CN104867530B - Conductive particle, electric conduction powder, conductive polymer composition and anisotropic conductive sheet - Google Patents
Conductive particle, electric conduction powder, conductive polymer composition and anisotropic conductive sheet Download PDFInfo
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- CN104867530B CN104867530B CN201510011506.7A CN201510011506A CN104867530B CN 104867530 B CN104867530 B CN 104867530B CN 201510011506 A CN201510011506 A CN 201510011506A CN 104867530 B CN104867530 B CN 104867530B
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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
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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
Abstract
The present invention is provided than the previous cheap and conductive particle with sufficiently high electric conductivity and electric conduction powder, conductive polymer composition and anisotropic conductive sheet comprising this conductive particle.The conductive particle (10) of embodiments of the present invention has：Globose nucleus (12) comprising Ni and P, the Pd coating (14) for covering core (12) surface and the Au coating (16) for covering Pd coating (14) surface.
Description
Technical field
The present invention relates to the conductive particle with the core that principal component is Ni, and it is related to leading comprising this conductive particle
Electrical powder, conductive polymer composition and anisotropic conductive sheet.
Background technology
Polymeric composition comprising conductive particle is as only conductive anisotropy is led in a thickness direction
Electric piece (ACF), anisotropy conductiving glue (ACP) and be widely used for the electrical connection between such as electronic unit.It is particularly each
Anisotropy conductive sheet is widely used for formation of the electrical connection in the compact electric apparatus such as mobile phone etc..In addition, use rubber (packet
Include synthetic rubber) as high molecular anisotropic conductive sheet circuit board etc. is also used for as pressure sensitive anisotropic conductive sheet
Inspection (such as impedance measuring) in the formation (such as PCR (registered trademark of JSR companies)) that is electrically connected temporarily.
For example, it is disclosed in Patent Documents 1 to 3 using the anisotropic conductive with ferromagnetic conductive particle
Piece.In these anisotropic conductive sheets, conductive particle arranges in a thickness direction, and the direction dispersion point in the face of piece
Cloth.If pressed in a thickness direction to piece, the conductive particle arranged in a thickness direction is close to each other, is formed conductive logical
Road.It is arranged in a thickness direction by magnetic field with ferromagnetic conductive particle.
Existing technical literature
Patent document
Patent document 1：International Publication No. 02/13320
Patent document 2：International Publication No. 2004/021018
Patent document 3：Japanese Unexamined Patent Publication 2012-174417 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2006-131978 bulletins
Patent document 5：Japanese Unexamined Patent Publication 2009-197317 bulletins
Invention content
However, previous conductive particle in order to obtain sufficiently high electric conductivity (sufficiently low volume resistivity, such as
0.3×10- 5Below Ω m), Au (gold) coating that thickness is, for example, 200nm (0.2 μm) is formd, there are of high cost to ask
Topic.In addition, in the purposes for requiring high moisture-resistance reliability, coating is difficult with other metals except Au.
The invention that the present invention is exactly to solve the above-mentioned problems and completes, to provide than previous inexpensively and with sufficiently high
The conductive particle of electric conductivity and moisture-resistance reliability and electric conduction powder, electroconductive polymer comprising this conductive particle
For the purpose of composition and anisotropic conductive sheet.
The conductive particle of embodiments of the present invention has：Globose nucleus comprising Ni and P, the Pd on the above-mentioned core surface of covering
The Au coating of coating and the above-mentioned Pd coating surfaces of covering.
In certain embodiment, above-mentioned Pd coating restores coating for non-electrolytic.
In certain embodiment, above-mentioned Au coating replaces coating for non-electrolytic.
In certain embodiment, the thickness of the above-mentioned Au coating of thickness ratio of above-mentioned Pd coating is big, and above-mentioned Au coating
Thickness is 5nm less than 40nm.The thickness of above-mentioned Pd coating is preferably greater than 5nm and is less than 300nm.
In certain embodiment, above-mentioned core also includes Cu and Sn.
In certain embodiment, less than a diameter of 1 μm or more 100 μm of above-mentioned core.The diameter of above-mentioned core be preferably 3 μm with
On.
The electric conduction powder of embodiments of the present invention is the powder for including conductive particle described in any one of the above embodiments,
Median particle diameter d50 in cumulative volume distribution curve is 100 μm of more than 3um hereinafter, and [(d90-d10)/d50]≤0.8.
The conductive polymer composition of embodiments of the present invention includes above-mentioned electric conduction powder and macromolecule, wherein,
Above-mentioned macromolecule is, for example, rubber, thermoplastic resin or thermosetting resin.
The anisotropic conductive sheet of embodiments of the present invention is formed by above-mentioned conductive polymer composition, above-mentioned conduction
Property particle arranges in a thickness direction.
The effect of invention
Pass through embodiments of the present invention, it is possible to provide than previous inexpensively and with sufficiently high electric conductivity and moisture-resistance reliability
Conductive particle and electric conduction powder, conductive polymer composition and anisotropy comprising this conductive particle lead
Electric piece.
Description of the drawings
Fig. 1 is the schematic cross-section of the conductive particle of embodiments of the present invention.
Fig. 2 is the figure of the cross-sectional SEM image for the conductive particle for representing embodiment.
Fig. 3 is the electric conductivity of the conductive particle (Pd coating+Au coating) and reference example (no Au coating) that represent embodiment
The volume resistivity of particle is to the chart of the dependence of Pd thickness of coating.
Fig. 4 is dependence of the volume resistivity to Au thickness of coating for the conductive particle for representing comparative example (no Pd coating)
Chart.
Fig. 5 is the schematic diagram of the structure of device used in the measure for the volume resistivity for representing conductive particle.
Specific embodiment
Below with reference to attached drawing to the conductive particle of embodiments of the present invention, electric conduction powder, electroconductive polymer group
It closes object and anisotropic conductive sheet illustrates.
Fig. 1 is the schematic cross-section of the conductive particle 10 of embodiments of the present invention.Conductive particle 10 has spherical shape
Core 12, Pd (palladium) coating 14 on covering core 12 surface, 14 surface of covering Pd coating Au coating 16.Core 12 containing Ni (nickel) and
P (phosphorus).The diameter of core 12 is for example below 1 μm or more 100 μm.If the diameter of fruit stone 12 is less than 1 μm, then due to the aggegation of core 12
Become serious and be difficult to as powder handling.If the diameter of fruit stone 12 is more than 100 μm, then overflowed from conductive path, such as draw
The possibility for playing the short circuit between adjacent wiring increases.The diameter of core 12 is preferably 3 μm or more, and preferably less than 30 μm.Such as
The diameter of fruit stone 12 is practical since the aggegation of the core 12 when carrying out plating Pd is mitigated at 3 μm or more.Such as fruit stone
12 it is direct at 30 μm hereinafter, reducing or disappearing from the spilling of conductive path.The conduction of aggregate as conductive particle 10
Property powder, the preferably median particle diameter d50 of cumulative volume distribution curve at 3 μm or more 100 μm hereinafter, and [(d90-d10)/
D50]≤0.8 powder.Median particle diameter d50 can be as the index of the average grain diameter of electric conduction powder.In addition, if [(d90-
D10)/d50] more than 0.8, then the deviation of grain size is excessive, there is the electric conductivity not contacted with wiring or electrode on conductive path
Particle, therefore there are the possibility that connection reliability reduces.D10 and d90 represents that cumulative volume percentage is 10% and 90% respectively
Grain size.In addition, unless otherwise instructed, the grain that the particle diameter distribution expression in this specification is acquired by laser diffraction scattering method
Diameter.
As the core 12 of conductive particle 10, such as the electric conductivity described in patent document 4 or 5 can be properly used
Grain.The NiP electric conduction powders that the manufacturing method recorded by patent document 5 manufactures due to for monodisperse and narrow particle size distribution, because
This has the advantages that the easily fabricated electric conduction powder for meeting the relationship of [(d90-d10)/d50]≤0.8.
Core 12 there is a situation where using Ni as principal component and also to include P (phosphorus), Cu (copper) and/or Sn (tin).P, Cu and Sn
All be in the balling process of core 12 using for the purpose of the growth or aggegation that inhibit core and as reaction treatment liquid raw material components and
Addition.For reduce core 12 itself resistivity the reason of, content of these elements in core 12 is preferably a small amount of.It is specific and
It says, in core 12, relative to entirety, the P of 1~15 mass % is preferably comprised, more preferably below 10 mass %.If the content of P
More than 15 mass %, then the volume resistivity of core 12 significantly rises, and impracticable.In addition, in core 12, relative to entirety, preferably
Comprising 0.01 mass %~18 mass % Cu.If the content of Cu is more than 18 mass %, there are cores 12 and Pd coating 14
The possibility that adaptation reduces.In addition, in core 12, relative to entirety, the Sn of the mass % of 0.05 mass %~10 is preferably comprised.Such as
The content of fruit Sn is more than 10 mass %, then there is a possibility that core 12 and the adaptation of Pd coating 14 reduce.In addition, core 12 is preferred
Sn is also included on the basis of Ni, P and Cu.Cu and Sn plays the catalyst that karyogenesis is reacted in powder of the manufacture using core 12
The effect of poisonous substance, therefore easily fabricated monodispersed, narrow particle size distribution powder.In addition, Cu and Sn is in NiP conductive particles
Eutectoid in developmental process.
Pd coating 14 is preferably non-electrolytic reduction coating.Non-electrolytic reduction coating has inferior unlike non-electrolytic substitution coating
Adaptation, and replace coating compared to non-electrolytic, pin hole lacks.Au coating 16 is preferably non-electrolytic substitution coating.Phase
Au coating is restored than non-electrolytic, non-electrolytic substitution Au coating and the adaptation of Pd coating 14 are more preferable.Since non-electrolytic replaces plating Au
Along with the dissolving of Pd coating 14 in reaction, therefore preferably make the thickness bigger of the thickness ratio Au coating 16 of Pd coating 14, and
The thickness of Au coating 16 is less than 40nm.If the thickness of Au coating is more than 40nm, have no in characteristic special variation but into
It causes to waste on this.It is preferred that the thickness of Pd coating 14 is more than 5nm and less than 300nm.If Pd coating in 5nm hereinafter, if
When non-electrolytic substitution plating Au is imposed on Pd coating, there are the possibility that Pd coating all dissolves.If Pd coating all dissolves, deposit
In the possibility that the adaptation of Au coating reduces or Au is not precipitated.In addition, if the thickness of Pd coating is more than 300nm, then it is special
Property on have no special variation but cause to waste in cost.In view of it is described above, in the feelings of reliability to be further improved
Under condition, preferably the thickness of Pd coating is more than 50nm and less than 200nm.
The conductive particle 10 of embodiments of the present invention has the Pd coating 14 on 12 surface of covering core and covering Pd coating
The Au coating 16 on surface 14, therefore, compared in the past more inexpensively and with sufficiently high electric conductivity and moisture-resistance reliability.Below
Illustrate its reason, but the following description does not limit embodiments of the present invention.
As the method that Au coating is formed on the particle (referred to as Ni particles) using Ni as principal component, there is non-electrolytic reduction
Type plates Au and non-electrolytic substituted type plating Au.In general, the plating of particle (powder) does not use plating (due to particle agglutination), because
This " non-electrolytic " omitted below and be only called " reduced form " or " substituted type ".
When substitution plating Au is carried out to Ni particles, in Ni dissolutions to plating solution, the electronics discharged with the ionization of Ni is plated
Au ions in liquid receive, and Au is precipitated in Ni particle surfaces.Since the position of Ni dissolutions and position that Au is precipitated are not necessarily consistent,
Therefore more pin hole is formd on substitution Au coating.When carrying out moisture-proof experiment (such as pressure cooking experiment), invaded from pin hole
Moisture aoxidize Ni, generate hydroxide.A part of hydroxide, which is present on Au coating, to be caused to generate what electric conductivity reduced
Problem.In addition, although substitution Au coating and the adaptation of Ni particles plate floor height than following reduction, plating thickness can not be increased
Degree.Such as it is difficult to by the way that plating is replaced to form thickness more than 100nm, especially more than 200nm Au coating.
On the other hand, in reduction plating Au, since the Au ions in plating solution from reducing agent by receiving electronics and as Au analysis
Go out, therefore without the dissolution of Ni.Therefore, compared to substitution Au coating, the pin hole for restoring Au coating is few, and can form thickness
Spend the Au coating of more than 200nm.But it is low with the adaptation of Ni particles to restore Au coating, the moisture-proof experiment of progress (such as pressure cooking
Experiment) when, there are problems that restoring the stripping of Au coating.
In addition, being initially formed substitution Au coating in Ni particle surfaces, then dual-purpose restores in a manner that covering replaces coating
Au coating, although can solve the above problems, in order to obtain enough electric conductivity, the integral thickness for needing to make Au coating is about
More than 200nm, therefore cost is higher.
In this regard, there is the conductive particle 10 of embodiments of the present invention the core comprising Ni and P (to be denoted as " NiP sometimes below
Core ") 12, the Au coating 16 of Pd coating 14 and covering Pd coating 14.Since Pd is more cheap than Au, conductive particle 10 at least because
It is more cheap than the conductive particle only with Au coating with Pd coating.
In addition, both Pd coating 14 and NiP cores 12 and Au coating 16 have good adaptation, it will not be peeling-off
Problem.Although moreover, not as good as Au, Pd still has very high electric conductivity, such as the volume electricity for the Pd coating that thickness is about 100nm
Resistance rate is 0.3 × 10- 5Ω m are hereinafter, sufficiently low.Also, compared with Au, ionization tendency bigger (the redox electricity of Pd
Position is lower), although being easy to aoxidize, since Pd coating 14 is covered by Au coating 16, conductive particle 10 has high moisture-proof
Reliability.
Pd coating 14 preferably restores coating.Compared to the film formed by substitution plating, the pin hole of film formed by reduction plating
It is few, it is dense, it is not easy to that grain boundary attack occurs.In addition, being plated compared to substitution, reduction plating is easily formed thickness coating.Due to Pd
Oxidation-reduction potential between the oxidation-reduction potential of Ni and the oxidation-reduction potential of Au, therefore the substitution reaction of Pd and Ni
Be not as fierce as the substitution reaction of Au and Ni.As a result, it is believed that the adaptation of Pd reduction coating 14 and NiP cores 12 is restored than Au and is plated
The adaptation higher of layer and NiP cores 12.If Au reduction coating is directly formed on NiP cores 12, it is believed that when Au is restored and plated
The fierce substitution reaction of the Au and Ni that occur as side reaction and reduce Au reduction coating and the adaptation of NiP cores 12.
Au coating 16 preferably replaces coating.The difference of the oxidation-reduction potential of Au and Pd is smaller, is not susceptible to Au's and Pd
Substitution reaction.It, can be in Pd by the substitution reaction of grain circle via Pd coating 14 and/or pin hole and Ni contained in NiP cores 12
Au coating 16 is formed on coating 14.By adjusting the thickness of Pd coating 14, the controllable thickness of Au coating 16 formed by substitution plating
Degree.If this is because being plated by replacing, Ze Li circle and/or pin hole are covered by Au coating 16, then Au coating 16 just stops shape
Into.Thickness of the thickness of Pd coating 14 preferably than Au coating 16 is big, and the thickness of Au coating 16 is preferably smaller than 40nm.If Au
The thickness of coating 16 is more than 40nm, then special variation is had no in characteristic but causes to waste in cost.If for example, Pd coating
14 thickness is more than such as 100nm, then can form the Au coating 16 less than 30nm.
In addition, Au coating 16 or reduction coating.The substitution reaction of side reaction Au and Pd when being plated due to reduction are not easy
Occur, therefore Au coating and the adaptation of Pd coating 14 are sufficiently high.But for the thickness for controlling Au coating 16, especially for
Good repeatability forms the thin Au coating 16 less than 40nm, preferably substitution plating.
The conductive particle 10 of embodiments of the present invention can be for example prepared by the following.
Prepare NiP powders as NiP cores 12, being made of NiP particles first.NiP is preferably recorded by patent document 5
Method manufacture.Specifically, nickel sulfate hexahydrate is prepared in a manner that the molar ratio of Ni and Cu is Ni/Cu=239 closes object and sulphur
Sour copper pentahydrate, is dissolved in pure water, makes 15 (dm3) aqueous metal salt.Then, sodium acetate is dissolved in pure water
In, it is 1.0 (kmol/m to make it3) concentration, add sodium hydroxide, made 15 (dm3) pH modulation aqueous solution.Then,
Above-mentioned aqueous metal salt and pH modulation aqueous solutions are stirred, form 30 (dm3) mixed aqueous solution, measure pH be shown as
8.1 value.Then, N is utilized on one side to above-mentioned mixed aqueous solution2Gas sparging maintains heating to exist by external heater on one side
343 (K), and continue to stir.Then, 15 (dm are made3) in pure water with 1.8 (kmol/m3) concentration dissolving Alendronate obtain
Reducing agent aqueous solution, it is heated to 343 (K) also by external heater.Then, by above-mentioned 30 (dm3) mixing it is water-soluble
Liquid and 15 (dm3) reducing agent aqueous solution so that temperature as 343 ± 1 (K) mode modulate after mix, restored by non-electrolytic
Method obtains NiP powders.
(plating Pd)
Prepare 300mL plating Pd build bath foam (such as island chemicals production パ レ ッ ト LMII, Pd a concentration of 10g/
L (liter)).
Prepare the reducing solution (such as パ レ ッ ト II of island chemicals production) using sodium formate as principal component of 550mL.
Pd is built after bath foam mixes with reducing solution, is diluted with pure water, obtains the Pd plating solutions (pH 5.5) of 3L.Pass through on one side
The heating of Pd plating solutions is maintained at 328K by external heater, is stirred on one side.
Prepare the reduction aqueous solution 300mL (pH 5.5) after the above-mentioned reducing solution of 50mL is diluted with pure water.In reductive water
NiP powders (quality 50g) are mixed in solution, are stirred at room temperature 10 minutes.
Later, the reduction aqueous solution for being dispersed with NiP powders is mixed into above-mentioned plating solution, Pd coating is formed by restoring plating
14。
In this way, obtain the NiP cores 12 covered by Pd coating 14.If carrying out Pd reduction platings under the conditions described above,
The Pd coating 14 of thickness about 115nm can be obtained.
In addition, 300mL ︰ are adjusted to by the mixing ratio that plating Pd is built to Yu Ye ︰ reducing solutions in above-mentioned plating Pd processes
500mL can control the thickness of Pd coating.For example, if plating Pd is made to build the mixing ratios of Yu Ye ︰ reducing solutions as 420mL ︰ 790mL,
Plating is carried out to the NiP cores 12 of 35g, then can obtain the Pd coating of thickness about 240nm.
(plating Au)
Mixing 0.1g dodecanes in bath foam (such as デ ィ ッ プ G-FP of island chemicals production) are built in the plating Au of 200mL
The potassium auricyanide of base sodium sulphate and 0.9g, is diluted with pure water, prepares the Au plating solutions (pH 4.0) of 2L.It is heated on one side by outside
The heating of Au plating solutions is maintained at 334K by device, is stirred on one side.
Then, it is mixed in aqueous solution of the concentration with 20g/L of 100mL dissolved with citric acid monohydrate by Pd coating
The powder (quality 35g) of the NiP cores 12 of 14 coverings, is stirred at room temperature 5 minutes.
Later, mixed dissolution has the above-mentioned aqueous solution of citric acid monohydrate and NiP powders in Au liquid is plated, and passes through substitution
Plating forms Au coating 16.If carrying out Au substitution platings under these conditions, the Au coating 16 of thickness about 20nm can be obtained.
In this way, obtain the conductive particle 10 that NiP cores 12 are covered by Pd coating 14 and Au coating 16.Fig. 2 expressions obtain in this way
The cross-sectional SEM image of the conductive particle 10 of the embodiment obtained.Confirm the state that NiP cores 12 are covered by Pd coating 14.It needs
It is relatively thin it is noted that since the thickness of Au coating 16 is 20nm, therefore be difficult in SEM image to confirm its presence.
In addition, the thickness of Pd coating 14 and Au coating 16 possessed by conductive particle can be according to conductive particle 10
Composition, the grain size (median particle diameter) of the density of NiP cores 12, NiP cores 12, Pd and Au density passed through using such as following formula
Calculating is obtained.For the composition analysis of conductive particle 10, a certain amount of conductive particle 10 can be dissolved in chloroazotic acid, use is pure
After water dilution, carried out using ICP apparatus for analyzing luminosity.
Thickness of coating (μm)=(quality %/100 of coating) × (1/ forms the density (g/cm of the element of coating3))×
(total surface area (the cm of 1/NiP cores3))×10,000
Wherein, the density of Au is 19.32g/cm3, the density of Pd is 11.99g/cm3, the density of NiP particles is 7.8g/
cm3, the total surface area of NiP cores is contained in the surface area (such as spherome surface product of median particle diameter d50) and sample of a core
NiP cores sum product.
Experimental example presented below carries out the feature of the conductive particle 10 of embodiments of the present invention in further detail
Explanation.Experimental example shown here is Examples 1 to 4 (Pd coating+Au coating), reference example 1~4 (no Au coating) and comparative example
1~4 (no Pd coating).Examples 1 to 4 forms Au coating on the Pd coating of reference example 1~4 respectively, and comparative example 1~4 is direct
Au substitution coating is formed on NiP cores 12.
In all of the embodiments illustrated, it is 20.0 μm for the median particle diameter d50 of the NiP powders of NiP cores 12, uses
[(d90-d10)/d50] is 0.7 powder.NiP powders have consisting of：Relative to P of the entirety containing 6.3 mass %,
The Cu of 3.3 mass %, the Sn of 0.2 mass %, remaining as Ni.
As described above, the thickness of the Pd coating in embodiment and reference example builds the mixed of bath foam and reducing solution by adjusting plating Pd
Composition and division in a proportion changes.As described above, the thickness of the Au coating in embodiment is limited by the presence of Pd coating of the thickness more than 100nm
System, the thickness of Au coating is about 20nm in any embodiment.In addition, the thickness of the Au coating in comparative example is by adjusting plating
The potassium auricyanide concentration of time and/or plating solution is applied to change.
The thickness and volume resistivity of each coating of the electric conduction powder of embodiment, reference example and comparative example are in 1~table of table 3
With Fig. 3~be represented in Fig. 4.Fig. 3 is to represent the conductive particle (Pd coating+Au coating) of embodiment and reference example (no Au coating)
Conductive particle volume resistivity to the chart of the dependence of Pd thickness of coating, Fig. 4 is to represent comparative example (no Pd coating)
Conductive particle volume resistivity to the chart of the dependence of Au thickness of coating.
As described above, the thickness of coating is obtained according to the composition analysis of electric conduction powder by calculating.In addition, each electric conductivity
The volume resistivity of powder is measured using device shown in fig. 5.1.15g powder samples are put into the barrel of internal diameter 11mm,
Ohmer is utilized (to put the ohmer of motor production day in the state of applying the pressure of 22MPa using the fixture (piston) of Cu
3541) whole resistance value is measured, volume resistivity is acquired using following formula according to the resistance value.
Volume resistivity=(resistance value of whole resistance value-fixture) × π × (11/2)2× 100/ thickness
In addition, the thickness of above formula be with cm units represent apply above-mentioned pressure when barrel in powder thickness (with pressurization side
To parallel).
[table 1]
[table 2]
[table 3]
From Fig. 3 and table 1,2 it is found that the Pd coating with about more than 115nm thickness electric conduction powder (Examples 1 to 4,
Reference example 1~4) volume resistivity 0.3 × 10- 5Ω m are hereinafter, sufficiently low.If the thickness of Pd coating is increased to about
240nm, even if then only Pd coating (reference example 4), volume resistivity is also 0.22 × 10- 5Below Ω m.From Tables 1 and 2
If comparison it is found that forming the Au coating of thickness about 20nm on Pd coating, volume resistivity reduces.Although volume resistance
The reduction very little of rate, but by forming Au coating, the increase of the volume resistivity caused by the oxidation of Pd coating can be inhibited.Au
Coating improves the moisture-resistance reliability of electric conduction powder.The electric conduction powder of Examples 1 to 4 tests (condition in pressure cooking：
125 DEG C, 95RH%, 2.2atm) in, even if after 100 hours, not finding the rising of volume resistivity and the variation of appearance yet.
On the other hand, from table 3 and Fig. 4 it is found that when only forming Au coating on NiP particles, even if the thickness of Au coating is
About 47nm, volume resistivity are also 0.47 × 10- 5Ω·m.That is, Au possessed by the conductive particle 10 of Examples 1 to 4
Although content is less than the half of the content of Au possessed by the conductive particle of comparative example 4, the conduction of Examples 1 to 4
The volume resistivity of property particle 10 is below the half of the conductive particle of comparative example 4.
In this way, by embodiments of the present invention, can obtain than it is in the past more cheap and with sufficiently high electric conductivity and
The conductive particle of moisture-resistance reliability and the electric conduction powder containing this conductive particle.
The conductive polymer composition of embodiments of the present invention contains above-mentioned electric conduction powder and macromolecule.In addition,
Unless otherwise noted, macromolecule has electric insulating quality.As macromolecule, can macromolecule material well known to various be used according to purposes
Material.High molecular material is, for example, rubber, thermoplastic resin, thermosetting resin or photo-curable resin.Embodiments of the present invention
Conductive polymer composition can be widely used in anisotropic conductive sheet (ACF), anisotropic conductive paste (ACP) etc..It is conductive
The content of property particle can be properly set according to purposes, percentage by volume about more than 3% 50% hereinafter, it is preferred that 5% with
Upper less than 30%.
The conductive particle 10 of above-mentioned electric conduction powder is formed due to having the core 12 based on Ni, is shown strong
It is magnetic.Therefore, profit can be formed as described in Patent Documents 1 to 3 using the polymeric composition of embodiments of the present invention
Make the anisotropic conductive sheet that conductive particle arranges in a thickness direction with magnetic field.If here, use rubber as macromolecule
Glue (or artificial rubber), then can obtain pressure sensitive anisotropic conductive sheet.Pressure sensitive anisotropic conductive sheet has following property
Matter, that is, electric conductivity is only shown when applying pressure (compression) on the thickness direction of piece, pressurization restores insulating properties after stopping.Pressure
Quick type anisotropic conductive sheet is suitable for being temporarily formed the use of electrical connection in the inspection of circuit board or semiconductor device etc.
On the way.As rubber, well known various rubber can be used (including elastomer).From viewpoints such as processability, heat resistances, preferably
Curable silicone rubber.
ACF or ACP can also be used for forming the electrical connection in the electric appliances such as liquid crystal display device, tablet computer, mobile phone.
In these purposes, macromolecule uses thermosetting resin or photo-curable resin.As thermosetting resin, such as various rings can be used
As photo-curable resin, acrylic resin can be used in oxygen resin.
Industrial availability
The present invention is suitable for conductive particle, electric conduction powder, conductive polymer composition and anisotropic conductive sheet.
Symbol explanation
10 conductive particles
12 cores (NiP cores)
14 Pd coating
16 Au coating.
Claims (8)
1. a kind of conductive particle, which is characterized in that including：
Globose nucleus comprising Ni and P,
Cover the core surface Pd coating and
The Au coating of the Pd coating surfaces is covered,
The thickness of Au coating is big described in the thickness ratio of the Pd coating, and the thickness of the Pd coating is more than 100nm and is less than
300nm, also, the thickness of the Au coating for 5nm less than 30nm.
2. conductive particle as described in claim 1, it is characterised in that：
The Pd coating restores coating for non-electrolytic.
3. conductive particle as claimed in claim 1 or 2, it is characterised in that：
The Au coating replaces coating for non-electrolytic.
4. conductive particle as claimed in claim 1 or 2, it is characterised in that：
The core also includes Cu and Sn.
5. conductive particle as claimed in claim 1 or 2, it is characterised in that：
Less than a diameter of 1 μm or more 100 μm of the core.
6. a kind of electric conduction powder, it includes conductive particle according to any one of claims 1 to 5, the spy of the powder
Sign is：
Median particle diameter d50 in cumulative volume distribution curve be 3 μm or more 100 μm hereinafter, and [(d90-d10)/d50]≤
0.8。
7. a kind of conductive polymer composition, it is characterised in that：
It includes the electric conduction powder and macromolecule described in claim 6, the macromolecule is rubber, thermoplastic resin or thermosetting
Property resin.
8. a kind of anisotropic conductive sheet, it is characterised in that：
It is formed as the conductive polymer composition described in claim 7, and the conductive particle arranges in a thickness direction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014-034966 | 2014-02-26 | ||
| JP2014034966A JP5943019B2 (en) | 2014-02-26 | 2014-02-26 | Conductive particles, conductive powder, conductive polymer composition and anisotropic conductive sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104867530A CN104867530A (en) | 2015-08-26 |
| CN104867530B true CN104867530B (en) | 2018-06-19 |
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| JP (1) | JP5943019B2 (en) |
| KR (1) | KR101690696B1 (en) |
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| TW (1) | TWI575077B (en) |
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|---|---|---|---|---|
| KR101959536B1 (en) | 2016-04-05 | 2019-03-18 | 주식회사 아이에스시 | Anisotropic sheet comprising conductive particles mixed different kind of particles |
| TWI761477B (en) * | 2017-03-30 | 2022-04-21 | 日商太陽油墨製造股份有限公司 | Conductive adhesive, cured product, electronic component, and manufacturing method of electronic component |
| KR20220016999A (en) * | 2017-06-22 | 2022-02-10 | 세키스이가가쿠 고교가부시키가이샤 | Electrically conductive particle, electrically conductive particle manufacturing method, electrically conductive material, and connecting structure |
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| JPH0797929B2 (en) | 1988-06-29 | 1995-10-25 | 井関農機株式会社 | Rolling control device for paddy farm machinery |
| JP2004021018A (en) | 2002-06-18 | 2004-01-22 | Casio Comput Co Ltd | Light source unit and display device |
| JP4188278B2 (en) * | 2004-05-06 | 2008-11-26 | 日本化学工業株式会社 | Anisotropic conductive film and heat seal connector |
| JP4451760B2 (en) * | 2004-11-09 | 2010-04-14 | 財団法人秋田県資源技術開発機構 | Method for producing spherical NiP fine particles and method for producing conductive particles for anisotropic conductive film |
| KR100879578B1 (en) * | 2007-04-23 | 2009-01-22 | 한화석유화학 주식회사 | Manufacturing method of conductive electroless plating powder |
| JP5327582B2 (en) * | 2007-10-18 | 2013-10-30 | 日立金属株式会社 | Reduction precipitation type spherical NiP fine particles and method for producing the same |
| JP5151920B2 (en) * | 2008-02-05 | 2013-02-27 | 日立化成工業株式会社 | Conductive particles and method for producing conductive particles |
| JP4957838B2 (en) * | 2009-08-06 | 2012-06-20 | 日立化成工業株式会社 | Conductive fine particles and anisotropic conductive materials |
| CN102605359A (en) * | 2011-01-25 | 2012-07-25 | 台湾上村股份有限公司 | Chemical palladium-gold plated film structure and manufacturing method thereof, copper wire or palladium-gold plated film packaging structure jointed by palladium-copper wire and packaging process thereof |
| JP2012174417A (en) | 2011-02-18 | 2012-09-10 | Jsr Corp | Anisotropic conductive sheet, method for connecting electronic member, and electronic part |
| KR20130058297A (en) * | 2011-11-25 | 2013-06-04 | 에이케이이노텍주식회사 | Electrical conductive powder and semiconductor test socket |
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| JP2015160958A (en) | 2015-09-07 |
| CN104867530A (en) | 2015-08-26 |
| TWI575077B (en) | 2017-03-21 |
| KR20150101376A (en) | 2015-09-03 |
| TW201542831A (en) | 2015-11-16 |
| JP5943019B2 (en) | 2016-06-29 |
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