CN104867530A - Conductive Particles, Conductive Powder, Conductive Polymer Composition And Aeolotropy Conducting Strip - Google Patents
Conductive Particles, Conductive Powder, Conductive Polymer Composition And Aeolotropy Conducting Strip Download PDFInfo
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- CN104867530A CN104867530A CN201510011506.7A CN201510011506A CN104867530A CN 104867530 A CN104867530 A CN 104867530A CN 201510011506 A CN201510011506 A CN 201510011506A CN 104867530 A CN104867530 A CN 104867530A
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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 provides the conductive particles which are lower in cost and possess enough high conductivity, conductive powder comprising the conductive particles, a conductive polymer composition and an aeolotropy conducting strip. The conductive particles 10 of the embodiment of the present invention possess a spherical core 12 containing Ni and P, a Pd plating layer 14 covering the surface of the core 12 and an Au plating layer 16 covering the surface of the Pd plating layer.
Description
Technical field
The present invention relates to and there is the conductive particle that principal component is the core of Ni, and relate to the electric conduction powder, conductive polymer composition and the anisotropic conductive sheet that comprise this conductive particle.
Background technology
The polymeric composition comprising conductive particle is as only having the anisotropic conductive sheet (ACF) of conductivity, anisotropy conductiving glue (ACP) and the electrical connection be widely used for such as between electronic unit in a thickness direction.Particularly anisotropic conductive sheet is widely used for the formation etc. of the electrical connection in the compact electric apparatus such as mobile phone.In addition, rubber (comprising synthetic rubber) is used as high molecular anisotropic conductive sheet as the formation (such as PCR (registered trade mark of JSR company)) of pressure sensitive anisotropic conductive sheet also for being electrically connected in the inspection (such as impedance measuring) of circuit board etc. temporarily.
Such as, in patent documentation 1 ~ 3, disclose the anisotropic conductive sheet using and there is ferromagnetic conductive particle.In these anisotropic conductive sheets, conductive particle arranges in a thickness direction, and direction dispersion distribution in the face of sheet.If exerted pressure to sheet in a thickness direction, then the conductive particle arranged in a thickness direction is close to each other, forms conductive path.There is ferromagnetic conductive particle arranged in a thickness direction by magnetic field.
Prior art document
Patent documentation
Patent documentation 1: No. 02/13320th, International Publication
Patent documentation 2: No. 2004/021018th, International Publication
Patent documentation 3: Japanese Unexamined Patent Publication 2012-174417 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2006-131978 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2009-197317 publication
Summary of the invention
But conductive particle in the past such as, in order to obtain sufficiently high conductivity (enough low specific insulation, 0.3 × 10
-5below Ω m), defining thickness is such as Au (gold) coating of 200nm (0.2 μm), there is the problem that cost is high.In addition, in the purposes requiring high moisture-resistance reliability, coating is difficult to use other metal outside Au.
The present invention is exactly the invention completed to solve the problem, to provide cheap than ever and have the conductive particle of sufficiently high conductivity and moisture-resistance reliability and comprise for the purpose of the electric conduction powder of this conductive particle, conductive polymer composition and anisotropic conductive sheet.
The conductive particle of embodiments of the present invention has: comprise the globose nucleus of Ni and P, cover the Pd coating on above-mentioned core surface and cover the Au coating of above-mentioned Pd coating surface.
In certain execution mode, above-mentioned Pd coating is non-electrolytic reduction coating.
In certain execution mode, above-mentioned Au coating is that non-electrolytic replaces coating.
In certain execution mode, the thickness of the above-mentioned Au coating of Thickness Ratio of above-mentioned Pd coating is large, and the thickness of above-mentioned Au coating is more than 5nm and is less than 40nm.The thickness of above-mentioned Pd coating is preferably greater than 5nm and is less than 300nm.
In certain execution mode, above-mentioned core also comprises Cu and Sn.
In certain execution mode, the diameter of above-mentioned core is more than 1 μm less than 100 μm.The diameter of above-mentioned core is preferably more than 3 μm.
The electric conduction powder of embodiments of the present invention is for comprising the powder of the conductive particle described in above-mentioned any one, median particle diameter d50 in its cumulative volume distribution curve is more than 3um less than 100 μm, and [(d90-d10)/d50]≤0.8.
The conductive polymer composition of embodiments of the present invention comprises above-mentioned electric conduction powder and macromolecule, and wherein, above-mentioned macromolecule is such as rubber, thermoplastic resin or thermosetting resin.
The anisotropic conductive sheet of embodiments of the present invention is formed by above-mentioned conductive polymer composition, and above-mentioned conductive particle arranges in a thickness direction.
The effect of invention
By embodiments of the present invention, can provide cheap than ever and there is the conductive particle of sufficiently high conductivity and moisture-resistance reliability and comprise the electric conduction powder of this conductive particle, conductive polymer composition and anisotropic conductive sheet.
Accompanying drawing explanation
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 of the conductive particle representing embodiment.
Fig. 3 represents that the specific insulation of the conductive particle (Pd coating+Au coating) of embodiment and the conductive particle of reference example (without Au coating) is to the dependent chart of Pd thickness of coating.
Fig. 4 is that the specific insulation of the conductive particle representing comparative example (without Pd coating) is to the dependent chart of Au thickness of coating.
Fig. 5 is the schematic diagram of the structure representing device used in the mensuration of the specific insulation of conductive particle.
Embodiment
Below with reference to accompanying drawing, the conductive particle of embodiments of the present invention, electric conduction powder, conductive polymer composition and anisotropic conductive sheet are described.
Fig. 1 is the schematic cross-section of the conductive particle 10 of embodiments of the present invention.The Au coating 16 that conductive particle 10 has spherical core 12, covers Pd (palladium) coating 14 on core 12 surface, covers Pd coating 14 surface.Core 12 is containing Ni (nickel) and P (phosphorus).The diameter of core 12 such as more than 1 μm less than 100 μm.If the diameter of fruit stone 12 is less than 1 μm, then because the aggegation of core 12 becomes serious and is difficult to as powder handling.If the diameter of fruit stone 12 is more than 100 μm, then overflow from conductive path, such as, cause the possibility of the short circuit between adjacent wiring to uprise.The diameter of core 12 is preferably more than 3 μm, and is preferably less than 30 μm.If the diameter of fruit stone 12 is more than 3 μm, because when carrying out plating Pd, the aggegation of core 12 is relaxed, therefore practical.Direct below 30 μm as fruit stone 12, reduces from the spilling of conductive path or disappears.As the electric conduction powder of the aggregate of conductive particle 10, the median particle diameter d50 of preferred cumulative volume distribution curve more than 3 μm less than 100 μm, and the powder of [(d90-d10)/d50]≤0.8.Median particle diameter d50 can be used as the index of the average grain diameter of electric conduction powder.In addition, if [(d90-d10)/d50] is more than 0.8, then the deviation of particle diameter is excessive, conductive path exists the conductive particle not with wiring or electrode contact, therefore there is the possibility that connection reliability reduces.D10 and d90 represents that cumulative volume percentage is the particle diameter of 10% and 90% respectively.In addition, if no special instructions, the domain size distribution in this specification represents the particle diameter of being tried to achieve by laser diffraction and scattering method.
As the core 12 of conductive particle 10, such as, can use the conductive particle recorded in patent documentation 4 or 5 aptly.The NiP electric conduction powder that the manufacture method recorded by patent documentation 5 is manufactured, due to for single dispersing and narrow particle size distribution, therefore has the advantage being easy to the electric conduction powder manufacturing satisfied [(d90-d10)/d50]≤0.8 relation.
It is principal component and the situation comprising P (phosphorus), Cu (copper) and/or Sn (tin) that core 12 exists with Ni.P, Cu and Sn all in the balling process of core 12 to suppress the raw material components as reaction treatment liquid for the purpose of the growth of core or aggegation to add.For the reason of the resistivity of reduction core 12 self, the content of these elements in core 12 is preferably a small amount of.Specifically, in core 12, relative to entirety, preferably comprise the P of 1 ~ 15 quality %, more preferably at below 10 quality %.If the content of P is more than 15 quality %, then the specific insulation of core 12 significantly rises, and impracticable.In addition, in core 12, relative to entirety, the Cu of 0.01 quality % ~ 18 quality % is preferably comprised.If the content of Cu is more than 18 quality %, then there is the possibility that core 12 reduces with the adaptation of Pd coating 14.In addition, in core 12, relative to entirety, the Sn of 0.05 quality % ~ 10 quality % is preferably comprised.If the content of Sn is more than 10 quality %, then there is the possibility that core 12 reduces with the adaptation of Pd coating 14.In addition, core 12 preferably also comprises Sn on the basis of Ni, P and Cu.Cu and Sn plays the effect of the catalyst poison of karyogenesis reaction when manufacturing the powder using core 12, be therefore easy to manufacture powder that is monodispersed, narrow particle size distribution.In addition, Cu and Sn eutectoid in the developmental process of NiP conductive particle.
Pd coating 14 is preferably non-electrolytic reduction coating.Non-electrolytic reduction coating has the adaptation inferior unlike non-electrolytic replacement coating, and compares non-electrolytic replacement coating, and the generation of pin hole is few.Au coating 16 is preferably non-electrolytic and replaces coating.Compare non-electrolytic reduction Au coating, the adaptation that non-electrolytic replaces Au coating and Pd coating 14 is better.Because non-electrolytic replaces the dissolving along with Pd coating 14 in plating Au reaction, therefore preferably make the thickness of the Thickness Ratio Au coating 16 of Pd coating 14 larger, and the thickness of Au coating 16 is less than 40nm.If the thickness of Au coating is more than 40nm, then characteristic there is no special change but cause waste on cost.The thickness of preferred Pd coating 14 is for being greater than 5nm and being less than 300nm.If Pd coating is at below 5nm, then, when imposing non-electrolytic replacement plating Au on Pd coating, there is the possibility that Pd coating all dissolves.If Pd coating all dissolves, then there is the possibility that adaptation reduces or Au does not separate out of Au coating.In addition, if the thickness of Pd coating is more than 300nm, then characteristic there is no special change but cause waste on cost.In view of the above, when improving reliability further, the thickness of preferred Pd coating is for being greater than 50nm and being less than 200nm.
The conductive particle 10 of embodiments of the present invention has the Pd coating 14 covering core 12 surface and the Au coating 16 covering Pd coating surface 14, therefore, more cheap than ever mutually and have sufficiently high conductivity and moisture-resistance reliability.Its reason is below described, but the following description does not limit embodiments of the present invention.
As in the upper method forming Au coating of the particle (referred to as Ni particle) taking Ni as principal component, non-electrolytic reduced form is had to plate Au and non-electrolytic substituted type plating Au.Generally speaking, the plating of particle (powder) does not use plating (due to particle agglutination), omits " non-electrolytic " and be only called " reduced form " or " substituted type " therefore.
When carrying out replacement plating Au to Ni particle, Ni stripping is in plating solution, and the electronics discharged along with the ionization of Ni is received by the Au ion in plating solution, separates out Au at Ni particle surface.Because the position of Ni stripping is not necessarily consistent with the position that Au separates out, therefore on replacement Au coating, define more pin hole.When carrying out protection against the tide experiment (such as pressure cooking experiment), the moisture invaded from pin hole makes Ni be oxidized, and generates hydroxide.Part hydroxide is present in problem Au coating causing producing conductivity reduction.In addition, although it is higher than following reduction coating with the adaptation of Ni particle to replace Au coating, thickness of coating cannot be increased.Such as be difficult to by replace plating formed thickness more than 100nm, the Au coating of especially more than 200nm.
On the other hand, in reduction plating Au, because the Au ion in plating solution is separated out as Au by receiving electronics from reducing agent, therefore without the stripping of Ni.Therefore, compared to replacement Au coating, the pin hole of reduction Au coating is few, and can form the Au coating of more than thickness 200nm.But the adaptation of reduction Au coating and Ni particle is low, when carrying out protection against the tide experiment (such as pressure cooking experiment), there is the problem that reduction Au coating is peeled off.
In addition, first formed at Ni particle surface and replace Au coating, then to cover the mode dual-purpose reduction Au coating replacing coating, although can solve the problem, but in order to obtain enough conductivity, need to make the integral thickness of Au coating at about more than 200nm, therefore cost is higher.
To this, the conductive particle 10 of embodiments of the present invention has the Au coating 16 of core (being sometimes designated as below " NiP core ") 12, Pd coating 14 and the covering Pd coating 14 comprising Ni and P.Because Pd is more cheap than Au, therefore conductive particle 10 is at least cheap than the conductive particle only with Au coating because having Pd coating.
In addition, Pd coating 14 both has good adaptation with NiP core 12 and Au coating 16, and the problem peeled off can not occur.Such as, and although still have very high conductivity not as good as Au, Pd, thickness is that the specific insulation of the Pd coating of about 100nm is 0.3 × 10
-5below Ω m is enough low.Further, compared with Au, the ionization tendency larger (oxidation-reduction potential is lower) of Pd, although be easy to oxidation, because Pd coating 14 is covered by Au coating 16, therefore conductive particle 10 has high moisture-resistance reliability.
Pd coating 14 preferably reduces coating.Compared to being plated the film formed by replacement, the pin hole being plated the film formed by reduction is few, dense, also not easily grain boundary attack occurs.In addition, compared to replacement plating, reduction plating is easy to form thickness coating.Because the oxidation-reduction potential of Pd is between the oxidation-reduction potential and the oxidation-reduction potential of Au of Ni, therefore the substitution reaction of Pd and Ni is fierce not as the substitution reaction of Au and Ni.Its result, can think and reduce the adaptation of coating 14 and NiP core 12 by Pd to reduce the adaptation of coating and NiP core 12 than Au higher.If directly form Au to reduce coating on NiP core 12, can think Au and the Ni occurred as side reaction when Au reduction plating fierceness substitution reaction and Au reduction coating and the adaptation of NiP core 12 are reduced.
Au coating 16 preferably replaces coating.The difference of the oxidation-reduction potential of Au and Pd is less, and the substitution reaction of Au and Pd not easily occurs.By the substitution reaction via Ni contained in grain circle of Pd coating 14 and/or pin hole and NiP core 12, Au coating 16 can be formed on Pd coating 14.By regulating the thickness of Pd coating 14, can control by replacing the thickness plating the Au coating 16 formed.This is because if by replacing plating, Ze Li circle and/or pin hole are covered by Au coating 16, so Au coating 16 just stops being formed.The thickness of Pd coating 14 is preferably large than the thickness of Au coating 16, and the thickness of Au coating 16 is preferably less than 40nm.If the thickness of Au coating 16 is more than 40nm, then characteristic there is no special change but cause waste on cost.Such as, if the thickness of Pd coating 14 exceedes such as 100nm, then can form the Au coating 16 being less than 30nm.
In addition, Au coating 16 also can be reduction coating.Because the substitution reaction of side reaction Au and Pd during reduction plating not easily occurs, therefore the adaptation of Au coating and Pd coating 14 is enough high.But in order to the thickness of control Au coating 16, especially in order to form the thin Au coating 16 being less than 40nm with good repeatability, preferably replace plating.
The conductive particle 10 of embodiments of the present invention such as obtains by following methods.
First prepare as NiP core 12, the NiP powder that is made up of NiP particle.The method manufacture that NiP records preferably by patent documentation 5.Specifically, the mode being Ni/Cu=239 with the mol ratio of Ni and Cu prepares nickel sulfate hexahydrate compound and copper sulfate pentahydrate, is dissolved in pure water, makes 15 (dm
3) aqueous metal salt.Then, sodium acetate is dissolved in pure water, is 1.0 (kmol/m
3) concentration, then add NaOH, made 15 (dm
3) pH modulate the aqueous solution.Then, above-mentioned aqueous metal salt and pH are modulated the aqueous solution and is uniformly mixed, form 30 (dm
3) mixed aqueous solution, measure pH be shown as 8.1 value.Then, N is utilized to above-mentioned mixed aqueous solution
2gas sparging is while maintain heating at 343 (K) by external heater, and Keep agitation.Then, 15 (dm are made
3) in pure water with 1.8 (kmol/m
3) concentration dissolve the reducing agent aqueous solution that obtains of Alendronate, it is also heated to 343 (K) by external heater.Then, by above-mentioned 30 (dm
3) mixed aqueous solution and 15 (dm
3) the reducing agent aqueous solution modulate rear mixing in the mode making temperature and become 343 ± 1 (K), obtain NiP powder by non-electrolytic reducing process.
(plating Pd)
The plating Pd preparing 300mL builds body lotion (the パ レ ッ ト LMII that such as island chemicals is produced, the concentration of Pd is 10g/L (liter)).
What prepare 550mL take sodium formate as the reducing solution (such as island chemicals produce パ レ ッ ト II) of principal component.
Pd is built after body lotion mixes with reducing solution, with pure water dilution, obtain the Pd plating solution (pH is 5.5) of 3L.While the heating of Pd plating solution is remained on 328K by external heater, stir.
Prepare the reductive water solution 300mL (pH is 5.5) after by the above-mentioned reducing solution pure water dilution of 50mL.In reductive water solution, mix NiP powder (quality 50g), at room temperature stir 10 minutes.
Afterwards, the reductive water solution being dispersed with NiP powder is mixed in above-mentioned plating solution, forms Pd coating 14 by reduction plating.
Like this, the NiP core 12 covered by Pd coating 14 is obtained.If carry out Pd reduction plating under the conditions described above, then can obtain the Pd coating 14 that thickness is about 115nm.
In addition, by the mixing ratio that plating Pd builds Yu Ye ︰ reducing solution being adjusted to 300mL ︰ 500mL in above-mentioned plating Pd operation, can the thickness of control Pd coating.Such as, if the mixing ratio making plating Pd build Yu Ye ︰ reducing solution is 420mL ︰ 790mL, plating is carried out to the NiP core 12 of 35g, then can obtain the Pd coating that thickness is about 240nm.
(plating Au)
Build the potassium auricyanide of mixing 0.1g lauryl sodium sulfate and 0.9g in body lotion (the デ ィ ッ プ G-FP that such as island chemicals is produced) at the plating Au of 200mL, with pure water dilution, prepare the Au plating solution (pH is 4.0) of 2L.While the heating of Au plating solution is remained on 334K by external heater, stir.
Then, be dissolved with in the aqueous solution of citric acid monohydrate with the concentration of 20g/L the powder (quality 35g) mixing the NiP core 12 covered by Pd coating 14 at 100mL, at room temperature stir 5 minutes.
Afterwards, in plating Au liquid, mixed dissolution has the above-mentioned aqueous solution and the NiP powder of citric acid monohydrate, forms Au coating 16 by replacing plating.If carry out Au under these conditions to replace plating, then can obtain the Au coating 16 that thickness is about 20nm.
Like this, the conductive particle 10 that NiP core 12 is covered by Pd coating 14 and Au coating 16 is obtained.Fig. 2 represents the cross-sectional SEM image of the conductive particle 10 of the embodiment obtained like this.The state that NiP core 12 is covered by Pd coating 14 can be confirmed.It should be noted that, the thickness due to Au coating 16 is 20nm, thinner, is therefore difficult to confirm that it exists in SEM image.
In addition, the thickness of the Pd coating 14 that has of conductive particle and Au coating 16 can utilize such as following formula to be obtained by calculating according to the density of the particle diameter (median particle diameter) of the density of the composition of conductive particle 10, NiP core 12, NiP core 12, Pd and Au.For the composition analysis of conductive particle 10, can a certain amount of conductive particle 10 be dissolved in chloroazotic acid, after pure water dilution, utilize ICP apparatus for analyzing luminosity to carry out.
Thickness of coating (μm)=(quality %/100 of coating) × (density (g/cm of the element of 1/ formation coating
3)) × (total surface area (cm of 1/NiP core
3)) × 10,000
Wherein, the density of Au is 19.32g/cm
3, the density of Pd is 11.99g/cm
3, the density of NiP particle is 7.8g/cm
3, the total surface area of NiP core is the surface area of a core (such as the spherome surface of median particle diameter d50 amasss) and the product of the sum of contained NiP core in test portion.
Below show experimental example, the feature of the conductive particle 10 of embodiments of the present invention is described in further detail.Experimental example shown here is embodiment 1 ~ 4 (Pd coating+Au coating), reference example 1 ~ 4 (without Au coating) and comparative example 1 ~ 4 (without Pd coating).Embodiment 1 ~ 4 forms Au coating respectively on the Pd coating of reference example 1 ~ 4, and comparative example 1 ~ 4 directly forms Au and replaces coating on NiP core 12.
In all of the embodiments illustrated, the median particle diameter d50 for the NiP powder of NiP core 12 is 20.0 μm, and use [(d90-d10)/d50] is the powder of 0.7.NiP powder has following composition: relative to entirety contain the P of 6.3 quality %, the Cu of 3.3 quality %, 0.2 quality % Sn, remaining as Ni.
As mentioned above, the mixing ratio that the thickness of the Pd coating in embodiment and reference example builds body lotion and reducing solution by adjustment plating Pd changes.As mentioned above, the thickness of the Au coating in embodiment by thickness more than the Pd coating of 100nm existence limit, in any embodiment, the thickness of Au coating is all about 20nm.In addition, the thickness of the Au coating in comparative example is changed by the potassium auricyanide concentration of adjustment plating time and/or plating solution.
Thickness and the specific insulation of each coating of the electric conduction powder of embodiment, reference example and comparative example represent in table 1 ~ table 3 and Fig. 3 ~ Fig. 4.Fig. 3 represents that the specific insulation of the conductive particle (Pd coating+Au coating) of embodiment and the conductive particle of reference example (without Au coating) is to the dependent chart of Pd thickness of coating, and Fig. 4 is that the specific insulation of the conductive particle representing comparative example (without Pd coating) is to the dependent chart of Au thickness of coating.
As mentioned above, the thickness of coating is obtained by calculating according to the composition analysis of electric conduction powder.In addition, the specific insulation of each electric conduction powder utilizes the device shown in Fig. 5 to measure.1.15g powder test portion is put into the barrel of internal diameter 11mm, under the state utilizing the fixture of Cu (piston) to apply the pressure of 22MPa, utilize ohmer (putting the ohmer 3541 that motor is produced day) to record overall resistance value, utilize following formula to try to achieve specific insulation according to this resistance value.
Specific insulation=(resistance value of overall resistance value-fixture) × π × (11/2)
2× 100/ thickness
In addition, the thickness of above formula is powder thickness (parallel with compression aspect) in barrel when applying above-mentioned pressure with cm unit representation.
[table 1]
[table 2]
[table 3]
From Fig. 3 and table 1,2, there is the specific insulation of the electric conduction powder (embodiment 1 ~ 4, reference example 1 ~ 4) of the Pd coating of about more than 115nm thickness 0.3 × 10
-5below Ω m is enough low.If the thickness of Pd coating is increased to about 240nm, even if then only there is Pd coating (reference example 4), specific insulation is also 0.22 × 10
-5below Ω m.From table 1 and table 2 relatively, if form the Au coating that thickness is about 20nm on Pd coating, then specific insulation reduces.Although the reduction of specific insulation is very little, by forming Au coating, the increase of the specific insulation that the oxidation because of Pd coating can be suppressed to cause.Au coating improves the moisture-resistance reliability of electric conduction powder.The electric conduction powder of embodiment 1 ~ 4, in pressure cooking experiment (condition: 125 DEG C, 95RH%, 2.2atm), even if after 100 hours, does not find the rising of specific insulation and the change of outward appearance yet.
On the other hand, from table 3 and Fig. 4, when NiP particle is only formed Au coating, even if the thickness of Au coating is about 47nm, specific insulation is also 0.47 × 10
-5Ω m.Namely, although 1/2nd of the content of the Au that the content of the Au that the conductive particle 10 of embodiment 1 ~ 4 has has less than the conductive particle of comparative example 4, the specific insulation of the conductive particle 10 of embodiment 1 ~ 4 comparative example 4 conductive particle less than 1/2nd.
Like this, by embodiments of the present invention, can obtain more cheap than ever and there is the conductive particle of sufficiently high conductivity and 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, various known macromolecular material can be used according to purposes.Macromolecular material is such as rubber, thermoplastic resin, thermosetting resin or photo-curable resin.The conductive polymer composition of embodiments of the present invention can be widely used in anisotropic conductive sheet (ACF), anisotropic conductive is stuck with paste (ACP) etc.The content of conductive particle can set aptly according to purposes, percentage by volume greatly about less than more than 3% 50%, preferably more than 5% less than 30%.
The conductive particle 10 forming above-mentioned electric conduction powder, owing to having the core 12 based on Ni, therefore shows ferromagnetism.Therefore, utilize the polymeric composition of embodiments of the present invention can as described in patent documentation 1 ~ 3 form the anisotropic conductive sheet utilizing magnetic field that conductive particle is arranged in a thickness direction.At this, if use rubber (or artificial rubber) as macromolecule, then pressure sensitive anisotropic conductive sheet can be obtained.Pressure sensitive anisotropic conductive sheet has following character, that is, show conductivity when only applying pressure (compression) on the thickness direction of sheet, and pressurization recovers insulating properties after stopping.Pressure sensitive anisotropic conductive sheet is suitable for the interim purposes forming electrical connection in the inspection of circuit board or semiconductor device etc.As rubber, known various rubber (comprising elastomer) can be used.From the viewpoint such as processability, thermal endurance, be preferably curable silicone rubber.
ACF or ACP also can be used for forming the electrical connection in the electrical equipment such as liquid crystal indicator, panel computer, mobile phone.In these purposes, macromolecule uses thermosetting resin or photo-curable resin.As thermosetting resin, such as, can use various epoxy resin, as photo-curable resin, can acrylic resin be used.
Utilizability in industry
The present invention is applicable to conductive particle, electric conduction powder, conductive polymer composition and anisotropic conductive sheet.
Bis explanation
10 conductive particles
12 cores (NiP core)
14 Pd coating
16 Au coating.
Claims (9)
1. a conductive particle, is characterized in that, comprising:
Comprise the globose nucleus of Ni and P,
Cover described core surface Pd coating and
Cover the Au coating of described Pd coating surface.
2. conductive particle as claimed in claim 1, is characterized in that:
Described Pd coating is non-electrolytic reduction coating.
3. conductive particle as claimed in claim 1 or 2, is characterized in that:
Described Au coating is that non-electrolytic replaces coating.
4. the conductive particle according to any one of claims 1 to 3, is characterized in that:
The thickness of Au coating described in the Thickness Ratio of described Pd coating is large, and the thickness of described Au coating is more than 5nm and is less than 40nm.
5. the conductive particle according to any one of Claims 1 to 4, is characterized in that:
Described core also comprises Cu and Sn.
6. the conductive particle according to any one of Claims 1 to 5, is characterized in that:
The diameter of described core is more than 1 μm less than 100 μm.
7. an electric conduction powder, it comprises the conductive particle according to any one of claim 1 ~ 6, and the feature of described powder is:
Median particle diameter d50 in cumulative volume distribution curve is more than 3 μm less than 100 μm, and [(d90-d10)/d50]≤0.8.
8. a conductive polymer composition, is characterized in that:
It comprises electric conduction powder according to claim 7 and macromolecule, and described macromolecule is rubber, thermoplastic resin or thermosetting resin.
9. an anisotropic conductive sheet, is characterized in that:
It is formed by conductive polymer composition according to claim 8, and described conductive particle arranges in a thickness direction.
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| 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 |
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| CN104867530B CN104867530B (en) | 2018-06-19 |
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| CN110603612A (en) * | 2017-06-22 | 2019-12-20 | 积水化学工业株式会社 | Conductive particle, method for producing conductive particle, conductive material, and connection structure |
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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 |
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| CN110603612A (en) * | 2017-06-22 | 2019-12-20 | 积水化学工业株式会社 | Conductive particle, method for producing conductive particle, conductive material, and connection structure |
| CN110603612B (en) * | 2017-06-22 | 2022-08-30 | 积水化学工业株式会社 | Conductive particle, method for producing conductive particle, conductive material, and connection structure |
Also Published As
| Publication number | Publication date |
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| KR101690696B1 (en) | 2016-12-28 |
| CN104867530B (en) | 2018-06-19 |
| JP2015160958A (en) | 2015-09-07 |
| TWI575077B (en) | 2017-03-21 |
| KR20150101376A (en) | 2015-09-03 |
| TW201542831A (en) | 2015-11-16 |
| JP5943019B2 (en) | 2016-06-29 |
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