WO2015194347A1 - 銅粉、その製造方法、及びそれを含む導電性組成物 - Google Patents

銅粉、その製造方法、及びそれを含む導電性組成物 Download PDF

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WO2015194347A1
WO2015194347A1 PCT/JP2015/065574 JP2015065574W WO2015194347A1 WO 2015194347 A1 WO2015194347 A1 WO 2015194347A1 JP 2015065574 W JP2015065574 W JP 2015065574W WO 2015194347 A1 WO2015194347 A1 WO 2015194347A1
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copper
copper powder
particles
value
less
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PCT/JP2015/065574
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English (en)
French (fr)
Japanese (ja)
Inventor
坂上　貴彦
陽一 小神
圭 穴井
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三井金属鉱業株式会社
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Priority to JP2015547184A priority Critical patent/JP6001796B2/ja
Priority to KR1020167031624A priority patent/KR101874500B1/ko
Priority to CN201580024747.3A priority patent/CN106457382B/zh
Publication of WO2015194347A1 publication Critical patent/WO2015194347A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17—Metallic particles coated with 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
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/026—Alloys based on copper
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • 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

Definitions

  • the present invention relates to copper powder. Moreover, this invention relates to the manufacturing method of copper powder, and the electroconductive composition containing it.
  • Copper powder is used for electrical conduction between the external electrode of the electronic device and the printed wiring of the printed wiring board. It is also used for a conductive paste for an interlayer connection material that fills a wiring layer of a printed wiring board, a through-through hole provided in a multilayer printed wiring board, a via that is a non-through hole, or the like.
  • copper powder is used in various applications such as conductive paste used for EMI shielding and electronic device connection, wiring paste for ceramic fired electronic parts such as capacitors and alumina substrates, etc. Appropriately shaped copper powder is used.
  • the above-mentioned copper powder is often used in the form of a conductive composition mixed with a binder resin or an organic solvent, for example, in the form of a conductive paste.
  • the conductivity of the conductor formed from the conductive composition depends on the proportion of the copper powder contained in the conductive composition. Even when the same proportion of copper powder is contained, the shape of the copper particles Affects the conductivity of the conductor. For example, in the case of copper powder composed of spherical copper particles, the conductivity of the conductor is greatly influenced by the content ratio of the copper powder, and it is not easy to increase the conductivity unless the content ratio of the copper powder is increased.
  • dendritic copper particles are less affected by the content of copper powder on the conductivity of the conductor than spherical particles. In other words, the conductivity of the conductor is unlikely to depend on the content ratio of the copper powder. This is because dendritic copper particles have more contact points between particles than spherical copper particles.
  • dendritic copper powder is not easy to be contained in a high content ratio in the conductive composition due to the low tap density. Further, dendritic copper powder is strongly aggregated and it is not easy to prepare a conductive composition with good dispersibility, and it is not easy to reduce the thickness of a conductor film formed from the conductive composition. Furthermore, it is difficult to fill the inside of a small diameter via, and it is difficult to cope with fine wiring.
  • rod-shaped copper powder In addition to spherical and dendritic copper powder, rod-shaped copper powder is also known.
  • Patent Document 1 describes a rod-shaped copper powder obtained by crushing dendritic copper powder. In this copper powder, crushed pieces generated by crushing dendritic copper powder are aggregated to form a rod-like shape.
  • the bar-shaped copper particles described in Patent Document 1 are agglomerated pieces as described above, since the tap density is high and the primary particles are coarse, the content ratio of the copper powder is increased similarly to the spherical copper particles. Otherwise, it is not easy to increase the conductivity of the conductor.
  • the average particle size is a relatively large particle size of around 10 ⁇ m, it is not easy to reduce the thickness of the conductor film, it is not easy to fill the inside of a small diameter via, and it is easy to form a pattern of fine wiring Not.
  • the object of the present invention is to improve the copper powder. Specifically, the conductivity of the conductor is less dependent on the content of the copper powder, the conductor film can be easily thinned, and the filling property in a small-diameter via is easy. It is desirable to provide a copper powder that is good and can easily form a fine wiring pattern.
  • the present invention is copper powder comprising copper particles or particles formed by coating the surface of a copper core with a metal other than copper,
  • the projected area equivalent circle diameter obtained by image analysis of the primary particles is 0.1 ⁇ m or more and 4.0 ⁇ m or less,
  • the present invention provides a copper powder having a shape factor value of 1.8 to 3.5 in accordance with an image solution of primary particles defined by [maximum diameter ⁇ maximum diameter ⁇ ⁇ ⁇ (4 ⁇ projected area)].
  • the present invention is a copper powder comprising copper particles or particles formed by coating a metal other than copper on the surface of a copper core material,
  • ⁇ 0.63 the powder density when an actual load of 0.63 kN is applied to an area of 20 mm ⁇
  • R 0.63 the powder specific resistance at that time
  • the value of ⁇ 0.63 is 3.
  • a copper powder having a value of 0 g / cm 3 to 5.0 g / cm 3 and an R 0.63 value of 9.0 ⁇ 10 ⁇ 1 ⁇ cm or less is provided.
  • the present invention is a copper powder comprising copper particles or particles formed by coating a metal other than copper on the surface of a copper core material
  • the specific resistance of the conductive film formed from 100 parts by mass of the copper powder and 10 parts by mass of resin is defined as R 10, and the ratio of the conductive film formed from 100 parts by mass of the copper powder and 15 parts by mass of resin.
  • R 10 the specific resistance of the conductive film formed from 100 parts by mass of the copper powder and 10 parts by mass of resin
  • the ratio of the conductive film formed from 100 parts by mass of the copper powder and 15 parts by mass of resin when the resistance was R 15, the value of R 10 is not more than 1 ⁇ 10 -4 ⁇ cm, in which the value of R 15 / R 10 to provide a copper powder is 10 or less.
  • FIG. 1 is a schematic diagram showing a copper powder as a raw material for the copper powder of the present invention, and a schematic diagram showing a process for producing the copper powder of the present invention from the raw material copper powder.
  • 2 is a scanning electron microscope image of the raw material copper powder used in Example 1.
  • FIG. 3 is a scanning electron microscope image of the copper powder obtained in Example 4.
  • FIG. 4 is a filled image of particles created based on the microscopic image shown in FIG.
  • the copper powder of the present invention consists of copper particles or particles in which the surface of the copper core material is coated with a metal other than copper.
  • the copper powder of the present invention comprises these particles, and in some cases contains a trace amount of inevitable impurities. Moreover, you may contain powder other than copper powder etc. as needed.
  • these particles are collectively referred to simply as “copper particles” for convenience.
  • the copper particles constituting the copper powder of the present invention preferably have a projected area equivalent circle diameter of 0.1 ⁇ m or more and 4.0 ⁇ m or less, and 0.3 ⁇ m or more and 3.5 ⁇ m or less obtained by image analysis of the primary particles. Is more preferably 0.5 ⁇ m or more and 3.0 ⁇ m or less.
  • the copper particles in the present invention belong to the category of fine particles.
  • the conductive film formed using the copper powder of the present invention can be thinned.
  • the copper powder of the present invention can be successfully filled into small-diameter vias, for example, small-diameter vias having a maximum diameter of 10 ⁇ m or more and 50 ⁇ m or less.
  • the projected area equivalent circle diameter is also called the Heywood diameter and is the diameter of a circle having the same area as the projected area of the particles.
  • the projected area equivalent circle diameter is measured for 20 or more particles, and the arithmetic average value is taken as the measured value.
  • the copper particles constituting the copper powder of the present invention have a shape factor value of 1.8 or more and 3.5 by image analysis of primary particles defined by [maximum diameter ⁇ maximum diameter ⁇ ⁇ ⁇ (4 ⁇ projected area)]. Preferably, it is 1.9 or more and 3.3 or less, more preferably 2.0 or more and 3.0 or less.
  • the shape factor 1 is the minimum value.
  • the shape factor is 1, the projected shape of the particle is a circle, and as this value increases from 1, the particle becomes gradually elongated. Therefore, the fact that the shape factor of the copper particles constituting the copper powder of the present invention is within the above range means that the copper particles have an elongated rod shape.
  • the conductive composition can maintain high conductivity that is not easily dependent on the ratio of the copper powder contained therein, and the conductive composition is prepared. Sometimes it is possible to obtain rigid rod-like particles in which copper particles are less likely to break.
  • the maximum diameter and projected area of any 20 or more individual particles are measured, the shape factor of each particle is obtained based on them, and the arithmetic average value is used as the measured value.
  • the maximum diameter is the maximum projected diameter of the particle, and specifically refers to the length of the long side of the minimum rectangle circumscribed by the projected image of the primary particle.
  • it is necessary to match the unit of the maximum diameter with the unit of the projected area for example, when the unit of the maximum diameter is ⁇ m, The unit is ⁇ m 2 ).
  • the copper particles constituting the copper powder of the present invention have a shape factor value in the above-described range, and a projected area equivalent circle diameter / circular ellipse equivalent diameter value of 0.40 or more and 0. Is preferably .65 or less, more preferably 0.42 or more and 0.63 or less, and still more preferably 0.45 or more and 0.62 or less.
  • the value of the projected area equivalent circle diameter / circumferential ellipse equivalent diameter is also an index of the shape of the particle, and 1 is the maximum value.
  • the value of the projected area equivalent circle diameter / circumferential ellipse equivalent diameter in the copper particles constituting the copper powder of the present invention within the above-mentioned range means that the copper particles have an elongated rod-like shape. ing.
  • the value of “projected area equivalent circle diameter / circumferential ellipse equivalent diameter” is within a predetermined range, high conductivity that is not easily dependent on the copper powder content in the conductive composition can be maintained, and paste processing can be performed. Sometimes it can be a rigid rod-like particle with few breaks.
  • the projected area equivalent circle diameter / circumferential ellipse equivalent diameter value is a value obtained by measuring the projected area equivalent circle diameter / circumferential circle equivalent diameter value for any 20 or more individual particles, and calculating the arithmetic average value thereof.
  • the circumference equivalent circle diameter is the diameter of a circle having the same circumference as the circumference of the particle.
  • the projected area, projected circumference, and projected maximum diameter of the particles which are the basis for calculating the parameters described so far, are based on the electron microscopic image of the copper powder of the present invention, and the individual particles are filled by visual inspection of the operator. This is determined by binarization software analysis using the filled image. When multiple particles overlap in the observation field of view, the overlapping particles are virtually separated into individual particles by visual inspection of the operator, and an outline is taken for each separated particle. An image that has been binarized after being painted black is created.
  • the software analysis can be calculated by, for example, automatic analysis using image analysis type particle size distribution software Mac-VIEW which is computer software available from Mountec Co., Ltd.
  • the copper particles constituting the copper powder of the present invention have a substantially rod shape.
  • the copper powder of the present invention preferably contains 35% or more of copper particles having such a substantially rod-like shape on a number basis, and the inclusion of 60% or more is a viewpoint of stabilizing the conductive performance with respect to the copper powder content. Is preferable. This ratio is obtained by observing the copper powder of the present invention with an electron microscope, and measuring the number of particles having a projected area equivalent circle diameter / circular ellipse equivalent diameter satisfying the above range for any 20 or more particles. It is obtained by calculating the proportion of the total number of particles.
  • substantially rod-like means that the value of the length of the long side / the length of the short side in the minimum rectangle used when obtaining the maximum diameter is preferably 3 or more and 20 or less, more preferably 3 The shape which is 15 or less is said.
  • the copper powder of the present invention comprising copper particles having a substantially rod-like shape is bulky due to the rod-like shape of the copper particles.
  • the bulk is lower than the copper powder of the present invention, and the conductive performance varies. It will be easy.
  • the copper powder composed of the dendritic copper particles becomes too bulky than the copper powder of the present invention, and the aggregation between the particles becomes strong.
  • the copper powder of the present invention preferably has a value of ⁇ 0.63 when the powder density when an actual load of 0.63 kN is applied to an area of 20 mm ⁇ is ⁇ 0.63 .
  • the value of ⁇ 0.63 is more preferably 3.1 g / cm 3 or more and 4.7 g / cm 3 or less, and still more preferably 3.3 g / cm 3 or more and 4.3 g / cm 3. cm 3 or less.
  • the copper powder of the present invention has a low powder resistance even in a low compression state due to the rod-like shape of the copper particles.
  • copper powder composed of spherical copper particles makes it easy to reduce the powder resistance sufficiently in the low compression state due to the small number of contact points between the particles. Instead, it shows low resistance only when it is in a highly compressed state.
  • the copper powder of the present invention preferably has a value of R 0.63 of R 0.63 when the powder specific resistance when an actual load of 0.63 kN is applied to an area of 20 mm ⁇ is R 0.63. .0 ⁇ and the 10 -1 [Omega] cm or less, more preferably 5.0 ⁇ 10 -1 ⁇ cm or less, or less and more preferably 5.0 ⁇ 10 -1 ⁇ cm.
  • the measurement conditions for the above-mentioned powder density and powder specific resistance were set when an actual load of 0.63 kN was applied to an area of 20 mm ⁇ (circular shape with a diameter of 20 mm).
  • copper particles When used as a body composition, copper particles must be in contact with each other to form a network of conductive paths even at a relatively low compressive stress level, such as the initial stage of curing of the composition. This is because the value used as the index is considered to correspond to the measurement condition of the present invention.
  • the above-mentioned powder density and powder specific resistance are measured by the following method. 5-7 g of copper powder whose mass has been measured in advance is put into a probe cylinder having a diameter of 20 mm of a dust resistance measuring apparatus.
  • the sample thickness and resistivity measuring instrument (4-probe method) when a load is gradually applied to the probe cylinder by a hydraulic jack is monitored.
  • the dust resistance value is calculated from the sample thickness, the cylinder area, and the resistance value when a load is applied.
  • the green density is calculated from the measured mass and the sample thickness.
  • the dust density and the dust resistivity when the cylinder load is 0.63 kN are calculated.
  • Specific examples of the device name include a dust resistance measurement system (Mitsubishi Chemical PD-41) and a resistance measurement device (Mitsubishi Chemical MCP-T600).
  • the resistance of the conductor formed from the conductive composition depends greatly on the content of the copper powder in the conductive composition.
  • the resistance value can be kept low. That is, as a result of the study by the present inventors, it has been found that the conductivity of the conductor is less dependent on the content ratio of the copper powder. The reason for this is not because the copper powder of the present invention comprising copper particles having a substantially rod-like shape has anisotropy in the shape of the copper particles and can achieve low resistance even under a low load. The present inventor has guessed.
  • the copper powder composed of copper particles having a spherical shape ensures sufficient contact between the particles unless the copper powder is highly blended due to the isotropic particle shape. And the resistance of the conductor cannot be reduced.
  • the value of R 10 is 1 ⁇ 10 It is preferably ⁇ 4 ⁇ cm or less, more preferably 8 ⁇ 10 ⁇ 4 ⁇ cm or less, and even more preferably 5 ⁇ 10 ⁇ 5 ⁇ cm or less.
  • the value of R 15 / R 10 is preferably 10 or less, and 7 or less. Is more preferable and 5 or less is still more preferable.
  • the copper particles themselves can be used as the particles constituting the particles, and the particles obtained by coating the surface of the copper core material with a metal other than copper (hereinafter referred to as “metal”). Also referred to as “coated copper particles”.
  • metal a metal other than copper
  • coated copper particles examples include silver, gold, platinum, tin, and nickel. Of these coated metals, it is particularly preferable to use silver, which is a noble metal that has high film-forming properties on copper and high conductivity and is relatively inexpensive.
  • the coating metal may continuously cover the entire surface of the copper core without gaps, or may be partially coated so that the surface of the copper core is partially exposed.
  • the ratio of the coated metal to the metal-coated copper particles is preferably 1% by mass or more and 30% by mass or less with respect to the mass of the metal-coated copper particles.
  • the conductivity of the conductor formed using the copper powder of the present invention as a raw material is less dependent on the content of the copper powder. This is advantageous in that when the conductor is produced by applying the conductive composition containing the copper powder of the present invention, the resistance of the conductor is less likely to vary even when uneven coating occurs. It is.
  • the binder resin is more preferentially filled in the via than the copper powder, and accordingly, the via is contained in the via.
  • the composition of the filled conductive composition is likely to change, the use of the copper powder of the present invention can suppress the change in resistance of the conductive composition to a small level even when the composition is changed. .
  • the conductive film to be measured for the specific resistances R 10 and R 15 described above is prepared by the following procedure.
  • the binder resin a liquid phenol thermosetting resin (PL-2243 manufactured by Gunei Chemical Industry Co., Ltd.) is used.
  • This binder resin and the copper powder of the present invention are mixed in the above-mentioned proportions, and 5 parts by mass of NMP and 0.1 part by mass of a leveling agent (KF-352A manufactured by Shin-Etsu Silicone) are added as a solvent.
  • KF-352A manufactured by Shin-Etsu Silicone
  • the conductive composition is obtained by further kneading five times under the conditions of a roll speed of 100 rpm and a gap between rolls of 10 ⁇ m.
  • This conductive composition is coated on a glass plate using a glass epoxy resin plate applicator, and an applied body is first formed so as to have a thickness of 30 ⁇ m.
  • the coated body thus obtained is fired to obtain a conductive film.
  • the firing conditions are 1 hour at 160 ° C. in a nitrogen atmosphere.
  • a method for measuring the specific resistances R 10 and R 15 of the conductive film is as follows.
  • the specific resistance is calculated from the film thickness of the conductive film left for 24 hours at 25 ° C. and 60% RH and the resistance value of the conductive film measured by the four probe method.
  • Examples of the resistance measuring device include Loresta GP manufactured by Mitsubishi Chemical Analytech.
  • the copper powder of the present invention is preferably made of a raw material having an irregular shape having a crushing starting point such as a “corner portion” or a “constriction portion” that is easily mechanically crushed as a particle shape.
  • a crushing starting point such as a “corner portion” or a “constriction portion” that is easily mechanically crushed as a particle shape.
  • the copper particles having a portion that can be generated by crushing for example, copper powder composed of dendritic copper particles, are used as the raw material for the particles that are long in one direction.
  • it has one of the features that the dendritic copper particles are crushed under specific conditions to obtain the target copper powder.
  • the dendritic copper particles as a raw material can be suitably produced by, for example, an electrolytic method.
  • the dendritic copper particles preferably have a volume cumulative particle size D 50 measured by a laser diffraction / scattering particle size distribution analyzer of 0.5 ⁇ m or more and 7.0 ⁇ m or less, and 1.0 ⁇ m or more and 6.0 ⁇ m or less. More preferably, it is 1.2 ⁇ m or more and 5.0 ⁇ m or less.
  • the copper particles when observed using a scanning electron microscope (hereinafter also referred to as “SEM”), it has one main shaft portion, and a plurality of branch portions branch obliquely from the main shaft, It has a dendritic shape that grows two-dimensionally or three-dimensionally, and the number of branch portions (number of branch portions / main shaft portion major axis L) with respect to the major axis L shown in FIG. 1 is 0.5 / ⁇ m or more. It is preferable to use those of 30.0 / ⁇ m or less, particularly 1.0 / ⁇ m or more and 25.0 / ⁇ m or less, particularly 3.0 / ⁇ m or more and 20.0 / ⁇ m or less.
  • SEM scanning electron microscope
  • the dendritic copper particles having the above-mentioned shape are 35% of the total copper particles. It is preferable to occupy at least several percent, particularly 60 percent or more.
  • the copper powder containing dendritic copper particles used as a raw material can be suitably produced by, for example, an electrolytic method.
  • an electrolysis method for example, an anode and a cathode are immersed in a sulfuric acid electrolytic solution containing copper ions, and a direct current is passed through the electrolyte to conduct electrolysis.
  • a method of scraping and collecting by an electric method, washing with water, drying, and producing electrolytic copper powder through a sieving step and the like as necessary can be exemplified.
  • electrolysis it is advantageous to add a small amount of chlorine to the electrolytic solution and scrape it off within a short time after deposition using an electrode having a predetermined surface roughness.
  • the chlorine concentration of the electrolytic solution is preferably adjusted to 3 mg / L or more and 300 mg / L or less, particularly 5 mg / L or more and 200 mg / L or less.
  • Rz as defined in JIS B 0601-2013 is preferably 0.001 ⁇ m or more and 2.0 ⁇ m or less, particularly preferably 0.1 ⁇ m or more and 1.0 ⁇ m or less.
  • the copper powder containing the above dendritic copper particles is crushed to produce the desired copper powder containing substantially rod-like copper particles.
  • a method in which excessive heat is not applied to the raw copper powder from the viewpoint of preventing plastic deformation, it is also preferable to employ a medialess crushing method that does not use media such as beads and balls.
  • a particularly preferred method is to force the slurry containing the raw material copper powder to pass through the narrow flow path under pressure, and in the dendritic copper particles as shown in FIG. In this method, the branch portion is crushed by bending and separating from the main shaft portion at the base portion.
  • the diameter of the narrow channel is preferably about 100 ⁇ m to 300 ⁇ m.
  • the applied pressure of the slurry is preferably 10 MPa or more and 100 MPa or less.
  • Such forced passage can be performed once or multiple times. By performing the forced passage a plurality of times, it is possible to obtain a copper powder containing copper particles having a target shape and particle size.
  • the crushing conditions the work volume per unit volume of the slurry calculated from the capacity of the narrow flow path through which the slurry passes, the slurry pressure and the number of passes of the slurry batch are multiplied. Is preferably 200 J or more and 30,000 J or less.
  • the work amount is particularly preferably 400 J or more and 25,000 J or less.
  • the apparatus capable of performing such operations include NanoVater from Yoshida Kikai Kogyo and NanoJet Pal from ordinary light.
  • the above is a manufacturing method in the case where the copper particles are made of copper itself.
  • the copper particles are made of metal-coated copper particles
  • the following manufacturing method can be adopted. That is, first, core material particles made of copper are manufactured using the above-described method. Next, a coating metal is arranged on the surface of the obtained core material particles.
  • a method for arranging the coating metal an appropriate method is adopted depending on the type of the coating metal. For example, when the coating metal is a metal nobler than copper, such as silver, a wet displacement plating method can be employed. Alternatively, a wet reduction plating method can be used.
  • the copper powder of the present invention is preferably used in the form of a conductive composition prepared by mixing with a binder resin or an organic solvent.
  • the conductive composition include a conductive paste, a conductive ink, a conductive adhesive, and an EMI shield.
  • These conductive compositions may be of a resin-curing type in which copper particles are pressure-bonded by curing of the resin to ensure conduction, or the organic components are volatilized by firing and the copper particles are sintered. It may be a fired mold that ensures conduction.
  • the proportion of copper powder in the conductive composition is preferably 30% by mass to 98% by mass, and more preferably 35% by mass to 95% by mass.
  • the conductive composition More preferably, it is 40 mass% or more and 90 mass% or less.
  • binder resins such as various thermosetting resins such as epoxy resins and phenol resins, curing agents, curing catalysts, organic solvents, and glass frits. These components are blended at an appropriate ratio depending on the specific use of the conductive composition.
  • the copper particles of the present invention are substantially rod-shaped, the number of contact points between the particles, when compared to spherical particles, even if the content ratio in the conductive composition is low, The resistance of the conductor can be lowered. Moreover, even if the non-uniform particle
  • the conductive composition containing the copper powder of the present invention is suitably used for, for example, electrical conduction between an external electrode of an electronic device and a printed wiring of a printed wiring board. Moreover, it is used suitably in order to form the printed wiring of a printed wiring board by a printing method.
  • the circulating electrolyte temperature was 40 ° C.
  • the Cu concentration was 15 g / L
  • the sulfuric acid (H 2 SO 4 ) concentration was 200 g / L
  • the chlorine concentration was 200 mg / L.
  • the current density was adjusted to 100 A / m 2 and electrolysis was performed for 30 minutes. Copper deposited on the cathode surface was recovered by scraping with a scraper at a frequency of once every 30 seconds, and then washed to obtain a hydrous copper powder cake equivalent to 1 kg of copper powder. This cake was dispersed in 3 L of water to form a slurry, and then washed with pure water to remove impurities to obtain electrolytic copper powder. This electrolytic copper powder is referred to as “raw material copper powder A”.
  • the major axis L has a major axis L of 0.5 to 7.0 ⁇ m, and the number of branches / major axis major axis L has a dendrite shape of 0.5 to 30.0 / ⁇ m. However, it was confirmed that it occupied 80% by number or more of all the copper particles.
  • An SEM image of the obtained dendritic copper particles is shown in FIG.
  • the target rod-shaped copper particle was manufactured by crushing the dendritic copper particle obtained by said (1).
  • a Nanomizer NM2-2000AR a high-speed shearing pulverizer from Yoshida Kikai Kogyo, was used.
  • this was mixed with denatured alcohol to form a slurry so that the solid content of the dendritic copper particles was 30% by mass, and this slurry was put into the pulverizer and crushed.
  • the operating conditions of the pulverizer were a slurry temperature of 20 ° C. or less, a pressure of 20 MPa, and a pass count of 100 (equivalent to a work amount of 10,000 J per unit slurry volume).
  • the copper powder containing the target rod-shaped copper particle was obtained.
  • the projected area equivalent circle diameter obtained by image analysis of the primary particles was 0.1 ⁇ m or more and 4.0 ⁇ m or less, and the projected area equivalent circle diameter / peripheral equivalent circle diameter value was 0.40 or more. It was confirmed that the copper particles of 0.65 or less accounted for 35% by number or more of the total copper particles.
  • Example 2 In Example 1, the Cu concentration was 20 g / L and the current density was 200 A / m 2 as the conditions for producing the copper powder of the raw material copper powder. Except for these, as in the case of the raw material copper powder A, a copper powder of dendritic copper particles was obtained. This copper powder is referred to as “raw material copper powder B”. Except this, it carried out similarly to Example 1, and obtained the copper powder containing the rod-shaped copper particle made into the objective.
  • Example 3 In Example 1, as a condition for producing copper powder of the raw material copper powder, an insoluble anode plate (DSE (manufactured by Permerek Electrode)) was used, the Cu concentration was 1 g / L, and the sulfuric acid (H 2 SO 4 ) concentration was 100 g. / L, the current density was 100 A / m 2 , the amount of circulating fluid was adjusted to 5 L / min, and conditions for electrolysis for 20 minutes were adopted. Except for these, as in the case of the raw material copper powder A, a copper powder of dendritic copper particles was obtained. This copper powder is referred to as “raw material copper powder C”.
  • DSE insoluble anode plate
  • the raw copper powder C was crushed under a pressure of 50 MPa and a pass count of 5 (equivalent to a work load of 1500 J per unit slurry volume). The rest was the same as in Example 1. Thus, the copper powder containing the target rod-shaped copper particle was obtained.
  • Example 4 Raw material copper powder C was used as the raw material copper powder.
  • the crushing conditions were a pressure of 20 MPa and a pass count of 100 (equivalent to a work amount of 10,000 J per unit slurry volume). Except these, it carried out similarly to Example 1, and obtained the copper powder containing the rod-shaped copper particle made into the objective.
  • the SEM image of the obtained copper powder is shown in FIG.
  • Example 5 Raw material copper powder A was used as the raw material copper powder. As the crushing conditions, first, a 100-pass treatment was performed at a pressure of 20 MPa, and then a 50-pass treatment (corresponding to a work volume of 23,000 J per unit slurry volume) was adopted at a pressure of 50 MPa. Except these, it carried out similarly to Example 1, and obtained the copper powder containing the rod-shaped copper particle made into the objective.
  • Example 6 Raw material copper powder C was used as the raw material copper powder.
  • the crushing conditions were a pressure of 20 MPa and a pass count of 25 (equivalent to a work load of 2500 J per slurry unit volume). Except these, it carried out similarly to Example 1, and obtained the copper powder containing the rod-shaped copper particle made into the objective.
  • Example 7 The copper powder obtained in Example 6 was subjected to silver displacement plating to obtain a copper powder obtained by coating the surface of rod-shaped copper particles with silver.
  • Comparative Example 1 Wet spherical copper particles (Mitsui Mining & Smelting Co., Ltd. D 50 value 1.0 .mu.m) was used as Comparative Example 1.
  • Example 1 of Patent Document 1 Japanese Patent Laid-Open No. 6-158103 related to the earlier application of the present applicant was further tested, and the obtained copper powder was used as Comparative Example 4.
  • the projected area equivalent circle diameter was measured by image analysis. Image analysis type particle size distribution software Mac-VIEW was used as a measuring device. The measurement was performed on 20 or more particles, the projected area equivalent circle diameter was measured for each particle, and the arithmetic average value was calculated. Moreover, about the copper powder obtained by the Example and the comparative example, the value of projected area circle equivalent diameter / circumference ellipse equivalent diameter was measured by the image analysis using the above-mentioned apparatus. The measurement is performed on 20 or more particles, and the projected area equivalent circle diameter and the circumference equivalent circle diameter are measured for each particle. A value was calculated, and an arithmetic average value of the value was further calculated.
  • the shape factor was measured by the image analysis using the above-mentioned apparatus. The measurement was conducted on 20 or more particles, the maximum projected diameter and the projected area were measured for each particle, the shape factor was calculated for each particle from these values, and the arithmetic mean value was calculated. The above results are shown in Table 1 below.
  • the particles were visually filled, and image analysis was performed on the filled image.
  • FIG. 4 shows a filled image corresponding to FIG.
  • FIG. 4 shows a filled image corresponding to FIG.
  • the maximum diameter of the opening of the bottomed via was 60 ⁇ m.
  • the bottomed via was filled with the conductive composition used for the measurement of the specific resistance R 10 using a screen printer.
  • the copper foil with a carrier was peeled off and cured at 160 ° C. for 1 hour in a nitrogen atmosphere to obtain a printed wiring board filled with a conductor inside the bottomed via.
  • the cross section of the bottomed via portion of this printed wiring board was polished, and the obtained cross section was observed with a scanning electron microscope (magnification 1,000 times).
  • the conductor film formed from the conductive composition containing the copper powder obtained in each example has a low resistance, and the resistance is hardly affected by the amount of the copper powder, Furthermore, it turns out that the surface is smooth. Moreover, it turns out that this electroconductive composition has the favorable filling property to a small diameter via
  • the copper powder consisting of the spherical copper particles of Comparative Example 1 is used, the resistance of the conductor film becomes higher than that of the example, and the resistance is easily affected by the amount of copper powder. . The same tendency as in Comparative Example 1 is observed for the copper powder composed of the flaky copper particles of Comparative Example 2.
  • the conductive composition could not be prepared due to the extremely low dispersibility.
  • the copper powder of Comparative Example 4 lacked the ability to fill a small diameter via due to the large particle size.
  • copper powder is provided in which the conductivity of the conductor is less dependent on the content of copper powder.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)
  • Conductive Materials (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Chemically Coating (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Non-Insulated Conductors (AREA)
PCT/JP2015/065574 2014-06-16 2015-05-29 銅粉、その製造方法、及びそれを含む導電性組成物 WO2015194347A1 (ja)

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KR1020167031624A KR101874500B1 (ko) 2014-06-16 2015-05-29 구리분, 그 제조 방법, 및 그것을 포함하는 도전성 조성물
CN201580024747.3A CN106457382B (zh) 2014-06-16 2015-05-29 铜粉、其制造方法以及包含该铜粉的导电性组合物

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JPS62199705A (ja) * 1986-02-25 1987-09-03 Fukuda Kinzoku Hakufun Kogyo Kk 微細粒状銅粉の製造方法
JPH0246641B2 (zh) * 1987-11-02 1990-10-16 Mitsui Mining & Smelting Co
JPH038209A (ja) * 1989-06-01 1991-01-16 Matsushita Electric Ind Co Ltd 厚膜用組成物
JP2000080408A (ja) * 1998-08-31 2000-03-21 Mitsui Mining & Smelting Co Ltd 微小銅粉の製造方法
JP2008013837A (ja) * 2006-07-10 2008-01-24 Sumitomo Metal Mining Co Ltd 微小銅粉及びその製造方法
JP2013019034A (ja) * 2011-07-13 2013-01-31 Mitsui Mining & Smelting Co Ltd デンドライト状銅粉
JP2013100592A (ja) * 2011-10-21 2013-05-23 Mitsui Mining & Smelting Co Ltd 銀被覆銅粉

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JPH0768562B2 (ja) 1992-11-25 1995-07-26 三井金属鉱業株式会社 半田付け可能な導電性塗料用銅粉の製造方法
US6036839A (en) * 1998-02-04 2000-03-14 Electrocopper Products Limited Low density high surface area copper powder and electrodeposition process for making same
JP2008122030A (ja) * 2006-11-15 2008-05-29 Mitsui Mining & Smelting Co Ltd ヒートパイプ構成原料
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Publication number Priority date Publication date Assignee Title
JPS6167702A (ja) * 1984-09-07 1986-04-07 Mitsui Mining & Smelting Co Ltd 導電性粉末及びこれを用いた導電性組成物
JPS62199705A (ja) * 1986-02-25 1987-09-03 Fukuda Kinzoku Hakufun Kogyo Kk 微細粒状銅粉の製造方法
JPH0246641B2 (zh) * 1987-11-02 1990-10-16 Mitsui Mining & Smelting Co
JPH038209A (ja) * 1989-06-01 1991-01-16 Matsushita Electric Ind Co Ltd 厚膜用組成物
JP2000080408A (ja) * 1998-08-31 2000-03-21 Mitsui Mining & Smelting Co Ltd 微小銅粉の製造方法
JP2008013837A (ja) * 2006-07-10 2008-01-24 Sumitomo Metal Mining Co Ltd 微小銅粉及びその製造方法
JP2013019034A (ja) * 2011-07-13 2013-01-31 Mitsui Mining & Smelting Co Ltd デンドライト状銅粉
JP2013100592A (ja) * 2011-10-21 2013-05-23 Mitsui Mining & Smelting Co Ltd 銀被覆銅粉

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JP6001796B2 (ja) 2016-10-05
KR101874500B1 (ko) 2018-07-04
CN106457382A (zh) 2017-02-22
KR20170008744A (ko) 2017-01-24

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