CN103547396B - It is coated to threadiness copper microgranule and the electric conductivity smears and the conductive film that comprise this coating threadiness copper microgranule - Google Patents
It is coated to threadiness copper microgranule and the electric conductivity smears and the conductive film that comprise this coating threadiness copper microgranule Download PDFInfo
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- CN103547396B CN103547396B CN201280024258.4A CN201280024258A CN103547396B CN 103547396 B CN103547396 B CN 103547396B CN 201280024258 A CN201280024258 A CN 201280024258A CN 103547396 B CN103547396 B CN 103547396B
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/062—Fibrous particles
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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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
- H01B1/02—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
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12181—Composite powder [e.g., coated, etc.]
Abstract
The present invention is a kind of coating threadiness copper microgranule, it is characterised in that be at least some of by the coating threadiness copper microgranule of the coating metal beyond copper removal of threadiness copper microgranule, more than a length of 1 μm of this threadiness copper microgranule and draw ratio is more than 10.
Description
Technical field
The present invention relates to coating threadiness copper microgranule, the electric conductivity smears comprising this coating threadiness copper microgranule and conduction
Property film.
Background technology
Spherical copper microgranule is excellent electric conductivity and cheap material, and therefore the raw material etc. as electric conductivity smears etc. is wide
Apply generally.This electric conductivity smears use at printed substrate etc. various print processes formed circuit material,
Various electrical contact components etc. utilize widely.
In order to improve the electric conductivity of this copper microgranule, stability further, such as, proposition has various micro-to this copper
The surface of grain is by coated with the metal beyond the copper that silver is representative.This technology is disclosed in such as Japanese Patent Publication 57-59283 public affairs
Report, Japanese Patent Publication 2-46641 publication or No. 4223754 description of patent.These coating spherical copper microgranules with only by
The metal particle that the noble metal of the high prices such as silver is formed is compared, and its electric conductivity is the most in no way inferior, and can lower manufacturing cost, therefore
It is worth height.
In recent years, the conductive material (transparent conductive material) with the transparency with transparent and electrically conductive film as representative is required
Purposes (such as, the purposes such as touch panel, flat faced display) drastically expand.Accompany with this, study in electric conductivity smears, lead
In the transparent conductive materials such as electrical epithelium, use spherical copper microgranule as conductive material.Then, electric conductivity smears is required energy
Enough form the performance of electric conductivity epithelium.
But, as it has been described above, using the conventional electric conductivity smears containing coating spherical copper microgranules such as useful silver as example
When the conductive layer of the transparent and electrically conductive film as utilized in touch panel etc. is formed with coating materials application, if in order to ensure sufficiently
Electric conductivity, increases the content of the spherical copper microgranule coating with silver, then deposit the problem that the transparency in the conductive layer declines.On the contrary,
If in order to ensure the transparency, reducing the content of the copper microgranule coating with silver, then deposit the problem that electric conductivity in the conductive layer declines.
That is, knowable in the past, in the transparent conductive material of the spherical copper microgranule coating containing noble metals such as useful silver, it is difficult to be satisfied by
Electric conductivity needed for the conductive layer of bright conductive film and the transparency.
Even if as it has been described above, containing the coating spherical copper microgranule of the noble metals such as useful silver in transparent conductive material as conduction
Material, it is also difficult to be satisfied by electric conductivity and the transparency of transparent conductive material.Additionally, the microgranule valency only formed by noble metals such as silver
Lattice are high, sometimes unfavorable on cost.And then, in order to obtain this microgranule, need to separate the operation of spheroidal particle, therefore exist this
The problem that the manufacture of metal particle spends the time in the extreme.
Summary of the invention
Then, it is an object of the invention to provide a kind of coating threadiness copper microgranule solving above-mentioned problem, it is contained in
Time in bright conductive material, electric conductivity and the transparency are the most excellent.
Then, the present inventor etc. conducts in-depth research to solve above-mentioned problem, and its result finds first,
Containing to the fibrous copper microgranule quilt formed by the copper as metal the most cheap compared with silver in transparent conductive material
During the coating threadiness copper microgranule covering the metal beyond the copper removals such as silver and formed, it is possible to formation electric conductivity and the transparency all excellences
Conductive material, completes the present invention.
That is, the present invention is with the following invention as purport.
(1) a kind of coating threadiness copper microgranule, it is characterised in that be threadiness copper microgranule at least some of by copper removal with
The coating threadiness copper microgranule of outer coating metal, more than a length of 1 μm of this threadiness copper microgranule and draw ratio is more than 10.
(2) the coating threadiness copper microgranule as described in (1), it is characterised in that the minor axis of threadiness copper microgranule be 1 μm with
Under, the minor axis in this threadiness copper microgranule be the existence ratio of more than 0.3 μm and copper coccoid that draw ratio is less than 1.5 be every
Root threadiness copper microgranule is less than 0.1.
(3) a kind of electric conductivity smears, it is characterised in that containing the coating threadiness copper microgranule described in (1) or (2).
(4) a kind of electric conductivity epithelium, it is characterised in that containing the coating threadiness copper microgranule described in (1) or (2).
(5) a kind of conductive film, it is characterised in that there is on base material the electric conductivity epithelium described in (4).
The coating threadiness copper microgranule of the present invention is at least some of by beyond copper removal of the surface of threadiness copper microgranule
The coating threadiness copper microgranule of coating metal, has more than a length of 1 μm of this threadiness copper microgranule and draw ratio is more than 10
Specific shape and composition.Therefore, by using this coating threadiness copper microgranule, the electric conductivity of combined with superior can be obtained
Electric conductivity smears, electric conductivity epithelium and conductive film with the transparency.
Accompanying drawing explanation
The observation figure that the coating threadiness copper microgranule of Fig. 1: the present invention utilizes digit microscope to obtain.
Detailed description of the invention
Hereinafter, the present invention is explained.
The coating threadiness copper microgranule of the present invention is at least some of by beyond copper removal of the surface of threadiness copper microgranule
The coating threadiness copper microgranule of coating metal, more than a length of 1 μm of this threadiness copper microgranule and draw ratio is more than 10.
The coating threadiness copper microgranule of the present invention is as described above by beyond the surface copper removal of threadiness copper microgranule
Coating metal and the fibrous copper microgranule that formed, as it is shown in figure 1, also maintain fiber shape after utilizing coating metal.With copper removal with
If the fibrous copper microgranule of outer coating metal is compared with not coating fibrous copper microgranule, steady the most in a solvent, in air
Qualitative excellence.As the metal beyond the copper removal of coating threadiness copper microgranule, precious metal element (gold platinum can be enumerated
Silver palladium rhodium iridium ruthenium osmium etc.), base metal elements (ferrum cobalt stannum etc.) etc..They can use a kind, it is also possible to group
Close use multiple.Wherein, from the viewpoint of electric conductivity and stability, preferably at least use silver.
As the method to the metal beyond the copper removals such as the coating silver of not coating fibrous copper microgranule, the most particularly limit
Fixed, electroless plating method is preferably used.In order to use electroless plating method that the surface of threadiness copper microgranule is coated to beyond copper removal
Metal, such as, when making silver coating, the silver-colored complex salt using silver nitrate, ammonium carbonate salts or edetate can be used molten
Liquid, makes the method that silver displacement separates out on the surface of threadiness copper microgranule；Maybe can use and threadiness copper microgranule is scattered in chela
Mixture solution, adds silver nitrate solution in this dispersion liquid, then adds reducing agent, makes silver tunicle separate out in this threadiness shot copper
The method etc. on the surface of son.
Additionally, for gold as metal copper removal beyond coating to not coating fibrous copper microgranule, for example, it is possible to adopt
With using gold chloride, gold potassium cyanide etc. as Jin Yuan, make the method that gold tunicle separates out the surface in this threadiness copper microgranule.For
Not coating fibrous copper microgranule is coated to nickel, it is for instance possible to use use Nickel dichloride., nickel acetate etc. as nickel source, makes nickel
Tunicle separates out the method on the surface in this threadiness copper microgranule.
(i.e., not being coated to) the threadiness copper microgranule of the state not having coated metal is described.
The length of threadiness copper microgranule needs to be more than 1 μm, more than preferably 5 μm, more than more preferably 10 μm.If fiber
The length of shape copper microgranule is less than 1 μm, then in the transparent conductive material of coating threadiness copper microgranule comprising the present invention, it is difficult to hold concurrently
Obtain electric conductivity well and the transparency.On the other hand, from the electric conductivity skin forming the coating threadiness copper microgranule comprising the present invention
From the viewpoint of the operation of smears when film, conductive film, the preferably length of fibrous particles is less than 500 μm.
Threadiness copper microgranule minor axis be preferably below 1 μm, below more preferably 0.5 μm, more preferably 0.2 μm with
Under, below particularly preferably 0.1 μm.If the minor axis of threadiness copper microgranule is more than 1 μm, the most sometimes at the coating fibre containing the present invention
In the transparent conductive material of dimension shape copper microgranule, the transparency is poor.
The draw ratio (minor axis of the length/fibrillar of fibrillar) of threadiness copper microgranule needs to be more than 10, preferably
It is more than 100, more preferably more than 300.If the draw ratio of threadiness copper microgranule is less than 10(i.e., if connecing torulose fiber
Shape copper microgranule), it is difficult to, in the transparent conductive material of the coating threadiness copper microgranule comprising the present invention, the get both transparency and conduction
Property.
In the coating threadiness copper microgranule of the present invention, preferably by the metal quilt beyond its whole surface copper removal
Cover but it also may exist and do not utilize metal to carry out coating and copper to be exposed to the part on surface.As coating threadiness copper microgranule
In copper removal beyond the content of coated metal, the quality overall relative to coating threadiness copper microgranule, preferably 1～50 matter
Amount %, more preferably 10～50 mass %, more preferably 15～30 mass %.If less than 1 mass %, the most sometimes as by making
Coating metal and the raising of the electric conductivity of effect that obtains is insufficient.On the other hand, if more than 50 mass %, it is likely that copper removal
The coating of metal in addition causes fee of material to increase, or the minor axis of coating threadiness copper microgranule increases.It addition, the amount of coating of metal
Can obtain measuring solution in strong acid by the coating threadiness copper particle dissolution such as making the present invention, this solution is carried out profit
With ICP(high-frequency inductive coupling plasma body) mensuration and obtain.
Obtain threadiness copper microgranule and the minor axis of following copper coccoid and the method for length (major diameter) and calculate every fibre
The method of the number of the copper coccoid in dimension shape copper microgranule is as described below.
That is, use transmission electron microscope (TEM), scanning electron microscope (SEM) etc., observe threadiness copper microgranule
Aggregation.In the observation of threadiness copper microgranule, it is, for example possible to use digit microscope (KEYENCE company system, " VHX-
1000, VHX-D500/510 ") etc..
Then, 100 fibrous copper microgranules are selected from this aggregation.These threadiness copper microgranule and fibres can be measured respectively
On dimension shape copper microgranule attachment or with the minor axis of copper coccoid of threadiness copper asperity contact and length, using their meansigma methods as
Minor axis and length.Additionally, by the length obtained by above-mentioned carrying out like that divided by minor axis, threadiness copper microgranule can be calculated
Draw ratio with copper coccoid.And then, by the number of the copper coccoid that calculating exists, by the number of copper coccoid divided by fiber
The radical (100) of shape copper microgranule, can calculate the number of the copper coccoid of every fibrous copper microgranule.
Here, observe the present invention fibrous copper microgranule time, threadiness copper particles o verlap and intensive in the case of, sometimes
Can not correctly evaluate threadiness copper microgranule and the shape of copper coccoid.Therefore, in which case it is possible to use ultrasonic wavelength-division
In bulk put etc. disperses intensive fibrous copper microgranule until adjacent fibrous copper microgranule is each other for the most closely sealed degree.
In not coating fibrous copper microgranule, minor axis is more than 0.3 μm and copper coccoid that draw ratio is less than 1.5
There is ratio being preferably every fibrous copper microgranule is less than 0.1, more preferably less than 0.08, more preferably 0.05
Below individual, most preferably it is completely absent.In the presence of above-mentioned copper coccoid is more than every fibrous copper microgranule 0.1, sometimes
In comprising the transparent conductive material of coating threadiness copper microgranule of the present invention, the transparency is poor.
Should illustrate, on the minor axis of transparent influential copper coccoid be more than 0.3 μm and draw ratio (copper coccoid
The minor axis of length/copper coccoid) it is less than 1.5.
Manufacture not coating fibrous copper microgranule described above and can use the most following method.I.e., it is possible to use from containing
There are copper ion, alkali compounds, the nitrogen-containing compound of stable complex and reproducibility compound can be formed with copper ion
Aqueous solution makes the method that threadiness copper microgranule separates out.Now, as reproducibility compound, be preferably used not with alkaline aqueous solution
In dissolved oxygen reaction reproducibility compound.
If the compound that use and the dissolved oxygen in alkaline aqueous solution react is as reproducibility compound, then at the fibre obtained
In dimension shape copper microgranule, the existence ratio of copper coccoid is more than every fibrous copper microgranule 0.1, i.e. sometimes can only obtain a large amount of
There is the fibrous copper microgranule of copper coccoid.
Here, " the reproducibility compound not reacted with dissolved oxygen " is according to following index definition.
First, adding few drops 10% sodium hydrate aqueous solution in pure water 500g, pH regulator is the alkaline water of 10.4 by preparation
Solution (water temperature 25 DEG C).With the dissolved oxygen concentration of this alkaline aqueous solution for " dissolved oxygen concentration 1 ".Specifically, dissolved oxygen concentration 1
For 8.3mg/L.It addition, in the mensuration of dissolved oxygen concentration, such as, use dissolved oxygen meter " DO-5509 " (Lutron company system).
Thereafter, the open cylinder type container of a diameter of 7.0cm is put into this alkaline aqueous solution of 100mL, then, to upper
The alkaline aqueous solution stated adds reproducibility compound so that concentration is 0.50mol/L, use magnetic stirrer to this aqueous solution with
The degree not having whirlpool is stirred so that it is dissolve.Also while continuing for stirring after dissolving, add reproducibility compound
After, behind 0.5 minute, 5 minutes, 10 minutes, 15 minutes and 30 minutes after adding reproducibility compound, measure in aqueous solution
Dissolved oxygen concentration.Then, with the dissolved oxygen concentration behind after adding reproducibility compound 10 minutes for " dissolved oxygen concentration 2 ".
Then, by with following formula (1), obtaining numerical value A.
A=(dissolved oxygen concentration 2)/(dissolved oxygen concentration 1) (1)
In the present invention, the reproducibility compound that numerical value A is more than 0.5 obtained in (1) formula is defined as " not with dissolving
The reproducibility compound of oxygen reaction ".Then, it is defined as " reacting with dissolved oxygen by the numerical value A reproducibility compound less than 0.5
Reproducibility compound ".
As the reproducibility compound not reacted with dissolved oxygen, can enumerate ascorbic acid, arabo-ascorbic acid, glucose or
Hydroxyl ammonium salt etc..The numerical value A of the reproducibility compound that these do not react with dissolved oxygen is more than 0.5.Wherein, it is preferably used and is selected from
One in ascorbic acid, arabo-ascorbic acid and glucose, most preferably with ascorbic acid.
In the prior art, when manufacturing fibrous copper microgranule, typically by using hydrazine as reaction solution contains
Reproducibility compound, makes this copper microgranule separate out.But, when using " the reproducibility compounds reacted with dissolved oxygen " such as hydrazines, sometimes
Can only obtain the fibrous copper microgranule that the existence ratio of copper coccoid increases.Or sometimes can not make threadiness copper microgranule self analysis
Go out.
Should illustrate, in the reproducibility compound hydrazine in the past used, the numerical value A obtained in above-mentioned formula (1) is 0.05 left side
Right.
In the present invention, it is preferred to make the dissolved oxygen concentration in the aqueous solution of threadiness copper microgranule precipitation maintain height by being used for
Scope.More specifically, as the water contained in this aqueous solution, water that dissolved oxygen concentration be 1mg/L more than is preferably used, more excellent
Choosing uses the water of more than 3mg/L.If using the dissolved oxygen concentration water less than 1mg/L, then the shot copper shape of every fibrous copper microgranule
The ratio of body goes above 0.1, and then, when being contained in transparent conductive material etc., sometimes can only obtain the threadiness of transparency difference
Copper microgranule.
Reproducibility compound as above is preferably being 0.5～5.0 molar equivalents relative to the copper ion in aqueous solution
Ratio use, more preferably use with the ratio of 0.75～3.0 molar equivalents.If using with the ratio less than 0.5 molar equivalent,
The most sometimes the formation efficiency of threadiness copper microgranule declines.On the other hand, even if using more than 5.0 molar equivalents, threadiness copper
The formation effect of microgranule also can be saturated, from viewpoints such as costs, the most preferably.
Copper ion can generate by making water solublity mantoquita be dissolved in water.As water solublity mantoquita, sulphuric acid can be enumerated
Copper, copper nitrate, copper chloride or copper acetate etc..Wherein, from the standpoint of the easness of fibrous copper microgranule forming the present invention,
Copper sulfate or copper nitrate can be preferably used.
As alkali compounds, there is no particular limitation, it is possible to use sodium hydroxide, potassium hydroxide etc..
The concentration of the alkali compounds in aqueous solution is preferably 15～50 mass %, more preferably 30～50 mass %, enters one
Step is preferably 35～45 mass %.If the concentration of alkali compounds is less than 15 mass %, the most sometimes become to be difficult to form the present invention's
Threadiness copper microgranule.On the other hand, if this concentration is more than 50 mass %, the operation of aqueous solution the most sometimes becomes difficulty.
The concentration of the copper ion in aqueous solution according to the hydroxide ion of above-mentioned alkali compounds and copper ion mole
Than regulation.That is, (hydroxide ion of alkali compounds)/(copper ion) is preferably 3000/1～6000/1 in order to molar ratio computing
The mode of scope set, be more preferably set as the scope of 3000/1～5000/1.If this mol ratio is less than 3000/1, then can not
The formation of suppression copper coccoid, and then, the existence ratio of copper coccoid is more than every fibrous copper microgranule 0.1.Or, sometimes
The shape of copper microgranule does not become threadiness and becomes spherical.On the other hand, if mol ratio is more than 6000/1, threadiness the most sometimes
The formation efficiency of copper microgranule is deteriorated.
As forming the nitrogen-containing compound of stable complex with divalent copper ion in aqueous, ammonia, second two can be enumerated
Amine or trien etc..Wherein, from the standpoint of the easness forming threadiness copper microgranule, it may be preferred to use second two
Amine.
It addition, from the viewpoint of the formation efficiency of threadiness copper microgranule, above-mentioned nitrogen-containing compound is preferably with relative to copper
1 mole of ion is that the ratio of more than 1 mole uses.
Then, the aqueous solution containing composition described above is heated with suitable thermal source, then, can be by making above-mentioned water
The heating of solution continues, or makes the liquid temperature of aqueous solution decline, and makes the precipitation of required fibrous copper microgranule occur.The most more preferably
The method of the latter, i.e. make the method that liquid temperature declines after heating.
There is no particular limitation for the heating-up temperature of aqueous solution, from the viewpoint of the precipitation efficiency balance with cost, preferably
It it is 50～100 DEG C.
The fibrous copper microgranule separated out can continue solid-liquid separation by methods such as filtration, centrifugation, pressure floatation
And reclaim.The most as required the fibrous copper microgranule reclaimed can also be washed, is dried.It addition, taking-up fiber
During shape copper microgranule, its surface easily aoxidizes, and the most preferably carries out operation under non-active gas atmosphere (such as, nitrogen atmosphere).
During additionally, take care of the fibrous copper microgranule taken out, preferably carry out under non-active gas atmosphere, such as nitrogen atmosphere
Keeping, or be redispersed in being dissolved with in the solution of the reproducibility compound of trace or have with oligodynamical there is anti-copper oxidative function
Organic solution etc. in and carry out keeping.
Furthermore, it is possible to after the fibrous copper microgranule separated out by above-mentioned such method being carried out solid-liquid separation and reclaiming, use
The solution of the reproducibility compound being dissolved with the trace such as water, ascorbic acid washs, and does not carry out the state of threadiness copper microgranule
Under keeping, but the metal beyond the most additional copper removal carries out the operation that is coated to, thus obtains the present invention's
Coating threadiness copper microgranule.From the viewpoint of the surface oxidation of suppression threadiness copper microgranule, more preferably the method.
As set forth above, it is possible to by there is the coating metal beyond the fibrous copper microgranule copper removal of given shape and shape
The coating threadiness copper microgranule of the present invention become is matched with adhesive ingredients and solvent etc. and makes it disperse, and makes leading of the present invention
Electrically smears.
As adhesive ingredients, there is no particular limitation, it is, for example possible to use acrylic resin (silicon Acrylote modification tree
Fat, fluorin modified crylic acid resin, polyurethane modified acrylic resin, epoxy modified acrylic resin etc.), polyester based resin, poly-
Urethane system resin, olefin-based resin, amide resin, imide resin, epoxy resin, organic siliconresin, vinyl acetate system tree
Fat；The starch of natural polymer, gelatin, agar etc.；Semi-synthetic high molecular carboxymethyl cellulose, hydroxyethyl cellulose, methyl
The cellulose derivatives such as cellulose, hydroxyethylmethyl-cellulose, hydroxypropyl methyl cellulose；Synthesize high molecular polyvinyl alcohol,
The water soluble polymers etc. such as polyacrylic macromolecule, polyacrylamide, poly(ethylene oxide), polyvinylpyrrolidone.
As above-mentioned solvent, there is no particular limitation, for example, it is possible to enumerate water, alcohols, glycols, cellosolve class, ketone,
The organic solvents such as esters, ethers, amide-type, hydro carbons.They can be used alone and can also two kinds of combination of the above use.Wherein,
Solvent with water, alcohols as main component is preferably used.
The compounding ratio of coating threadiness copper microgranule and binding agent in the electric conductivity smears of the present invention is with coating fiber
The volume (A) of shape copper microgranule is preferably 1/100～5/1, more preferably 1/ with volume ratio (A/B) meter of the volume (B) of binding agent
20～1/1.If coating threadiness copper microgranule the most coating threadiness copper microgranule less is the journey less than 1/100 with the volume ratio of binding agent
Degree, the most sometimes in the electric conductivity smears obtained, or in the electric conductivity epithelium obtained by this smears etc., electric conductivity reduces.Separately
On the one hand, if binding agent few be the degree more than 5/1 to volume ratio, when the most sometimes making electric conductivity epithelium etc., become surface and put down
Slip, the electric conductivity epithelium of transparency difference, or applying conductive smears, when base material, declines with the adaptation of base material sometimes.
From the viewpoint of the balancing good of electric conductivity, operability etc., the solid in the electric conductivity smears of the present invention becomes
Divide (total of the solid constituent of coating threadiness copper microgranule, binding agent and other additive as required of the present invention) concentration
It is preferably 1～99 mass %, more preferably 1～50 mass %.
Additionally, from operability, to excellences such as the coating easiness of base material from the viewpoint of, the electric conductivity smears of the present invention
It is preferably 0.5～100mPa s the viscosity of 20 DEG C, more preferably 1～50mPa s.
In the electric conductivity smears of the present invention, can make as required in the range of the effect not damaging the present invention
With cross-linking agent such as aldehyde system, epoxy, melamine series, isocyanates systems.
By being filmed the electric conductivity smears of the present invention, the electric conductivity epithelium of the present invention can be obtained.And then, logical
Cross and this electric conductivity epithelium is formed on base material, the conductive film of the present invention can be obtained.The electric conductivity epithelium of the present invention and leading
Electrically film is the transparency and the film of electric conductivity all excellences.
As the forming method of electric conductivity epithelium, can enumerate the electric conductivity coating agent of the present invention in plastic foil etc.
On substrate surface, then, after drying, make it solidify as desired, thus form the so-called liquid phase membrane formation process of film.As painting
Cloth method, it is possible to use roller rubbing method, rod coating method, Dipcoat method, method of spin coating, casting method, mold pressing rubbing method, scraper plate
The methods such as rubbing method, gravure coating process, curtain formula rubbing method, spraying process, scraper for coating method.
From viewpoints such as practicality, the film thickness of electric conductivity epithelium can be such as about 0.1～10 μm.
Additionally, for the electric conductivity epithelium or the conductive film that form the coating threadiness copper microgranule containing the present invention, it is possible to
Only the coating threadiness copper microgranule of the present invention is coated on the substrate surfaces such as plastic foil to use, formed as required and be used for protecting
The method protecting the coating of the coating threadiness copper microgranule of this coating.
Embodiment
Hereinafter, the present invention is specifically described according to embodiment.It addition, the present invention is not limited to these embodiments.
About the not coating fibrous copper used in the coating threadiness copper microgranule obtained in embodiment and comparative example
Microgranule or the threadiness silver evaluation methodology of microgranule or assay method are as described below.
The evaluation of the reproducibility compound not reacted with dissolved oxygen
Based on utilize above-mentioned formula (1) ［ that is, A=(dissolved oxygen concentration 2)/(dissolved oxygen concentration 1) ］ to reproducibility compound
The judgment standard of the reaction with dissolved oxygen, the reactivity to the reproducibility compound used in embodiment and comparative example with dissolved oxygen
It is evaluated.
Should illustrate, the dissolved oxygen concentration in the alkaline aqueous solution that dissolved oxygen concentration 1 measures for as described above carrying out.
In aqueous solution after the rear 10 points of kinds of interpolation of the self-reductivity compound that dissolved oxygen concentration 2 measures for as described above carrying out
Dissolved oxygen concentration.
2. the dissolved oxygen concentration in alkaline aqueous solution
Dissolved oxygen meter " DO-5509 " (Lutron company system) is used to be measured.
3. threadiness copper microgranule and the minor axis of copper coccoid and length
Prepare the aggregation of threadiness copper microgranule, so that this threadiness copper microgranule is the most closely sealed, use super
Sound wave dispersal device disperses lightly.Thereafter, digit microscope (KEYENCE company system, " VHX-1000, VHX-are used
D500/510 ") observe.Among aggregation, select 100 fibrous copper microgranules, measure respective threadiness copper microgranule and shot copper
The minor axis of shape body and length, with their meansigma methods as minor axis with length.
4. threadiness copper microgranule and the draw ratio of copper coccoid
By length that will obtain in above-mentioned 3. divided by minor axis, calculate threadiness copper microgranule and the draw ratio of copper coccoid.
5. the number of the copper coccoid of every fibrous copper microgranule
Prepare the aggregation of threadiness copper microgranule, so that this threadiness copper microgranule is the most closely sealed, use super
Sound wave dispersal device disperses lightly.Thereafter, digit microscope (KEYENCE company system, " VHX-1000, VHX-are used
D500/510 ") observe.Among aggregation, select 100 fibrous copper microgranules, calculate the shot copper shape in this threadiness copper microgranule
The number of body, by the number of copper coccoid divided by the radical (100) of threadiness copper microgranule, thus it is micro-to calculate every fibrous copper
The number of the copper coccoid of grain.
6. the metal amount of coating to threadiness copper microgranule
The coating threadiness copper microgranule obtained in embodiment is extracted to glass beaker, dissolves with nitric acid, with dilute
Solution is as measuring solution.To this mensuration solution implement utilize JARRELL ASH company of ICP(Japan system) quantitative assessment.So
After, by the content ratio of quantitative each metal (that is, the metal beyond copper and copper removal), calculate metal and threadiness copper microgranule is coated to
Amount.It addition, in the embodiment of this specification, use silver as the metal beyond copper removal, therefore the amount of coating of metal refers to silver
Amount of coating.
7. coating threadiness copper microgranule and the stability of not coating fibrous copper microgranule
By micro-for the fibrous copper not being coated to of use in the coating threadiness copper microgranule obtained in embodiment and comparative example
Grain impregnated in water 7 days, at room temperature stands.Thereafter, the X-ray of " the RINT-TTR III " that use RIGAKU company is utilized
Diffraction approach, confirms to be coated to the material beyond the copper removal on the surface of threadiness copper microgranule or coating fibrous copper microgranule and silver
The presence or absence of the peak value of (such as, copper oxide etc.), thus carry out the detection of this material.Use following benchmark, carry out the evaluation of stability.
Zero: do not detect the material beyond copper removal and silver.
×: the material beyond detection copper removal and silver.
8. it is coated to specific insulation and the resistance change (unit: Ω cm) of threadiness copper microgranule
Make the not coating fibrous copper microgranule used in the coating threadiness copper microgranule obtained in embodiment or comparative example
After being scattered in aqueous ascorbic acid (10 mass %), by utilizing the pressure filtration (filter: aperture is the PTFE of 1 μm of nitrogen
Membrane filter, ADVANTECH company system) reclaim, make particulate layer on the filter and be stacked as the sample of lamellar.The sample that will obtain
After product carry out constant pressure and dry 30 minutes with the drying machine being set as 60 DEG C, the drying under reduced pressure carried out 1 hour processes.Use resistivity
Meter (DIA Instruments company system, LORESTA AP, MCP-T400), measures the volume electricity of each microgranule being laminated for lamellar
Resistance rate.
Then, by sample in drying machine, carry out 180 DEG C under air atmosphere, after the heat treated of 1 hour, with above-mentioned with
Sample ground measures the specific insulation of each microgranule being laminated for lamellar, the change of evaluation resistance value caused by heat treated.
(the manufacture example 1 of not coating fibrous copper microgranule)
In the three-neck flask of 300mL, using the sodium hydroxide (NACALAI company system) of the 108.0g as alkali compounds
It is dissolved in the pure water (dissolved oxygen concentration of 27 DEG C: 8.7mg/L) of 180.0g.Then, interpolation makes as making copper ion generate
The cupric nitrate trihydrate (NACALAI company system) of 0.15g of mantoquita be dissolved in aqueous solution obtained by the pure water of 6.2g, and
As the ethylenediamine (NACALAI company system) of the 0.81g of nitrogen-containing compound, being stirred with 200rpm, preparation is uniform blue
Aqueous solution.Here, the mol ratio of the hydroxide ion in this aqueous solution Yu copper ion is set to 4500/1.
The ascorbic acid as reproducibility compound (NACALAI company system, the above-mentioned number of 1.2g is added in this aqueous solution
Value A:0.88) aqueous solution (4.4 mass %), with 200rpm continue stirring, three-neck flask be impregnated in the hot bath of 80 DEG C.Liquid
The color of body is the most thin out from blueness, is changed to almost colourless transparent after 30 minutes.
After 30 minutes, add (4.4 matter of the aqueous ascorbic acid as reproducibility compound of 4.8g
Amount %), continue stir about 1 minute.Thereafter, stopping stirring, mentioned from hot bath by three-neck flask, its result is with being visually confirmed to be
Threadiness copper microgranule is separated out in cooling procedure.Should illustrate, in reaction, for being full of the state of air in three-neck flask.
By the fibrous copper microgranule separated out by utilize nitrogen pressure filtration (aperture is the PTFE film filter of 1 μm,
ADVANTECH company system) reclaim, wash 1 time with aqueous ascorbic acid (10 mass %), after pure water 3 times,
It is dried in being set in the drying machine of 50 DEG C.With it for " not coating threadiness copper particle 1 ".To this not coating threadiness copper microgranule 1
Carry out the evaluation of above-mentioned 3., 4. and 5..Evaluation result is shown in table 1.This evaluation result is in embodiment 1～4 and the fibre of comparative example 1
Shown in the project of the shape of dimension shape copper microgranule.
[table 1]
(the manufacture example 2 of not coating fibrous copper microgranule)
In the three-neck flask of 300mL, using the sodium hydroxide (NACALAI company system) of the 108.0g as alkali compounds
It is dissolved in the pure water (dissolved oxygen concentration of 27 DEG C: 8.7mg/L) of 180.0g.Then, interpolation makes as making copper ion generate
The cupric nitrate trihydrate (NACALAI company system) of 0.22g of mantoquita be dissolved in aqueous solution obtained by the pure water of 9.2g, and
As the ethylenediamine (NACALAI company system) of the 1.2g of nitrogen-containing compound, it is stirred with 200rpm, the uniform blue water of preparation
Solution.Here, the mol ratio of the hydroxide ion in this aqueous solution Yu copper ion is set to 3000/1.
In this solution add 0.34g the hydrazine monohydrate as reproducibility compound (with Wako Pure Chemical Industries company system,
Above-mentioned numerical value A:0.05) aqueous solution (55 mass %), continues stirring with 200rpm, three-neck flask impregnated in the hot bath of 80 DEG C.
The color of liquid is changed to water white transparency from blueness at once, produces precipitate.Then, after 60 minutes by three-neck flask from hot bath
Mention.Should illustrate, in reaction, for being full of the state of air in three-neck flask.The precipitate obtained is used similarly to Example 1
Method reclaim, with it for " coating fibrous copper microgranule 2 ".This coating threadiness copper microgranule 2 is carried out above-mentioned 3., 4.
With 5. evaluation.Evaluation result is shown in table 1.This evaluation result is in the shape of embodiment 5 and the fibrous copper microgranule of comparative example 2
Shown in project.
(embodiment 1)
In the plastic containers being placed with stirrer chip, add " not coating threadiness copper particle 1 " and the 18g of 0.01g
Aqueous ascorbic acid (10 mass %), make suspension.By this suspension at room temperature while being stirred with 700rpm,
While adding the silver-plated prepreg solution of displaced type non-electrolytic (chemical conversion industrial group of four countries system, " SSP-700P ") of 2g, add follow-up
Continuous stirring 5 minutes.And then, continue stirring with 700rpm, with within 5 minutes, dripping the displaced type electroless plating silvering solution (four countries of 0.5g
Chemical conversion industrial group system, " SSP-700M ") and the ion exchange water of 19.5g carry out the solution that is obtained by mixing, its result, this suspension
The tone of liquid is changed to Sandy from bronzing.
The pressure filtration that this suspension is utilized nitrogen process (filter: aperture is the PTFE film filter of 1 μm,
ADVANTECH company system), washed by ion exchange water, thus make microgranule and be laminated for the sample of lamellar on the filter
Product.By this sample is dried in being set in the drying machine of 60 DEG C, can obtain with the state being piled up on filter
With the coating fibrous copper microgranule of silver.The coating threadiness copper microgranule obtained is carried out the evaluation of above-mentioned 6., 7. and 8..Evaluate
Result is shown in table 1.
(embodiment 2)
Except by displaced type electroless plating silvering solution (chemical conversion industrial group of four countries the system, " SSP-of 0.5g in embodiment 1
700M ") and the ion exchange water of the 19.5g respective combined amount of solution that carries out being obtained by mixing be changed to beyond 1g and 19g, logical
Cross method similarly to Example 1, obtain the coating threadiness copper microgranule coating with silver.To the coating threadiness copper microgranule obtained
Carry out evaluation similarly to Example 1.Evaluation result is shown in table 1.
(embodiment 3)
Except by displaced type electroless plating silvering solution (chemical conversion industrial group of four countries the system, " SSP-of 0.5g in embodiment 1
700M ") and the ion exchange water of the 19.5g respective combined amount of solution that carries out being obtained by mixing be changed to 0.2g and 19.8g with
Outward, by method similarly to Example 1, the coating threadiness copper microgranule coating with silver is obtained.To the coating threadiness obtained
Copper microgranule carries out evaluation similarly to Example 1.Evaluation result is shown in table 1.
(embodiment 4)
Except by displaced type electroless plating silvering solution (chemical conversion industrial group of four countries the system, " SSP-of 0.5g in embodiment 1
700M ") and the ion exchange water of the 19.5g respective combined amount of solution that carries out being obtained by mixing be changed to 0.1g and 19.9g with
Outward, by method similarly to Example 1, the coating threadiness copper microgranule coating with silver is obtained.To the coating threadiness obtained
Copper microgranule carries out evaluation similarly to Example 1.Evaluation result is shown in table 1.
(embodiment 5)
In addition to using " coating threadiness copper particle 2 " replacements " coating fibrous copper particle 1 ", by with enforcement
The method that example 1 is same, obtains the coating threadiness copper microgranule coating with silver.To the coating threadiness copper microgranule obtained to except volume
Project beyond resistivity carries out evaluation similarly to Example 1.Evaluation result is shown in table 1.
(comparative example 1)
" coating threadiness copper particle 1 " is not utilized the coating treatment of metal, carries out commenting similarly to Example 1
Valency.Evaluation result is shown in table 1.
(comparative example 2)
" coating threadiness copper particle 2 " is not utilized the coating treatment of metal and in addition to specific insulation
Project carries out evaluation similarly to Example 1.Evaluation result is shown in table 1.
(comparative example 3)
The minor axis as threadiness silver microgranule to 6g is 0.1 μm and the nano silver wire dispersion liquid of a length of 30 μm
(Aldrich system, model 739448, the dispersion liquid being scattered in isopropanol with the ratio of 0.5 mass % by nano silver wire) enters
Row utilizes the pressure filtration of nitrogen to process (filter: aperture is the PTFE film filter of 1 μm, ADVANTECH company system), is produced on
On filter, threadiness silver particulate layer is stacked as the sample of lamellar.By this sample constant pressure and dry 30 in being set in the drying machine of 60 DEG C
After minute, the drying under reduced pressure carried out 1 hour processes.
Sample after drying under reduced pressure is processed use resistrivity meter (DIA Instruments company system, LORESTA AP,
MCP-T400), specific insulation is measured.The volume resistivity value at initial stage is 5.7 × 10-5(Ω cm).Thereafter, carry out 180 DEG C,
Volume resistivity value after the heat treated of 1 hour is 5.0 × 10-5(Ω cm).
Embodiment 1～5 obtains coating threadiness copper microgranule be can by more than a length of 1 μm, draw ratio be more than 10
Fibrous copper microgranule obtain easily and excellent in stability coating threadiness copper microgranule.
The coating threadiness copper microgranule especially obtained in embodiment 1～4 be by minor axis be below 1 μm and draw ratio very
Greatly, minor axis is that the fibrous copper microgranule silver that the existence ratio of more than 0.3 μm and copper coccoid that draw ratio is less than 1.5 is few enters
The coating threadiness copper microgranule that row is coating and obtains.Therefore, compared with not coating fibrous copper microgranule (comparative example 1), volume
Resistivity is low value, i.e. illustrates good electric conductivity.This electric conductivity is almost identical with threadiness silver microgranule (comparative example 3), with
The fibrous particles only formed by silver is compared the most in no way inferior.
On the other hand, in comparative example 1 and 2, use not by micro-for the fibrous copper of the coating metal beyond the copper removal of surface
Grain is evaluated.This threadiness copper microgranule is not the fibrous copper microgranule in stability with good characteristic.
Additionally, embodiment 1～4 be illustrate first can control to more than a length of 1 μm, draw ratio be the fiber of more than 10
The embodiment of the silver-colored amount of coating of shape copper microgranule.Almost without seeing reality in the same manner as the threadiness silver microgranule shown in comparative example 3
Executing the change of the volume resistivity value caused by heat treated of the coating threadiness copper microgranule of the silver in example 1～4, characteristic is good.Separately
On the one hand, comparative example 1 is not by the fibrous copper microgranule of the coating metal beyond the copper removal of surface, the therefore body after heat treated
Long-pending resistivity increases significantly, and electric conductivity is deteriorated.
Industrial applicability
The coating threadiness copper microgranule of the application of the invention, can obtain the electric conductivity of combined with superior and leading of the transparency
Electrically smears, electric conductivity epithelium and conductive film, the most useful.
Claims (4)
1. a coating threadiness copper microgranule, it is characterised in that be at least some of coating by silver, the fiber of threadiness copper microgranule
More than a length of 1 μm of shape copper microgranule, minor axis is below 1 μm and draw ratio is more than 10 coating threadiness copper microgranule, wherein,
Minor axis is more than 0.3 μm and copper coccoid that draw ratio is less than 1.5 is less than 0.1 in every fibrous copper microgranule.
2. an electric conductivity smears, it is characterised in that containing the coating threadiness copper microgranule described in claim 1.
3. an electric conductivity epithelium, it is characterised in that containing the coating threadiness copper microgranule described in claim 1.
4. a conductive film, it is characterised in that there is on base material the electric conductivity epithelium described in claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-132345 | 2011-06-14 | ||
| JP2011132345 | 2011-06-14 | ||
| PCT/JP2012/065187 WO2012173171A1 (en) | 2011-06-14 | 2012-06-14 | Coated fibrous copper microparticles, and electrically conductive coating agent and electrically conductive film each containing said coated fibrous copper microparticles |
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| Publication Number | Publication Date |
|---|---|
| CN103547396A CN103547396A (en) | 2014-01-29 |
| CN103547396B true CN103547396B (en) | 2016-09-28 |
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| CN201280024258.4A Active CN103547396B (en) | 2011-06-14 | 2012-06-14 | It is coated to threadiness copper microgranule and the electric conductivity smears and the conductive film that comprise this coating threadiness copper microgranule |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20140120360A1 (en) |
| JP (1) | JP6076249B2 (en) |
| KR (1) | KR20140020286A (en) |
| CN (1) | CN103547396B (en) |
| WO (1) | WO2012173171A1 (en) |
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| US20150147584A1 (en) * | 2012-06-11 | 2015-05-28 | Unitika Ltd. | Fibrous copper microparticles and method for manufacturing same |
| KR20170102977A (en) * | 2015-01-09 | 2017-09-12 | 클락슨 유니버시티 | Coated copper foil and a method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01119602A (en) * | 1987-11-02 | 1989-05-11 | Mitsui Mining & Smelting Co Ltd | Production of silver-coated copper powder |
| JPH03150302A (en) * | 1989-11-02 | 1991-06-26 | Sumitomo Metal Mining Co Ltd | Fibrous copper powder and manufacture thereof |
| JP3560333B2 (en) * | 2001-03-08 | 2004-09-02 | 独立行政法人 科学技術振興機構 | Metal nanowire and method for producing the same |
| CN101232963B (en) * | 2005-07-25 | 2011-05-04 | 住友金属矿山株式会社 | Copper fine particle dispersion liquid and method for producing same |
| JP2009215573A (en) * | 2008-03-07 | 2009-09-24 | Fujifilm Corp | Rod-shaped metal particle, manufacturing method therefor, composition containing rod-shaped metal particle, and antistatic material |
| JP5162383B2 (en) * | 2008-09-09 | 2013-03-13 | 国立大学法人東北大学 | Method for producing silver-coated copper fines |
| EP2681745B1 (en) * | 2011-02-28 | 2020-05-20 | Nthdegree Technologies Worldwide Inc. | Metallic nanofiber ink, substantially transparent conductor, and fabrication method |
-
2012
- 2012-06-14 WO PCT/JP2012/065187 patent/WO2012173171A1/en active Application Filing
- 2012-06-14 JP JP2013520573A patent/JP6076249B2/en active Active
- 2012-06-14 CN CN201280024258.4A patent/CN103547396B/en active Active
- 2012-06-14 KR KR1020137027406A patent/KR20140020286A/en not_active Application Discontinuation
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| JPWO2012173171A1 (en) | 2015-02-23 |
| CN103547396A (en) | 2014-01-29 |
| KR20140020286A (en) | 2014-02-18 |
| WO2012173171A1 (en) | 2012-12-20 |
| JP6076249B2 (en) | 2017-02-08 |
| US20140120360A1 (en) | 2014-05-01 |
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