust viscosity.Such as, propose thin slice copper powder before the applicant and comprise its conductive paste (with reference to patent document 1).
A kind of thin slice copper powder is described, its to be particle diameter the be thin slice copper powder of less than 10 μm, standard deviation S D of size distribution and weight build-up particle diameter D in patent document 1 50ratio and SD/D 50value be less than 0.5, weight build-up particle diameter D 90with weight build-up particle diameter D 10ratio and D 90/ D 10value be less than 4.0.In addition, a kind of thin slice copper powder in the document, is described, its to be particle diameter the be thin slice copper powder of less than 10 μm, SD/D 50value be 0.15 ~ 0.35, length-width ratio ([thickness]/[D 50]) value be 0.3 ~ 0.7.According to having the thin slice copper powder recorded in the document of this formation, the circuit of fine pattern can be formed.
Prior art document
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-119501 publication
Summary of the invention
But, along with further miniaturization and the high performance of electronic unit, to the further miniaturization of the material requirements wherein used.Therefore, also micronize is required for the raw material of conductive composition and laminar copper powder.But, when the conductive paste by the laminar copper powder after comprising micronize forms conducting film, there is the tendency that the gas produced when the sintering of film is difficult to escape, result from this and the continuity of electrode film is deteriorated.
Therefore, problem of the present invention is to provide the composite copper particle and manufacture method thereof that can eliminate the various shortcomings that above-mentioned prior art has.
The invention provides a kind of composite copper particle, it is flat copper particle and the multiple inorganic oxide particle Composites finer than this flat copper particle,
Above-mentioned inorganic oxide particle exists unevenly on the surface of above-mentioned flat copper particle.
In addition, the invention provides a kind of manufacture method of composite copper particle, the mixed powder of the powder of spherical raw material copper powder and inorganic oxide uses microballon to carry out dispersion treatment by it, the copper particle plastic deformation of this raw material copper powder is made to become flat, and the particle of this inorganic oxide of surface configuration in this copper particle
Wherein, as the powder of above-mentioned inorganic oxide, use the volume-cumulative particle diameter D under the cumulative volume 50 capacity % utilizing dynamic light scattering formula particle size distribution method to obtain 50(nm) with the particle diameter D obtained that converted by BET specific surface area bETratio and D 50/ D bETit is the powder of more than 60.
Accompanying drawing explanation
Fig. 1 is the image representing the result of the composite copper particle obtained in embodiment 1 being carried out to the Elemental redistribution of copper.
Fig. 2 is the image representing the result of the composite copper particle obtained in embodiment 1 being carried out to the Elemental redistribution of zirconium.
Fig. 3 is the image representing the result of the composite copper particle obtained in embodiment 1 being carried out to the Elemental redistribution of aluminium.
Fig. 4 is the curve map of the measurement result of the thermo-mechanical analysis represented about the copper particle obtained in embodiment 1 to 3 and comparative example 1 and 2.
Detailed description of the invention
Preferred embodiment be described the present invention is based on it below.Composite copper particle of the present invention is formed as the copper particle of mother metal and multiple inorganic oxide particle Composite.Copper particle as mother metal is the flat copper particle with flat shape.With the particle that the inorganic oxide particle of mother metal Composite is finer than the flat copper particle as mother metal.
One of feature that composite copper particle of the present invention has is the state of inorganic oxide particle relative to the Composite of the flat copper particle as mother metal.Specifically, inorganic oxide particle exists unevenly on the surface of flat copper particle." exist unevenly on surface " and refer to that inorganic oxide particle anisotropically exists in the whole region on the surface of flat copper particle, inorganic oxide particle distributes the part concentrated in surface.That is, the surface of flat copper particle has: there is the region of inorganic oxide particle and inorganic oxide particle domain of the existence and there is not in fact region and the inorganic oxide particle not domain of the existence of inorganic oxide particle.Inorganic oxide particle exists unevenly on the surface of flat copper particle and has the following advantage described.Namely, when using composite copper particle of the present invention to modulate the conductive compositions such as conductive paste, burn till the film of this conductive composition and to form electronic circuit etc., if inorganic oxide particle exists unevenly on the surface of flat copper particle, then this uneven Present site and inorganic oxide particle domain of the existence are compared with inorganic oxide particle not domain of the existence, and composite copper particle combination each other becomes and is difficult to occur.This position being difficult to occur to combine plays a role as the escape route of the gas of generation when burning till.Consequently, the expansion of the electrode sometimes produced when burning till can effectively be prevented.Thereby, it is possible to the rising of the resistance of the electronic circuit suppressing to use composite copper particle of the present invention and formed etc., and surface smoothness becomes good.On the other hand, when using surface to there is not the flat copper particle of inorganic oxide particle, combine with face because when burning till, flat copper particle is easy each other, so be difficult to the escape route forming gas.Consequently, the expansion of easy generating electrodes when burning till.
In the present invention, inorganic oxide particle exists unevenly and refers to, such as shown in Fig. 1 to Fig. 3 described later, composite copper particle of the present invention is being carried out UMT processing and Formation cross-section, Elemental redistribution (elementalmapping is being carried out to this cross section, also referred to as " element map ") time, around composite copper particle, observe inorganic oxide particle domain of the existence and inorganic oxide particle not domain of the existence.On the other hand, when the surrounding of composite copper particle whole regional observation to the situation of inorganic oxide particle domain of the existence and contrary whole regional observation around composite copper particle to inorganic oxide particle not domain of the existence, do not meet " inorganic oxide particle exists unevenly ".
Particularly in inorganic oxide particle domain of the existence, as shown in Fig. 2 described later, multiple inorganic oxide particle cohesion and to form agglomerate from effectively preventing the successional aspect of electrode be preferred.
For inorganic oxide particle, such as, its part can be utilized to imbed the surface of flat copper particle and the anchoring effect produced, be configured in the surface of flat copper particle.Or utilize the cohesiveness (surface energy) produced between inorganic oxide particle and flat copper particle, inorganic oxide particle is configured in the surface of flat copper particle.In addition, sometimes also utilize (surface energy) that inorganic oxide particle produces each other, inorganic oxide particle is each state of aggregation.
In order to make inorganic oxide particle exist unevenly on the surface of flat copper particle, as long as manufacture composite copper particle of the present invention according to such as manufacture method described later.
The Be very effective played when the surface making inorganic oxide particle in flat copper particle exists unevenly, the ratio of inorganic oxide particle shared by composite copper particle of the present invention is preferably more than 0.001 quality % and below 5.0 quality %, be more preferably more than 0.01 quality % and below 3.0 quality %, more preferably more than 0.01 quality % and below 2.0 quality %.The ratio of inorganic oxide particle can be measured by such as inductively coupled plasma emission spectrophotometer (ICP-AES).
As long as inorganic oxide particle exists only in the surface of flat copper particle, the inside of flat copper particle also can not be present in.But, there is inorganic oxide particle in the inside of flat copper particle not hinder.The Be very effective played when the surface making inorganic oxide particle in flat copper particle exists unevenly, the ratio being preferably present in the inorganic oxide particle of the inside of flat copper particle is less.From this viewpoint, in the inorganic oxide particle contained by composite copper particle of the present invention, the ratio being present in the inorganic oxide particle of the inside of flat copper particle is preferably below 1.0 quality %, is more preferably below 0.7 quality %.This ratio can be measured by the Elemental redistribution being such as object with the cross section of composite copper particle of the present invention.So-called " being present in the inorganic oxide particle of the inside of flat copper particle " is the inorganic oxide particle of the state do not exposed completely on the surface of composite copper particle of the present invention.
Composite copper particle of the present invention has the shape of reflection as the flat of the shape of the flat copper particle of mother metal.When the flat degree of composite copper particle of the present invention represents with the ratio d/t of the major diameter d in plate face and thickness t and length-width ratio, be preferably more than 5 and less than 30, be more preferably more than 5 and less than 25, more preferably more than 7 and less than 20.By composite copper particle of the present invention, there is so flat degree, thus its compactness such as the electronic circuit formed by composite copper particle of the present invention uprise, and effectively can suppress the rising of resistance.
When measuring the length-width ratio of composite copper particle of the present invention, come major diameter d and the thickness t in the plate face of this particle of Observe and measure by electron microscope.Specifically, after the photo of particle is taken in use scanning electron microscope (SEM), calculated by the major diameter d in the plate face of the particle in photo and the ratio of thickness t.
Composite copper particle of the present invention preferably except being also particulate except flat.By for flat and be particulate, use composite copper particle of the present invention and the compactness of electronic circuit formed etc. uprises further, effectively can suppress the rising of resistance further.From this viewpoint, the volume-cumulative particle diameter D under the cumulative volume 50 volume % utilizing laser diffraction and scattering formula particle size distribution method to obtain of composite copper particle of the present invention 50be preferably more than 0.1 μm and less than 10 μm, be more preferably more than 0.2 μm and less than 9.0 μm, more preferably more than 0.3 μm and less than 7.0 μm.
Its particle diameter of particle one highest wisdom of copper diminishes, then there is the tendency that sintering starts temperature reduction together therewith.This tendency is also applicable to composite copper particle of the present invention.But according to the concrete purposes of composite copper particle of the present invention, preferably sintering does not start the reduction of temperature sometimes.About this point, in composite copper particle of the present invention, result from and there is inorganic oxide particle on the surface of the flat copper particle as mother metal, the reduction that sintering starts temperature is inhibited.In other words, although composite copper particle of the present invention is particulate, the sintering starting temperature same degree with the sintering of the copper powder used in the past can be maintained and start temperature.
Composite copper particle of the present invention preferably except also having wide size distribution except flat.If the size distribution with the composite copper particle of the present invention of flat pattern is wide, then the compactness of the electronic circuit formed by composite copper particle of the present invention etc. uprises.Consequently, the favourable effect that effectively can suppress the rising of resistance has been given play to.From this viewpoint, as the parameter of the width of size distribution, adopt the maximum particle diameter D utilizing laser diffraction and scattering formula particle size distribution method to obtain maxwith D 50ratio and D max/ D 50value time, this value is preferably more than 3 and less than 10, is more preferably more than 3 and less than 9, more preferably more than 3 and less than 8.
In order to the size distribution making composite copper particle of the present invention have above-mentioned scope, as long as such as in the preferred manufacture method of composite copper particle of the present invention described later, condition when suitably setting makes raw material copper powder become flat.
The size forming the flat copper particle as mother metal of composite copper particle of the present invention is identical with the size of above-mentioned composite copper particle of the present invention.On the other hand, about the size of inorganic oxide particle, to be in a ratio of particulate as condition with flat copper particle, the particle diameter (hereinafter also referred to " BET conversion particle diameter ") converted by BET specific surface area is preferably more than 1nm and below 500nm, be more preferably more than 1nm and below 400nm, more preferably more than 1nm and below 300nm.By inorganic oxide particle and the flat copper particle Composite of the size by having this scope, effectively can suppress the expansion of electrode, can effectively suppress to sinter the reduction starting temperature simultaneously.
In order to the measurement example of the BET conversion particle diameter and the BET specific surface area of carrying out of obtaining inorganic oxide particle is as carried out as follows.That is, the gas adsorption method calculating specific area by the gas flow being adsorbed on surface is adopted to measure.As concrete determinator, the Monosorb of such as YUASAIONICS Inc. can be used.
As inorganic oxide particle, use the particle than copper more high rigidity, this aspect easily making this inorganic oxide particle be configured in the surface of flat copper particle from the preferred manufacture method at composite copper particle of the present invention described later is preferred.Hardness refers to the hardness of the material using Moh's hardness scale to measure.
If consider above item, be such as aluminium oxide, zirconia, silica, barium titanate, yittrium oxide, zinc oxide etc. as the preferred material of inorganic oxide particle.These materials can be used alone a kind or two or more combinationally used.
Can only be made up of copper with the flat copper particle of inorganic oxide particle Composite, or it is (following still can to comprise other metallic elements or semimetallic elements apart from copper, for convenience's sake, they are referred to " metallic element ") and form.When flat copper particle comprises other metallic elements, as this metallic element, the material etc. of the sintering behavior that the displays such as such as aluminium, zirconium, yttrium, silicon can be used different from copper.These metallic elements can be used alone a kind, or two or more are combinationally used.By making flat copper particle comprise other metallic elements, give play to the favourable effect of the sintering behavior that can control copper.
Other metallic elements comprised in flat copper particle can exist with the state of metal simple-substance, or also can exist with the compound of the state of the alloy with copper, metallic element (such as oxide).From the above-mentioned effect made by playing containing other metallic elements significant viewpoint further, other metallic elements are preferably contained in flat copper particle with the state of the compound of the metallic elements such as oxide.
Other metallic elements can be present in flat copper particle equably, or also unevenly can be present in specific position.The result of the research of the present inventor is distinguished, preferably the uneven surface being present in flat copper particle of other metallic elements.The present inventor thinks that its reason is that near surface easily has an impact to sintering behavior.
Other metallic elements are uneven when being present in flat copper particle surperficial, and this metallic element preferably exists roughly equably in the whole region on the surface of flat copper particle.Result from and become such existence, easily can control sintering behavior when burning till, work mutually with the flat copper particle of the particle diameter using wide region, easily carry out the design of the thickness of electrode, so preferably.
The proportional Functionality, quality and appealing design relative to the copper in flat copper particle of the present invention that contains of other metallic elements elects more than 0.001 quality % as and below 5.0 quality %, be more preferably more than 0.01 quality % and below 3.0 quality %, more preferably more than 0.05 quality % and below 1.0 quality %.By containing other metallic elements with the ratio of this scope, become further significantly by the above-mentioned effect played containing this metallic element.
Then, the preferred manufacture method of Collections of microparticles body of the present invention is described.In this manufacture method, microballon is used to carry out dispersion treatment to the mixed powder of the powder of spherical raw material copper powder and inorganic oxide.By this dispersion treatment, the copper particle plastic deformation of raw material copper powder is made to become flat, and the particle of this inorganic oxide of surface configuration in this copper particle.Now importantly, as the powder of inorganic oxide, use the powder that the degree of cohesion is high.The powder of the inorganic oxide that the degree of being condensed by use is high, when by the powder Composite of spherical raw material copper powder and inorganic oxide, can make the uneven existence of inorganic oxide particle.From this viewpoint, as the powder of inorganic oxide, use the volume-cumulative particle diameter D under the cumulative volume 50 capacity % utilizing dynamic light scattering formula particle size distribution method to obtain 50(nm) with the particle diameter D converted by BET specific surface area bETratio and D 50/ D bETbe more than 60 powder be favourable.D 50/ D bETbe the index of the degree of the cohesion representing powder, this value is larger, means that the degree of the cohesion of powder is higher.Further, by using D 50/ D bETbe the powder of the inorganic oxide of more than 60, its state of aggregation is reflected on the composite copper particle as object, and inorganic oxide particle is configured in the surface of flat copper particle with the state of uneven existence.
From the view point of making inorganic oxide particle in the uneven existence in the surface of flat copper particle, preferred D 50/ D bETvalue comparatively large, but when this value is excessive, there is the tendency being difficult to spherical raw material copper powder to mix with the powder of inorganic oxide.From this viewpoint, D 50/ D bETvalue be preferably more than 60 and less than 300, more preferably more than 60 and less than 100.
When using microballon to carry out dispersion treatment to the mixed powder of the powder of spherical raw material copper powder and inorganic oxide, as microballon, use diameter to be preferably more than 0.005mm and below 1.0mm, be more preferably more than 0.05mm and below 0.5mm, more preferably more than 0.05mm and the microballon of below 0.3mm.As long as the material of microballon, than the material of copper and inorganic oxide particle more high rigidity, preferably uses such as aluminium oxide, zirconia, silica etc.
The use amount of microballon is preferably more than 50 quality % and below 90 quality % relative to the capacity of the processor as handling object, is more preferably more than 60 quality % and below 85 quality %, more preferably more than 65 quality % and below 85 quality %.
Such as ball mill can be used in the dispersion treatment employing microballon.When using ball mill, time required for dispersion treatment is also different from capacity of processor etc., but general use capacity for more than 0.1L and the ball mill of below 300L time, preferably be set to more than 5 minutes and less than 90 minutes relative to raw material copper powder 1kg, be more preferably set to more than 10 minutes and less than 70 minutes.By adopting this condition, can the state of aggregation of the powder of inorganic oxide be maintained to a certain degree, and by spherical raw material copper powder successfully flattening, can will be in the powder configuration of the inorganic oxide of state of aggregation, be fixed on the surface of flat copper particle simultaneously.
Inorganic oxide particle is in the front and back with flat copper powder compoundedization, and its particle diameter (primary particle size) is change not.Therefore, the particle diameter as the powder of the inorganic oxide of raw material use is identical with the particle diameter of the inorganic oxide particle comprised in composite copper particle of the present invention.On the other hand, the raw material copper powder used as raw material is flattened due to the dispersion treatment by employing microballon, so change in the front and back shape of Composite and size.Under state before dispersion treatment, raw material copper powder is made up of the aggregate of spherical copper particle, uses the volume-cumulative particle diameter D under the cumulative volume 50 capacity % utilizing laser diffraction and scattering formula particle size distribution method to obtain 50be more than 0.03 μm and more than less than 8 μm, particularly 0.05 μm set out in the aspect of the composite copper particle of particulate and the raw material copper powder of less than 7 μm is easy to get calmly is preferred.In addition, as raw material copper powder, also can use spherical beyond the copper particle of shape, but in this case, be sometimes difficult to the composite copper particle obtaining there is desired flat pattern.In addition, spherical copper particle is favourable from the aspect easily manufactured compared with the copper particle of other shapes.
Raw material copper powder preferably its degree of condensing is high.Thereby, it is possible to improve the degree of the cohesion of the composite copper particle obtained.From this viewpoint, to the maximum particle diameter D based on laser diffraction and scattering formula particle size distribution method that raw material copper powder measures maxwith D 50ratio and D max/ D 50value be preferably more than 2 and less than 15, be more preferably more than 3 and less than 13, more preferably more than 3 and less than 10.As long as the raw material copper powder with such size distribution is the condition of setting by the dry process such as being such as atomized, when wet-type reduction manufactures raw material copper powder suitably.Or, can by will the copper powder of these method manufactures be utilized to mix or classification and obtaining.
When containing other metallic elements beyond copper removal in target composite copper particle, it is favourable for making this metallic element contain in raw material copper powder in advance.Such as when using aluminium element as other metallic elements, can adopt in the following method.Such as in dry process, aluminum mixture in the liquation of the copper of melting.In damp process, in the reduction process of copper, add the aluminum oxides such as aluminium oxide.In the raw material copper powder manufactured by these methods, aluminium element is mainly present in the position of the near surface in particle.
By carrying out dispersion treatment as above, obtain target composite copper particle.Such operation and the composite copper particle obtained are used with the form comprising the conductive composition of this composite copper particle.Such as used with the form of conductive paste, conductive ink.This conductive paste contains such as composite copper particle of the present invention, organic excipients (vehicle) and frit.This organic excipients comprises resinous principle and solvent.As resinous principle, such as acrylic resin, epoxy resin, ethyl cellulose, carboxyethyl cellulose etc. can be listed.As solvent, the ether series solvents such as the terpenic series such as terpineol and dihydro-terpineol solvent, ethyl carbitol and BC can be listed.As frit, pyrex, barium borosilicate glass, zinc borosilicate glass etc. can be listed.The ratio of the Collections of microparticles body in conductive paste is preferably set to 36 ~ 97.5 quality %.The ratio of frit is preferably set to 1.5 ~ 14 quality %.The ratio of organic excipients is preferably set to 1 ~ 50 quality %.As the conductive component in this conductive paste, can only use composite copper particle of the present invention, or also this Collections of microparticles body and other copper particulate combinations can be used.By composite copper particle of the present invention and other copper particulate combinations being used, the viscosity adjustment critically carrying out paste further becomes easy.
Embodiment
Below, by embodiment, the present invention is described in more detail.But scope of the present invention is not restricted to described embodiment.Unless otherwise specified, " % " and " part " refers to " quality % " and " mass parts " respectively.
(embodiment 1)
(1) preparation of raw material copper powder
The CB-3000 of mining company of Mitsui Metal Co., Ltd. is used as raw material copper powder.The D of this raw material copper powder max/ D 50value be 3.5, D 50it is 3.2 μm.D 50and D maxji Zhuan Inc. MicrotracX-100 is used to measure.This raw material copper powder contains the aluminium of 0.25%.Aluminium is present in the near surface in particle with the state of simple substance.
(2) preparation of the powder of inorganic oxide
Powder as inorganic oxide uses zirconic powder.The D of this powder 50/ D bETvalue be 70, BET conversion particle diameter D bETfor 15nm.D 50the ZetasizerZS of Malvern Inc. is used to measure.D bETthe Monosorb of YUASAIONICS Inc. is used to measure.
(3) manufacture of composite copper particle
Put in ball mill by the powder 100g of raw material copper powder 1000g and inorganic oxide, mixing and make mixed powder, also dropping into diameter is further that the microballon of the zirconia of 0.2mm carries out dispersion treatment.The amount of microballon is set to 70% relative to the capacity of processor.The volume of ball mill is 2L, and the dispersion treatment time is set to 20 minutes.Thus, target composite copper particle is obtained.Measure inorganic oxide particle ratio shared in composite copper particle by above-mentioned method, result is 0.5%.
To obtained compound copper powder, by UMT (Ultramicrotom, ultra-thin section) processing cut out cross section, STEM (ScanningTransmissionElectronMicroscopy is utilized to this cross section, scanning transmission electron microscope)-EDS (EnergyDispersiveSpectroscopy, energy disperse spectroscopy) carries out Elemental redistribution.The element distributed is copper, zirconium and aluminium.The results are shown in Fig. 1 to Fig. 3.Distinguish by these figure are clear, composite copper particle has flat shape, and at it, surface is uneven has zirconic particle.Particularly distinguish the multiple cohesion of zirconic particle and define agglomerate.Distinguish in addition, as in the flat copper particle of mother metal, aluminium not at inside particles, but is unevenly present in surface.
(embodiment 2)
Replace the zirconic powder used in embodiment 1, use the powder of aluminium oxide.The D of this powder 50/ D bETvalue be 60, BET conversion particle diameter D bETfor 10nm.Operation obtains composite copper particle similarly to Example 1 in addition.Measure inorganic oxide particle ratio shared in composite copper particle by above-mentioned method, result is 0.5%.
(embodiment 3)
Replace the raw material copper powder used in embodiment 1, use D max/ D 50value be 2.5, D 50it is the raw material copper powder of 3.3 μm.This raw material copper powder comprises the aluminium element of 0.13%.Aluminium element is present in the near surface in particle.Operation obtains composite copper particle similarly to Example 2 in addition.Measure inorganic oxide particle ratio shared in composite copper particle by above-mentioned method, result is 0.5%.
(comparative example 1)
Do not use zirconic powder in embodiment 1 and carry out the process of ball mill.Operation obtains flat copper particle similarly to Example 1 in addition.
(comparative example 2)
Do not use the powder of aluminium oxide in embodiment 3 and carry out the process of ball mill.Operation obtains flat copper particle similarly to Example 3 in addition.
(evaluating 1)
To the copper particle obtained in embodiment and comparative example, carry out thermo-mechanical analysis (TMA) and measure.As determinator, use the TMA/SS6300 of SeikoInstruments Inc..Atmosphere is set to nitrogen, measures with the programming rate of 10 DEG C/min.The results are shown in Fig. 4.Indicated by result as shown in this diagram, distinguish that the composite copper particle obtained in each embodiment is compared with the copper particle obtained in comparative example, thermal contraction starts temperature, namely sintering starts temperature is equal or higher.
(evaluating 2)
The copper particle obtained in embodiment and comparative example is used as raw material, modulation conductive paste.In conductive paste, the ratio of copper particle is 70%, and the ratio of terpineol is 25%, and the ratio of ethyl cellulose is 5%.Use applicator to be applied to the surface of aluminum oxide substrate this conductive paste, form the film that thickness is 20 μm.By this film under nitrogen atmosphere, burn till 1 hour at 800 DEG C.The surface state of the conducting film obtained by burning till by visualization, evaluates the continuity of electrode.Electrode being had successional average evaluation is "○", and successional average evaluation will do not had to be "×".The results are shown in following table 1.As indicated by the result shown in this table, when using the composite copper particle obtained in embodiment, do not observe the discontinuities such as the expansion of electrode, on the other hand, when using the copper particle obtained in comparative example, observe the expansion of electrode.
Utilizability in industry
According to the present invention, may be provided in while maintaining and starting temperature with the sintering of the sintering temperature equal extent of in the past used copper powder, easily can manufacture composite copper particle and the manufacture method thereof of the electrode be inhibited of expansion.

Claims (10)

1. a composite copper particle, it is flat copper particle and the multiple inorganic oxide particle Composites finer than this flat copper particle,
Described inorganic oxide particle exists unevenly on the surface of the flat-shaped copper particle of described shoulder.
2. composite copper particle according to claim 1, wherein, the volume-cumulative particle diameter D under the cumulative volume 50 volume % utilizing laser diffraction and scattering formula particle size distribution method to obtain 50be more than 0.1 μm and less than 10 μm.
3. composite copper particle according to claim 1 and 2, wherein, the length-width ratio represented with the major diameter d in plate face and ratio and the d/t of thickness t is more than 5 and less than 30.
4. composite copper particle according to any one of claim 1 to 3, wherein, described inorganic oxide particle be more than 1nm and below 500nm by the BET specific surface area particle diameter obtained that converts.
5. composite copper particle according to any one of claim 1 to 4, wherein, utilizes the maximum particle diameter D that laser diffraction and scattering formula particle size distribution method obtains maxwith D 50ratio and D max/ D 50value be more than 3 and less than 10.
6. composite copper particle according to any one of claim 1 to 5, wherein, described inorganic oxide and copper are in a ratio of high rigidity.
7. a conductive composition, it comprises the composite copper particle according to any one of claim 1 to 6.
8. the manufacture method of a composite copper particle, the mixed powder of the powder of spherical raw material copper powder and inorganic oxide uses microballon to carry out dispersion treatment by it, the copper particle plastic deformation of this raw material copper powder is made to become flat, and the particle of this inorganic oxide of surface configuration in this copper particle
Wherein, as the powder of described inorganic oxide, use the volume-cumulative particle diameter D under the cumulative volume 50 capacity % utilizing dynamic light scattering formula particle size distribution method to obtain 50(nm) with the particle diameter D obtained that converted by BET specific surface area bETratio and D 50/ D bETit is the powder of more than 60.
9. the manufacture method of composite copper particle according to claim 8, wherein, to the maximum particle diameter D that described raw material copper powder utilizes laser diffraction and scattering formula particle size distribution method to measure maxwith D 50ratio and D max/ D 50value be more than 2 and less than 15.
10. the manufacture method of composite copper particle according to claim 8 or claim 9, wherein, as described raw material copper powder, uses the copper powder also comprising other metallic elements apart from copper.
CN201480043903.6A 2013-08-07 2014-08-01 Composite copper particles and production method therefor Pending CN105451914A (en)

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Application publication date: 20160330