CN104246909B - Electrocondution slurry, solidfied material, electrode and electronic equipment - Google Patents
Electrocondution slurry, solidfied material, electrode and electronic equipment Download PDFInfo
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- CN104246909B CN104246909B CN201380017276.4A CN201380017276A CN104246909B CN 104246909 B CN104246909 B CN 104246909B CN 201380017276 A CN201380017276 A CN 201380017276A CN 104246909 B CN104246909 B CN 104246909B
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0218—Composite particles, i.e. first metal coated with second metal
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0245—Flakes, flat particles or lamellar particles
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3485—Applying solder paste, slurry or powder
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- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention relates to a kind of electrocondution slurry, contain conductive filling (A), thermosetting phenolic resin (B), unrighted acid (C) and organic solvent (D).More specifically, tabular of the conductive filling (A) of the electrocondution slurry containing below the volume % of more than 0.1 volume % 30 is coated to particle (a1), the tabular be coated to particle (a1) using copper or copper alloy as core, by shell of silver, the thickness degree of the shell be more than 0.02 μm, and aspect ratio be more than 2.
Description
Technical field
The solidfied material obtained the present invention relates to a kind of electrocondution slurry, by the electrocondution slurry, the electrode being made up of the solidfied material
And electronic equipment.
Background technology
So-called electrocondution slurry is typically referred to silver (Ag) or copper (Cu), nickel (Ni), tin (Sn), aluminium (Al), carbon black etc.
The thermosetting binder resins such as granular conductive filling and phenolic resin or epoxy resin and organic solvent coordinate and
The conductive composition being made.Moreover, electrocondution slurry easily and imperceptibly can form variously-shaped by silk-screen printing etc.
Electrode, therefore be applied on various electronic equipments or electronic product.
At present, as the conductive filling of excellent electric conductivity, copper and silver have been used.However, its problem is, copper because
Cheap and be widely used, its reverse side is due to easy oxidation, so as to cause the electric conductivity of electrocondution slurry unstable.It is another
Aspect, silver is but expensive even if the problem of being also nearly free from similar is oxidized.Therefore, in this field, generally with silver
Particle is used together, or is replaced, and uses the composite particles as formed by silver covering copper particle.
But, with electrocondution slurry formation electrode, the on this electrode face that this kind of composite particles are used as to conductive filling
When welding electronic unit, there is the situation of the wellability difference of the solder metal melted.Particularly using tin-silver-copper etc.
Lead-free solder powder solder slurry in, this problem is notable.Its reason be it is various, still, it is generally recognized that its reason
One of be because fusion welding in tin and electrode in composite particles react to form alloy, between solder metal-electrode
Interfacial energy increase, result is that fusion welding metal is not wetted by extension.
The method of the wellability difference of solder in the electrocondution slurry of Argent grain or above-mentioned composite particles is used as solution, such as
Described in patent document 1, it is known to use as adhesive resin thermoplastic resin and glass transition temperature be 60~100 DEG C or so
Saturated polyester.
Citation
Patent document 1：Japanese Unexamined Patent Publication 6-295616 publications.
The content of the invention
But, the present inventor has carried out detailed analysis and discussion based on the new starting point as shown below, and the present inventor obtains
Know not having by the use of the electrocondution slurry using thermoplastic resin as adhesive and fully eliminate the not enough situation of wellability.
First, the inside of the electrode obtained by electrocondution slurry is by the self-existent conductive filler in the form of contacting with each other
Phase and be made up of the substantial continuous phase that the adhesive resin for riddling its space is made.
Then, Fig. 1 is that existing electrocondution slurry (equivalent to comparative example 1 described later) is being coated on glass baseplate and made
Solidification after electrode on and make solder slurry melt when the sectional view based on SEM (SEM).Such as Fig. 1 institutes
Show, be able to confirm that the pattern that scaling powder (Flux) extends in the way of covering the solder alloy (white lug boss) after melting.More
Specifically, when making solder slurry (solder paster) melting on the electrode being made up of existing electrocondution slurry, the liquid oozed out
State scaling powder is impregnated into electrode interior in the way of covering solder metal, to enter with the state that adhesive resin mixes.
However, when the scaling powder for constituting solder slurry is excessively entering into electrode interior, solder paste should be suppressed on surface
The activating agent of the surface oxidation of solder metal in material is reduced, i.e. be lost in from the surrounding field of solder metal, therefore, it is possible to produce
The lack of fill-out of fusion welding metal.
Fig. 2 is the SEM sectional views of the electrode obtained by existing electrocondution slurry.As shown in Figure 2, it is known that：Scaling powder enters
It is that scaling powder forms independent phase to the result in adhesive resin phase.The adhesive resin is by the thermosetting by being heating and curing
Property phenolic resin formed, although adhesive resin is mutually the phase of rigid, but can not entirely prevent being impregnated with for scaling powder.Its
As a result show：For example when being used as adhesive resin by the thermoplastic resin of heating and softening using polyester resin is this kind of, all the more
Scaling powder can not be suppressed and be impregnated into inside.
On the other hand, as shown in Fig. 3 SEM sectional views, solder slurry is made in the electrode obtained by existing electrocondution slurry
During upper melting, the solder metal of melting is also impregnated into electrode interior.But, being soaked in a certain degree ensures welded joint
It is essential in intensity, when fusion welding metal too reaches deep, that situation, the fusion weld doses on electrode subtracts
It is few.
Like that, as shown in figure 4, fusion welding metal may be described as being ostracised the state of (segregation, segregation) on electrode
(partly referring to figure (1)), is as a result judged as wellability poor.At this moment, because solder is melted at a relatively high temperature, thus it is logical
Often think in the case where adhesive is mutually the electrode being made up of thermoplastic resin, the solder metal of melting more accelerates to be impregnated into
Inside the resin of softening.On the other hand, when the infiltration of fusion welding metal expands on electrode, there is not such repel (partially
Analysis, segregation) (partly referring to figure (2)), welding (soldering) is good.
The invention problem to be solved
The tremendous contribution of the present invention is：A kind of there is provided new electrocondution slurry, obtain by the electrocondution slurry solidfied material, by this
Electrode, the electronic unit with the electrode and the electronic equipment for possessing the electronic unit that solidfied material is made, the new conductive paste
Material, is impregnated with so as to the formation welding leaching on various base materials by effectively suppressing the inside of fusion welding metal and scaling powder
The excellent electrode of lubricant nature, the electrode formed by electrocondution slurry, with by solder metal formed it is electrical, mechanical engagement property and
The electrode of excellent electric conductivity.
The method for solving problem
The present inventor concentrate one's attention on to have studied using thermosetting resin (such as phenolic resin) as in the electrocondution slurry of adhesive,
Scaling powder or fusion welding metal is how set not to reach electrode deep.Its result is found：The coated particle of given shape is substantially
Horizontal direction avoids scaling powder and/or fusion welding metal being impregnated with vertical direction, suppresses excessive so as to realize
Be impregnated with.Furthermore, the present inventor also found simultaneously：Surface seems the import volume mistake of the coated particle of the beneficial given shape
When many, on the contrary, band is used as the variation or the deterioration of operability of the overall static state of electrocondution slurry and/or dynamic viscosity.
The present inventor is repeatedly analyzed and inquired into, and is as a result found：Only add the given shape of proper range amount coated
Grain, helps to solve above-mentioned various problems.Furthermore, it was found that also contribute to solve above-mentioned various ask using specific additive
Topic.
A kind of electrocondution slurry of the present invention contains conductive filling (A), thermosetting phenolic resin (B), unsaturated fat
Sour (C) and organic solvent (D).More specifically, the conductive filling (A) of the electrocondution slurry is to contain more than 0.1 volume % 30
Below volume % tabular is coated to particle (a1), the tabular be coated to particle using copper or copper alloy as core, by shell of silver,
The thickness degree of the shell is more than 0.02 μm and aspect ratio is more than 2.
Based on the electrocondution slurry, it can prevent or suppress scaling powder and/or fusion welding metal arrival electrode depth
Portion.Moreover, based on the electrocondution slurry, the variation of the overall static state of electrocondution slurry and/or dynamic viscosity can be being suppressed
Simultaneously, moreover it is possible to maintain good operability.In addition, as good operational specific one, slurry during silk-screen printing
Processing, expansion of the slurry on mask become easy.Moreover, in the transfer of silk-screen printing, can suppress or prevent attached
On impressing part (squeegee).
In addition, on above-mentioned electrocondution slurry, preferred embodiment is：The ball conversion that above-mentioned tabular is coated to particle (a1) is flat
An equal particle diameter is less than more than 0.1 μm 50 μm, moreover, the tabular is coated to 99% accumulation particle diameter of particle (a1)
D99 is less than 100 μm.
Furthermore, on above-mentioned electrocondution slurry, other preferred embodiments are：Above-mentioned conductive filling (A) also contains with copper
Spherical coated particle (a2) of the aspect ratio less than 2 for core, using silver as shell and/or using copper alloy as core, using silver to be outer
Spherical coated particle (a3) of the aspect ratio of shell less than 2.
Furthermore, on above-mentioned electrocondution slurry, other preferred embodiments are：Form the copper alloy of above-mentioned spherical coated particle (a3)
Alloy atom be nickel and/or zinc.
Furthermore, on above-mentioned electrocondution slurry, other preferred embodiments are：Form the copper alloy of above-mentioned spherical coated particle (a3)
Alloy atom content be below 30 atom %.
Furthermore, on above-mentioned electrocondution slurry, other preferred embodiments are：Above-mentioned thermosetting phenolic resin (B) is resol type
(resol type) phenolic resin.
Furthermore, on above-mentioned electrocondution slurry, other preferred embodiments are：Above-mentioned unrighted acid (C) is that carbon number is more than 6
Less than 20 unrighted acid.
Furthermore, on above-mentioned electrocondution slurry, other preferred embodiments are：Above-mentioned (D) composition be gylcol ether and/or
Terpene alcohols.
Furthermore, on above-mentioned electrocondution slurry, other preferred embodiments are：Above-mentioned conductive filling (A) is 100 parts by weight
When (being converted with solid content), above-mentioned thermosetting phenolic resin (B), above-mentioned unrighted acid (C) and above-mentioned organic solvent (D)
Content as described below：
Above-mentioned thermosetting phenolic resin (B)：More than 3 parts by weight below 30 parts by weight；
Above-mentioned unrighted acid (C)：More than 0.01 parts by weight below 5 parts by weight；
Above-mentioned organic solvent (D)：More than 3 parts by weight below 50 parts by weight.
Also, it is preferred that mode is：Also can be using the solidfied material for making above-mentioned electrocondution slurry be heating and curing to obtain or by this
The electrode that solidfied material is made.
In addition, as specific application examples, preferred embodiment is：It is placed with above-mentioned solidfied material or on above-mentioned electrode logical
The electronic equipment for the electronic unit crossed in the welding of solder slurry.
Furthermore, preferred embodiment is：The solder powder used in above-mentioned solder slurry is tin series lead-free solder powder.
But, " tabular is coated to particle " so-called in the application is not limited to a part of required of the particle surface
The meaning with plane.For example, the particle either formed by the microcosmic curved surface seen is generally planar when still macroscopically seeing
Situation, or see in the section of the particle situation of the line of general planar, be contained in " the tabular in the application
In coated particle ".Furthermore, " spherical coated particle " so-called in the application is not limited to the particle for real spherical shape
Particle the meaning.For example, if aspect ratio is less than 2, its section is elliptical shape or the local line for seeing general planar
Elliptical shape, is also contained in " the spherical coated particle " of the application.
Invention effect
Based on the electrocondution slurry of the present invention, it can prevent or suppress scaling powder and/or fusion welding metal is impregnated with
To electrode interior.Therefore, based on the present invention electrocondution slurry, can be formed on various base materials electric conductivity well and also fusion weld
The wellability of material also excellent electrode.
As a result, the electrocondution slurry based on the present invention, can form electric conductivity well and melt on various base materials
The wellability of solder also excellent electrode.
Brief description of the drawings
Fig. 1 is after existing electrocondution slurry (equivalent to comparative example 1) is coated on glass substrate and is allowed to solidification
On electrode, also make solder slurry melt when the cross-sectional image based on sweep electron microscope (SEM).
Fig. 2 be represent scaling powder be immersed in the electrode obtained by existing electrocondution slurry (equivalent to comparative example 1) inside,
It is the SEM cross-sectional images for the pattern to form island scaling powder phase with the result that adhesive resin mixes.
Fig. 3 represents that the diffusion of fusion welding metal is impregnated into and obtained by existing electrocondution slurry (equivalent to comparative example 1)
The SEM sectional views of the pattern of the inside of electrode.
In Fig. 4, photo (1) is when representing to make on existing electrocondution slurry (equivalent to comparative example 1) melting of solder slurry
Generate the optical photograph of the pattern of non-wetting (repelling (segregation, segregation)).Furthermore, photo (2) is represented by this implementation
On the electrode that the electrocondution slurry (equivalent to embodiment 1) of mode is made fusion welding well the pattern of infiltration spread optics shine
Piece.
Fig. 5 is the schematic diagram for the primary particle that tabular is coated to particle (a1).
Fig. 6 is to represent to block fusion welding metal (at this moment to refer in particular to being coated to practical physical by the tabular of (a1) composition
Tin) diffusion be impregnated into electrode interior with the formation of the electrocondution slurry of present embodiment pattern SEM sectional views.
Fig. 7 is Fig. 6 enlarged drawing.
Fig. 8 is the enlarged drawing of the particle swarm of the generation Ke Kendaer empty (Kirkendall void) in Fig. 6.
Fig. 9 is by having used the coated particle using copper-nickel-zinc alloy as core, by shell of silver to be used as conductive filler
(a3) sectional view for the electrode that the electrocondution slurry (corresponding with embodiment 17) of composition is made.
Embodiment
The electrocondution slurry of present embodiment be by containing defined tabular be coated to particle (a1) (hereinafter also referred to (a1) into
Part) conductive filling (A) (hereinafter also referred to (A) composition), thermosetting phenolic resin (B) (hereinafter also referred to (B) composition)
And unrighted acid (C) (hereinafter also referred to (C) composition) is matched with organic solvent (D) (hereinafter also referred to (D) composition)
Conductive composition.
The tabular that (A) composition of present embodiment contains more than 0.1 volume % below 30 volume % is coated to particle (a1)
(hereinafter also referred to (a1) composition), the tabular be coated to particle (a1) using copper or copper alloy as core, by shell of silver, the shell
Thickness degree be more than 0.02 μm and aspect ratio is more than 2.In addition, as the alloy atom for forming copper alloy, enumerate gold,
Silver, tin, nickel and zinc etc..Furthermore, (a1) composition by core of copper alloy, it is difficult to produce Ke Kendaer cavitations described later.
Fig. 5 is the ideograph (schematic diagram) for the primary particle 100 that tabular is coated to particle (a1).(a1) composition be with copper or
Person's copper alloy is core 10, with coated particle that silver is shell 20.(a1) composition is somebody's turn to do because its shape, by present embodiment
The obtained electrode of electrocondution slurry in, choose one part or all it is almost parallel relative to the in-plane of base material (at least
Out of plumb) position.In addition, the material for constituting core 10 both can be copper itself or copper and other metals (such as gold,
Silver, tin, nickel, zinc etc.) alloy.In addition, for the viewpoint for preventing corrosion, alloy kind is particularly preferably selected from nickel (Ni) and zinc
At least one of (Zn).Furthermore, the aspect ratio (hereinafter also referred to " AR ") of (a1) composition will turn into the one of (a1) composition
When maximum length in secondary particle is that L, thickness are t, it is referred to as aspect ratio (Aspect Ratio) than (L/t).
In the electrode obtained by the electrocondution slurry of present embodiment, above-mentioned (a1) composition be arranged at its a part or
Person is all on the position almost parallel relative to the in-plane of base material, as a result as shown in 6 or Fig. 7, because being capable of physics ground resistance
Disconnected solder alloy element (situation of two figures is tin) diffusion is impregnated into the electrode using the electrocondution slurry formation of present embodiment,
So the non-wetting of the fusion welding metal on electrode can be prevented or suppressed.More specifically, it is able to confirm that：Based on this
The tabular of embodiment is coated to the presence of particle (a1), and scaling powder and/or fusion weld are avoided in generally horizontal directions
Material metal is impregnated with vertical direction, can realize that suppressing excessive is impregnated with.
Moreover, what is interesting is the present inventors have additionally discovered that：The tabular that surface seems beneficial is coated to leading for particle (a1)
Enter amount it is excessive when, the variation or the deterioration of operability of static state and/or dynamic viscosity that electrocondution slurry is overall are brought on the contrary.This
Inventor further analyzes repeatedly and the result of discussion is：It also found：Conductive filling (A) is in more than 0.1 volume % 30
Particle (a1) is coated to containing tabular in below volume % scope, above-mentioned scaling powder or fusion welding can be solved simultaneously
Be impregnated with or present embodiment electrocondution slurry viscosity stability or operability during silk-screen printing etc. the problem of.
T in Fig. 5sMean the average thickness of shell formed in (a1) composition by silver, it is contemplated that present embodiment
When the electric conductivity of electrocondution slurry or the wellability of solder metal etc., preferably more than 0.02 μm, more preferably more than 0.05 μm 5 μm with
Under.The average thickness of shell still more preferably is less than more than 0.1 μm 1 μm.Even in addition, using copper or copper alloy as
Core, by shell of silver, tabular that aspect ratio is more than 2 be coated to particle, if using the thickness of the shell less than 0.02 μm
Material replace (a1) composition, it is not preferred at several aspects.When specifically, using the shell of such thickness, the resistance of electrode
Become sometimes big.Furthermore, scaling powder becomes easy to being impregnated with for the electrode interior, moreover, fusion welding gold on this electrode
The wellability of category can also be deteriorated.
T in Fig. 5cMean the thickness of the copper of formation core in (a1) composition or the particle of copper alloy, its value has no
It is particularly limited to.But, from wellability of printing, electric conductivity or solder metal for the electrocondution slurry for improving present embodiment etc.
Viewpoint for, preferably less than more than 0.1 μm 10 μm, more preferably about more than 0.3 μm, less than about 5 μm.Moreover, more
Further preferred copper or the thickness of the particle of copper alloy are more than about 0.5 μm about 3 μm or so following.
As described above, the L in Fig. 5 means the maximum length for the primary particle to form (a1) composition, t means that it is maximum
Thickness.Herein, on the surface of (a1) composition, the distance of fusion welding metal conduction (diffusion) is longer, more can effectively prevent
The diffusion in fusion welding metal to the electrode deep is impregnated with.According to this viewpoint, L is preferably more than 0.2 μm, more preferably about
More than 0.2 μm, less than about 100 μm.Moreover, more preferably L is less than more than about 2 μm about 50 μm.Furthermore, t is preferably 0.1
More than μm, more preferably about more than 0.1 μm, less than about 10 μm.Moreover, further preferably t is more than about 0.9 μm, greatly
Less than about 5 μm.
L, t, t of present embodimentsAnd tcEach value measured respectively by following method.
(1) solidfied material that is made up using any method mechanical cutting of the electrocondution slurry of present embodiment is consolidated using this
The electrode that compound is obtained.
(2) observe the section using sweep electron microscope (SEM) and image.
(3) section of the coated particle of some tabular silver based on composition (a1) composition occurred in obtained image
Region, at least directly measures L, t, t in five placessAnd tc, seek its average value.
As described above, in the present embodiment, (a1) composition is that its aspect ratio is more than 2.By using such (a1) into
Part, can effectively suppress or prevent fusion welding metal and/or scaling powder diffusion be impregnated into by present embodiment
The electrode interior that electrocondution slurry is made.Based on the insight that, the aspect ratio preferably about more than 2, about 100 of (a1) composition
Hereinafter, more preferably about more than 2.2, about less than 20.
Herein, the aspect ratio of representational (a1) composition of present embodiment can be obtained as described below.
First, the solidfied material or electrode of mechanical cutting present embodiment, the SEM cross-sectional images for obtaining 500 times or so (are joined
According to Fig. 6).Then, using the image as field range, the coated particle ((a1) composition) of some tabular silver is therefrom selected.Then,
Based on the L and t of (a1) composition, the aspect ratio (AR of some particle is obtained1).Then, similarly different five with
On field range, be coated to particle for amounting at least 100 tabulars, obtain its aspect ratio, they are added, obtain average
Value, thereby determines that the aspect ratio of (a1) composition.
The electrocondution slurry of present embodiment contains (a1) composition of the aspect ratio with above-mentioned defined.Therefore, as Fig. 6 with
And shown in Fig. 7, because can physically block fusion welding metal (referring exclusively to tin alloy in two figures) diffusion to be impregnated into by the slurry
The electrode interior being made, is improved so the wellability of the fusion welding metal on the electrode is bad.
Furthermore, the content that the tabular in conductive filling (A) ((A) composition) is coated to particle (a1) ((a1) composition) is
Below the volume % of more than 0.1 volume % 30.By using such volume ratio, the electrocondution slurry of present embodiment with when
Between the viscosity stability (change of viscosity stability) of passage become good, restrained effectively fusion welding metal and/
Or scaling powder is impregnated into the electrode interior obtained by the electrocondution slurry.The result is that the solder wettability and electric conductivity of the electrode
It is improved.Based on the insight that, the tabular in conductive filling (A) is coated to content preferably 0.3 body of particle (a1)
Product more than %, more preferably below 30 volume %, below the volume % of more than 0.5 volume % 30.
Furthermore, the granular size of (a1) composition is not particularly limited.But, in present embodiment, it is contemplated that electrocondution slurry
Viscosity or the flatness on surface of solidfied material (film) that is obtained by the electrocondution slurry etc., the average primary particle of ball conversion is straight
Preferably about more than 0.1 μm, less than about 50 μm of footpath.Moreover, more preferably about more than 0.5 μm, less than about 30 μm.And
And, preferred average a diameter of less than more than about 1.0 μm about 20 μm of the primary particle of ball conversion.Furthermore, (a1) composition
99% accumulation particle diameter D99 is preferably less than 100 μm, more preferably less than 70 μm.Moreover, preferred 99% accumulation particle
Diameter D99 is less than 50 μm.In addition, each particle diameter can use such as laser diffraction/scattering formula distribution of particles to determine device (for example
Micro- tracking meter (マ イ Network ロ ト ラ Star Network) FRA9220 of Leeds＆Northrup company systems) etc. obtain.
(a1) composition can also use commercial goods, but can use atomization method (atomize method) or plating
The various known method manufactures such as method.In the case of the latter's method, for example, obtained by (X), (Y) below progress.
(X) by using various machines, flat processing cathode copper powder or electrolysis copper alloy powder, copper reduction end or
Person reduces the raw material copper powders or raw material copper alloy at copper alloy powder and atomized copper powder end or atomization copper alloy powder etc.
Powder, makes its primary particle turn into above-mentioned thickness tcWriting board shape.
(Y) after (X), pass through electrolytic plating method or non-electrolytic plating method, so as to get tabular particle it is silver-plated.
In addition, by galvanoplastic, can not only be removed in galvanizing process be present in spherical bronze powder as raw material or
Oxide scale film on the surface of person's copper alloy powder, and can be than more uniform and be as one man coated on its surface using silver
On.The result is that exposed few coated particle of copper can be obtained.
Furthermore, as the other preferred embodiments that can be used, as needed, (A) composition also includes using copper as core, using silver as
Spherical coated particle (a2) (hereinafter also referred to (a2) composition) of the aspect ratio of shell less than 2 and/or using copper alloy as
The spherical coated particle (a3) (hereinafter also referred to (a3) composition) of core, the aspect ratio using silver as shell less than 2.By using (a2)
Composition and/or (a3) composition, when can allocate the viscosity of the electrocondution slurry of present embodiment or silk-screen printing can be controlled
Operability etc..Based on the insight that, the aspect ratio of (a2) composition and (a3) composition is preferably about more than 1 about 1.8
Hereinafter, more preferably about more than 1 about less than 1.5.In addition, such aspect ratio can use the method as (a1) composition
Obtain.
Furthermore, the content for forming the alloy atom of the copper alloy of (a3) composition is not particularly limited, but in order to ensure this reality
Apply the electric conductivity of the electrocondution slurry of mode, the content of alloy atom is preferably below 30 atom %, more preferably 20 atom % with
Under.The content of further preferred alloy atom is below 15 atom %.
In addition, as constitute (a3) composition slug particle, be preferably selected from copper-nickel alloy particle, copper-admiro particle with
And copper-nickel-zinc alloying pellet is any.Therefore, from corrosion resistance and suppression the leading based on alloying for improving slug particle
From the viewpoint of electrically deteriorating, nickel and/or zinc are preferably selected as alloy atom.
Furthermore, the content for constituting the alloy atom of the copper alloy of above-mentioned (a3) composition is not particularly limited.But, from making electricity
From the viewpoint of attachment function is so as to more can definitely improve good electric conductivity, other manner preferably is：
The content for forming the alloy atom of the copper alloy of spherical coated particle (a3) is below 30 atom %.
Furthermore, as one of (a3) composition, the weight rate of each atom is not particularly limited in copper-nickel alloy particle.
But, from the electric conductivity of electrocondution slurry or the viscosity stability of the electrocondution slurry and suppression Ke Kenda described later of the present invention
From the viewpoint of your cavity, copper: nickel is preferred to use about 99: about 1~about 85: about 15 scope.It is used as (a3) composition
One, the weight rate of each atom is not particularly limited in copper-zinc alloy particle.But, as nickel, from electric conductivity, glue
From the viewpoint of spending stability and suppressing empty, copper: zinc is preferred to use about 99: about 1~about 70: about 30 model
Enclose.Furthermore, as one of (a3) composition, the weight rate of each atom is not particularly limited in copper-nickel-zinc alloying pellet.But
It is, from the viewpoint of electric conductivity, viscosity stability, suppression cavity, copper: (nickel and zinc) is preferred to use about 99: about 1~big
About 70: about 30 scope.
Furthermore, the content of (a2) composition and/or (a3) composition in (A) composition is not particularly limited.But, from this
The viscosity stability of the electrocondution slurry of embodiment, the solder wettability of the electrode obtained by the electrocondution slurry and electric conductivity, with
And during silk-screen printing operability etc. from the viewpoint of, preferably approximately below the volume % of more than 70 volume % about 99.9 are more excellent
Select below the volume % of more than about 80 volume % about 99.5.Furthermore, further preferred range is more than about 90 volume %
Below about 99 volume %.
(a2) thickness of composition and the respective shell formed by silver of (a3) composition is not particularly limited.But, from this
The viscosity stability of the electrocondution slurry of embodiment, the solder wettability of the electrode obtained by the electrocondution slurry and electric conductivity, with
And during silk-screen printing operability etc. from the viewpoint of, preferably approximately less than more than 0.02 μm about 5 μm, more preferably from about 0.05
Less than about 3 μm more than μm.Furthermore, further preferred range is less than more than about 0.1 μm about 1 μm.In addition, such
Thickness can be obtained with the method same with (a1) composition.
(a2) thickness (diameter) of the core of the thickness (diameter) of the core of composition and (a3) composition is also not particularly limited.But
It is, it is contemplated that the electric conductivity of the electrocondution slurry of present embodiment, fusion welding metal phase are for the electricity that is obtained by the electrocondution slurry
Wellability of pole etc., more preferably from about all preferably approximately less than more than 0.1 μm about 20 μm, less than more than 0.3 μm about 15 μm.
(a2) composition and (a3) composition can use commercial goods, can also be manufactured with the method same with (a1) composition.
In addition, (a2) composition is the coated particle of silver using copper as slug particle.Moreover, being produced sometimes at the interface of the silver and copper
So-called Ke Kendaer cavities.So-called Ke Kendaer (Kirkendall) cavity is typically referred in certain metal and other herein
In the diffusion couple of metal contact, due to the former relative to the diffusion coefficient of the latter and the latter relative to the former diffusion coefficient not
Empty phenomenon is produced with and the contact interface.
When the phenomenon is applied to the electrocondution slurry of present embodiment, on the electrode obtained by the electrocondution slurry, for example, make
When having used the solder slurry melting of tin class lead-free solder powder, the core of tin atom and formation (a2) composition in fusion welding
Copper atom reacts, and forms alloy.At this moment, because the side of copper atom one is compared with tin atom, diffusion velocity is fast, so copper atom is to molten
Melt the side of solder metal one and there occurs more Mass movements.Its result is as shown in figure 8, sometimes in core-shell circle of (a2) composition
Face produces cavity.
On the other hand, because slug particle is copper alloy, (a3) composition is difficult to produce Ke Kendaer in core-shell interfaces
Cavity.Furthermore, when using (a3) composition, have fusion welding metal phase to the electrode that is made up of the electrocondution slurry of present embodiment
The advantage that wellability is improved.
Fig. 9 is made as having been used in (a3) composition using copper-nickel-zinc alloying pellet electrocondution slurry by obtained from core
The microscope enlarged photograph in the section of electrode.Almost do not see Ke Kenda in core-shell interfaces as shown in figure 9, being able to confirm that
You are empty.
In addition, using the situation of (a2) composition and (a3) composition simultaneously, the volume ratio of (a2) composition and (a3) composition does not have
It is particularly limited to.But, in the present embodiment, preferably approximately 1: about 9~about 9: about 1, more preferably from about 2: about 8~
About 8: about 2.Furthermore, further preferred range is about 3: about 7~about 7: about 3.
In addition, as needed, the conductive filler in addition to (a1) composition~(a3) composition can also be contained in (A) composition
Thing (hereinafter referred to as (a4) composition).Specifically, Argent grain, copper particle, nickel particle, copper-nickel alloy particle, gold are for example enumerated
Grain, the particle obtained by the alloy of these metals, nickel are coated to copper particle, are coated to copper particle, carbon particle of silver and nickel etc. successively.Again
The content of (a4) composition in person, (A) composition is also not particularly limited.But, (a1) composition and (a2) composition and/or
(a3) in the case that composition is in terms of 100 volume %, from solder metal is improved to the electricity that is made up of the electrocondution slurry of present embodiment
From the viewpoint of the wellability of pole, the electric conductivity of the electrocondution slurry of present embodiment, corrosion resistance of (A) composition etc., preferably adopt
With below the volume % of more than 0 volume % about 30 scope.
Furthermore, the purpose for using (B) composition is, fixed in the electrode obtained by the electrocondution slurry of present embodiment
(A) composition, while suppression fusion welding and liquid scaling powder are impregnated with to the diffusion of electrode interior.As one of (B) composition, do not have
There is special limitation, various known thermosetting phenolic resins, such as thermoplastic phenolic resin or resol type phenolic aldehyde tree can be used
Fat etc..In addition, can form the solidfied material of the present invention at relatively low temperatures from the burn into for suppressing (A) composition, make the solidification
The intensity of thing is appropriate and from the viewpoint of improving the adhesion of the solidfied material and base material, and thermosetting phenolic resin (B) is preferably
Resol type phenol resin.Furthermore, as one of the phenol as raw material, enumerate carbolic acid, cresols, amyl phenol, bis-phenol
A, butylphenol, octyl phenol, nonyl phenol, dodecyl phenol (dodecylphenol) etc..Furthermore, it is used as formaldehydes
One, enumerate formalin, paraformaldehyde etc..
In addition, together with (B) composition, other thermosetting binder resins can also be used (hereinafter referred to as on a small quantity simultaneously
(B ') composition).One of this kind of (B ') composition has thermosetting epoxy resin, melamine resin (melamine resin, melamine
Resin), polyamide-imide resin, polyimide resin etc..
Furthermore, as (C) composition, various known unrighted acids are enumerated, such as ω -3, ω -6, ω -9 not
Saturated fatty acid.As concrete example, stearic acid, sorbic acid, oleic acid, linoleic acid, 6 are enumerated, 10,14- hexadecatrienoic acids (6,
10,14-hexadecatrienoic acid, hiragonic acid, ヒ ラ go acid), eleostearic acid, punicic acid (プ ニ カ acid,
Punicic acid), linolenic acid, parinaric acid (モ ロ Network チ acid, moroctic acid), arachidonic acid etc..Its
In, from the viewpoint of wellability that can further improve fusion welding etc., the carbon number of unrighted acid (C) is (still
Except the carbon of decarboxylate) preferably approximately more than 6 about less than 20, preferably less than more than 16 20 unrighted acid.Wherein, especially
It is preferably selected from least one of oleic acid, linoleic acid and linolenic acid.In addition, because over time, present embodiment
The viscosity of electrocondution slurry have the tendency of easily to increase, so do not preferably use above-mentioned carbon number be about more than 6 about 20 with
Under saturated fatty acid (such as stearic acid) replace (C) composition.
In addition, using the reasons why (C) composition improves wellability and indefinite.It is generally recognised that, heating this embodiment party
During the electrocondution slurry of formula, its unsaturated bond is acted on (B) composition, the hardness increase for the continuous phase being made up of (B) composition, as a result
Liquid scaling powder is inhibited to be impregnated with to the diffusion of electrode interior.
Furthermore, as (D) composition, the fat such as enumerating ethanol, normal propyl alcohol (n-propanol), isopropanol, isobutanol
Race's alcohol；The terpenol of tertiary peonol (the Le terpaeonel of mono- ピ オ ネ of タ mono-) etc.；Carbiphene (diethylene
Glycol monoethyl ether), diethylene glycol monobutyl ehter (diethylene glycol monobutyl ether), two
Glycol list ethyl ether acetate (diethylene glycol monoethyl ether acetate ethylene glycol ethyl ethers ether acetic acids
Ester), diethylene glycol monobutyl ehter acetate (diethylene glycol monobutyl ether acetate), butyl card must
Glycol ether (glycol ether) class of alcohol (butyl carbitol), hexyl Carbitol (hexyl carbitol) etc.；Vinegar
Isopropyl propionate (vinegar acid isopropyl), ethyl propionate (ehyl propionate), benzoic acid butyl ester, oneself two
The esters of diethyl phthalate (diethyl adipate) etc.；N-hexane (n-hexane), dodecane (dodecane), tetradecene
Etc. (tetradecene) hydro carbons (hydrocarbon).One kind can be used alone in they, or can also be applied in combination two
Plant or two or more.Furthermore, because over time, the electrocondution slurry of present embodiment is difficult to viscosify, so especially excellent
Select and above-mentioned gylcol ether and/or terpene alcohols are used in (D) composition.It is especially considering that terpene alcohols dissolves (B)
Composition and (C) composition react the resin of the HMW of generation, therefore, restrained effectively the electrocondution slurry of present embodiment
Thickening.
The content (i.e. the content of filler composition) of (A) composition is not particularly limited in the electrocondution slurry of present embodiment,
But in view of electric conductivity or with the adhesion (being tightly engaged into property) of base material etc., 1 is integrally used as using the slurry that eliminates (D) composition
During volume fraction, preferably about more than 0.3 about less than 0.7, more preferably about more than 0.4 about less than 0.65.Enter one
The preferred scope about more than 0.45 about less than 0.6 of step.
Furthermore, the content (i.e. the content of adhesive composition) of (B) composition and (C) composition in the electrocondution slurry of present embodiment
It is not particularly limited, still, it is contemplated that electric conductivity or with the adhesion of base material etc., is integrally made with the slurry for eliminating (D) composition
During for 1 volume fraction, preferably about more than 0.7 or about less than 0.3, more preferably from about more than 0.65 or about less than 0.4.
Further preferred range about more than 0.6 or about less than 0.45.
Furthermore, the content of (A) composition~(D) composition is not particularly limited in the electrocondution slurry of present embodiment, still,
In terms of making the action effect of present embodiment for preferred degree, from the viscosity stability and printing adaptability of the slurry and
From the viewpoint of electric conductivity for the solidfied material being made up of the slurry etc., it is usually preferred to：It is 100 parts by weight (with solid using (A) composition
Composition converts) when, the content of (B) composition, (C) composition and (D) composition is as described below.
(B) composition：More than about 3 parts by weight below about 30 parts by weight, more than preferably approximately 5 parts by weight about 20 weight
Below part.
(C) composition：More than about 0.01 parts by weight below about 5 parts by weight, more than preferably approximately 0.03 parts by weight about
Below 2.5 parts by weight.
(D) composition：More than about 3 parts by weight below about 50 parts by weight, more than preferably approximately 5 parts by weight about 30 weight
Below part.
In addition, as needed, the curing accelerator of (B) composition can be coordinated (to remove in the electrocondution slurry of present embodiment
Equivalent to the material of (C) composition), thixotropic agent (thixo), fire retardant, viscosity modifier, smoothing agent, antioxidant, plasticizer,
The additive of activating agent, coupling agent etc.., can for example for the purpose of improving the electrocondution slurry of present embodiment and the adhesion of base material
To utilize coupling agent.As the example of coupling agent, silane system coupling agent, titanium system coupling agent, zirconium system coupling agent, the coupling of aluminium system are enumerated
Agent, chromium system coupling agent etc..
Using utensil known in gyratory shaker or planetary stirring machine, three-high mill etc., by stir mixing it is above-mentioned it is each into
Part can obtain the electrocondution slurry of present embodiment.Furthermore, the viscosity of obtained slurry is not particularly limited.But, based on cloth
The 10rpm (25 DEG C) of Luke Field rotary viscosimeter value, it is preferred to use about more than 0.1Pas about 300Pas
Following scope.
The solidfied material of present embodiment is that the electrocondution slurry of present embodiment is coated on various base materials and in fire-bar
Make under part (D) composition volatilize obtained from.Heating condition is not particularly limited.But, preferably approximately more than 130 DEG C of heating-up temperature
Less than about 200 DEG C, preferably approximately less than about 2 hours more than 0.2 hour heat time.
The species of base material is not particularly limited.Because the electrocondution slurry of present embodiment is the material of non-sintered type, institute
, can not only using the electrode of the ceramic electronic components as chip capacitor (chip condenser, superminiature capacitor) etc.
Enough using ceramic material as base material, and the electrocondution slurry of present embodiment can also apply to the base material or glass of glass etc.
Resin base material of epoxy resin, polyamide, polyimide resin, polyester resin etc. etc..
Coating method is also not particularly limited., can according to the purposes of the electrocondution slurry of present embodiment or its viscosity etc.
Using the various coating means such as silk-screen printing or distributor (dispenser).In addition, by being coated with repeatedly, can also make
The electrocondution slurry thick-film of present embodiment.
The shape of the solidfied material obtained by the electrocondution slurry of present embodiment is also not particularly limited.For example, the solidfied material
Can be plane (round shape, polygon-shaped etc.), any shape of wire.As one of the solidfied material of wire, enumerate in print
Wired circuit formed to wire on brush circuit board etc..
Moreover, the electrocondution slurry of above-mentioned embodiment, has mainly as the electrode being directly applied on electronic unit
With.The electronic equipment of present embodiment is placed with above-mentioned solidfied material or on above-mentioned electrode and welded by solder slurry
The various electronic units connected.
The solder metal used in solder slurry can be any of the solder containing lead and lead-free solder.As
Lead-free solder, such as Sn-Pb systems [Sn-35Pb], Sn-Ag systems [Sn-3.5Ag etc.], Sn-Cu systems [Sn-0.7Cu can be used
Deng], the lead powder of Sn-Ag-Cu systems [Sn-3Ag-0.5Cu etc.] end.That is, from the viewpoint of environmental protection, used in solder slurry
The preferred tin series lead-free solder powder of solder powder.In addition, these solder powders can also be containing In, Bi, Ge etc. metal member
Element.
<Embodiment>
Hereinafter, present embodiment is specifically described by each embodiment, it is apparent that being not to utilize these embodiments
To limit the scope of above-mentioned embodiment.In addition, table 1 is the list of following embodiment and each condition of comparative example.
Table 1
<(A) allotment of composition makes>
Embodiment 1
As shown in table 1, by the volume % of (a1) composition 20 below mixing, the volume % of (a2) composition 80, allotment makes (A)
Composition.
(a1) composition：The commercially available coated copper powders of tabular silver (trade name " HP0420M1 ", happiness star metal system, silver-colored shell
About 0.28 μm of thickness, average about 8 μm of the primary particle diameter of ball conversion, about 40 μm of 99% accumulation particle diameter D99).
(a2) composition：Spherical silver is coated to copper powders, and (trade name " 1400Y ", Mitsui Metal Co., Ltd.'s mining industry (strain) system, ball conversion are average
About 6 μm of primary particle diameter, about 12 μm of 99% accumulation particle diameter D99).
Then, using planet strrier should 85 parts of (A) composition (wherein (a1) composition 17 parts and 68 parts of (a2) composition),
It is used as 8.91 parts of the commercially available resol type phenol resin (trade name " BRL-275 ", Showa macromolecule (strain) system) of (B) composition, conduct
(C) 0.09 part of the oleic acid (and Wako Pure Chemical Industries (strain) system) of composition and it is used as the carbiphene acetate of (D) composition
6 parts of (hereinafter referred to as DEGA) is sufficiently mixed.Then, also mixed with three-high mill, allotment makes electrocondution slurry.In addition, such as the institute of table 1
Show, the volume % of (A) composition during removing (D) composition in the electrocondution slurry is 50.9%.Furthermore, (B) composition and (C) into
The volume % of part is 49.1%.
Embodiment 2
In addition to the oleic acid in embodiment 1 is replaced using linoleic acid, it is other in the same manner as in Example 1, allotment makes conductive
Slurry.
Embodiment 3
In addition to the oleic acid in embodiment 1 is replaced using leukotrienes, it is other in the same manner as in Example 1, allotment makes conductive
Slurry.
Embodiment 4
In embodiment 1, except the thickness using the shell relative to core be 0.15 μm, the average primary particle of ball conversion it is straight
Outside about 8 μm of footpath, about 40 μm of the 99% accumulation particle diameter D99 coated copper particle of tabular silver are as (a1) composition, its
It allocates in the same manner as in Example 1 and makes electrocondution slurry.
Embodiment 5
In embodiment 1, except the thickness using the shell relative to core be 0.5 μm, the average primary particle of ball conversion it is straight
Outside about 9 μm of footpath, about 41 μm of the 99% accumulation particle diameter D99 coated copper particle of tabular silver are as (a1) composition, its
It allocates in the same manner as in Example 1 and makes electrocondution slurry.
Embodiment 6
In embodiment 1, except the thickness using the shell relative to core is 0.75 μm, the average primary particle of ball conversion
Outside about 9 μm of diameter, about 41 μm of the 99% accumulation particle diameter D99 coated copper particle of tabular silver are as (a1) composition,
It is other in the same manner as in Example 1, allotment make electrocondution slurry.
Embodiment 7~8
In embodiment 1, in addition to the number of change (B) composition and (C) composition as shown in table 1, other and embodiment 1
Equally, allotment makes electrocondution slurry.
Embodiment 9
In embodiment 1, except the thickness using the shell relative to core be 0.02 μm, ball conversion particle diameter be 7 μm,
D99 for 40 μm 25 parts of conduct (a1) compositions of tabular particle, using 60 parts of above-mentioned " 1400Y " as (a2) composition outside, its
As it, allotment makes electrocondution slurry.
Embodiment 10~12
In embodiment 1, except used in change as shown in table 1 in addition to (A) composition, it is other in the same manner as in Example 1, adjust
With making electrocondution slurry.
Embodiment 13
In embodiment 1, by the volume % of (a1) composition 10 below mixing, the volume % of (a3) composition 90, allotment makes
(A) composition.
(a1) composition：The commercially available coated copper powders (trade name " HP0420M1 ") of tabular silver.
(a3) composition：Being coated to particle using copper-nickel alloy as the spherical silver of core, (about 0.12 μm of the thickness of outer shell, copper are closed
Nickel content in gold is 14 atom %, average about 2 μm of the primary particle diameter of ball conversion, 99% accumulation particle diameter D99 about 8
μm)。
Then, using planet strrier be sufficiently mixed 85 parts of (A) composition (wherein 8.5 parts of (a1) composition and (a3) into
Parts 76.5 parts), 8.91 parts of " BRL-275 (trade name) " as (B) composition, 0.09 part of oleic acid, Yi Jizuo as (C) composition
For DEGA6 parts of (D) composition.Thereafter further mixed with three-high mill, allotment makes electrocondution slurry.
Embodiment 14
In embodiment 13, except using the spherical silver using copper-nickel alloy as core to be coated to particle, (thickness of outer shell is about
0.12 μm, the content of nickel in copper alloy be 6 atom %, average about 2 μm of the primary particle diameter of ball conversion, 99% accumulation particle
About 8 μm of diameter D99) as outside (a3) composition, other as embodiment 13, allotment makes electrocondution slurry.
Embodiment 15
In embodiment 13, except using the spherical silver using copper-nickel alloy as core to be coated to particle, (thickness of outer shell is about
0.12 μm, the content of nickel in copper alloy be 1.3 atom %, average about 2 μm of the primary particle diameter of ball conversion, 99% accumulation
About 8 μm of grain diameter D99) as outside (a3) composition, other as embodiment 13, allotment makes electrocondution slurry.
Embodiment 16
In embodiment 13, except using the spherical silver using copper-zinc alloy as core to be coated to particle, (thickness of outer shell is about
0.12 μm, the content of zinc in copper alloy be 5.3 atom %, average about 2 μm of the primary particle diameter of ball conversion, 99% accumulation
About 10 μm of grain diameter D99) as outside (a3) composition, other as embodiment 13, allotment makes electrocondution slurry.
Embodiment 17
In embodiment 13, except using the spherical silver using copper-nickel-zinc alloy as core to be coated to the particle (thickness of outer shell
About 0.12 μm, the content of the nickel in copper alloy and zinc be respectively 7.7 atom %, 6.9 atom %, the average primary particle of ball conversion
About 3 μm of diameter, about 9 μm of 99% accumulation particle diameter D99) as outside (a3) composition, it is other as embodiment 13, adjust
With making electrocondution slurry.
Embodiment 18~19
After using (a3) composition shown in embodiment 13, (a2) composition shown in embodiment 1 is added, respectively with table 1
Shown ratio adjusts them, in addition, other as embodiment 13, and allotment makes electrocondution slurry.
Embodiment 20
Using (a3) composition shown in embodiment 13, commercially available Argent grain (trade name is added：AGC-239, FUKUDA METAL's paper tinsel
Powder industry (strain) system, average about 8 μm of primary particle diameter, about 40 μm of D99) (a4) composition is used as, afterwards, respectively with table 1
Shown ratio adjusts them, in addition, other as embodiment 13, and allotment makes electrocondution slurry.
Embodiment 21
Using (a3) composition shown in embodiment 13, above-mentioned " AGC-239 " is added as (a4) composition and is added
DEGA6 parts and tertiary 2 parts of conduct (D) compositions of peonol, afterwards, adjust them with the ratio shown in table 1 respectively, in addition, its
It is as embodiment 13, and allotment makes electrocondution slurry.
Comparative example 1
In embodiment 1, commercially available Argent grain (trade name is used instead of two kinds of (a1) composition and (a2) composition：AGC-
239th, FUKUDA METAL's paper tinsel powder industrial (strain) system, average about 8 μm of primary particle diameter, about 40 μm of D99.It is expressed as in table 1
(a4) composition), in addition, it is other in the same manner as in Example 1, allotment make electrocondution slurry.
Comparative example 2
In embodiment 1, by more 9 parts of the quantitative change of (B) composition and without using (C) composition, in addition, it is other with it is real
Apply as example 1, allotment makes electrocondution slurry.
Comparative example 3
In embodiment 1, it is coated for 0.009 μm of commercially available tabular silver using silver-colored shell thickness instead of (a1) composition
Copper particle (average about 8 μm of the primary particle diameter of ball conversion, about 40 μm of D99), in addition, it is other in the same manner as in Example 1,
Allotment makes electrocondution slurry.
Comparative example 4
In embodiment 1, commercially available epoxy resin (commodity are used instead of the resol type phenol resin as (B) composition
Name " jER828 ", Mitsubishi's resin (strain) system), in addition, it is other in the same manner as in Example 1, allotment make electrocondution slurry.
Comparative example 5~7
In embodiment 1, except change (a1) composition as shown in table 1, (a2) composition, (B) composition, (C) composition and (D) composition
Usage amount beyond, it is other in the same manner as in Example 1, allotment make electrocondution slurry.
Comparative example 8
In embodiment 1, using planet strrier be sufficiently mixed 85 parts of (A) composition (wherein 0.05 part of (a1) composition and
(a2) 84.95 parts of composition), 50.9 parts of " BRL-275 " as (B) composition, 0.09 part of oleic acid, the Yi Jizuo as (C) composition
For DEGA6 parts of (D) composition.Then, also mixed with three-high mill, allotment makes electrocondution slurry.In addition, being removed in the electrocondution slurry
The volume % for removing (A) composition during (D) composition is 50.9%.Furthermore, the volume % of (B) composition and (C) composition is 49.1%.
<The evaluation of the viscosity stability of electrocondution slurry>
On each embodiment and the various electrocondution slurries of each comparative example, commercially available Brookfield swinging is utilized
Viscosimeter (model HBT), is determined after just allocating the viscosity after making and being incubated 24 hours in 25 DEG C of thermostat respectively
Viscosity, based on calculating formula as shown below, the rate of viscosity increase of the electrocondution slurry is calculated using following calculating formula.In addition, surveying
It is scheduled on and carries out at room temperature.
<Calculating formula>
Rate of viscosity increase=[(25 DEG C, insulation 168 hours after viscosity-electrocondution slurry under 10rpm just allocated
The viscosity under 10rpm after making) ÷ (viscosity under 10rpm that electrocondution slurry is just allocated after making)] × 100
It is additionally contemplated that：Above-mentioned heat-retaining condition is the gluing in this experiment using temperature accelerated test as the heat-retaining condition being intended to
Degree increment rate has probably reproduced the rate of viscosity increase after being taken care of six months or so under less than 10 DEG C of environment more than 0 DEG C.Furthermore,
Rate of viscosity increase is evaluated based on following index.
◎ (fabulous)：Rate of viscosity increase is less than 20%
Zero (good)：Rate of viscosity increase is less than more than 20% 50%
△ (bad)：Rate of viscosity increase is more than 50%
As shown in table 1, it is thus identified that the viscosity stability of the electrocondution slurry of the embodiment 21 containing tertiary peonol is extremely excellent,
It is worth in this respect specifically mentioned.
<The making of electrode>
Using hollowed-out mask (stencill mask), (length about 35mm × width about 22mm × thickness is about
0.2mm), on glass substrate (length about 77mm × width about 27mm × thickness about 1.5mm), each reality is printed respectively
Apply the electrocondution slurry of example and each comparative example.The glass substrate obtained by the processing is put into thermostat, added at 150 DEG C
Heat 30 minutes, while solvent is volatilized, by solidifying adhesive resin, makes solidfied material (electrode).
<The evaluation of the electric conductivity of electrode>
On each embodiment and the various solidfied materials of each comparative example, using four terminals (probe) method, determine in room temperature
Under resistivity.Numerical value is smaller, it is meant that the electric conductivity of electrode is better.
<The evaluation of weldability, wellability>
There is the hollow metal mask (25 × width of length, 20 × thickness 0.2mm) in 6.5mm hole using center, with implementation
Example 1 electrocondution slurry formation electrode on, print Sn-3Ag-0.5Cu alloys solder slurry (trade name " VAPY LF219 ",
Waste river chemical industry (strain) system).Then, in an atmosphere, preparation heating 90 seconds at 150 DEG C, then at 240 DEG C, by just
Formula heating makes after solder melts completely, natural cooling.Then, with magnifying glass (10~20 times) or digital microscope (100~
200 times) pattern that the infiltration of solder metal extends is observed, evaluate wellability with following standard.On other embodiments and
The electrode of comparative example, is similarly welded, and evaluates their " wellability ".In addition, " wellability " is entered based on following index
Row is evaluated.
Zero (good)：Solder slurry is melted according to the shape after hollowed printing.
△ (level that can be used in limited purposes)：Solder surface produces concavo-convex, poor flatness.
× (poor)：On electrode, solder condenses and formed the state for repelling (segregation, segregation).
<The evaluation that fusion welding metal and scaling powder are impregnated with>
The glass substrate after welding of each embodiment viewed from above and each comparative example, visually observes fusion welding
Metal and solder soldering fluid are impregnated into the state of electrode (diffusion is impregnated with).Furthermore, with Cross section polishing (cross-sectional
Polishing) method cuts off each glass substrate, is observed using scanning electron microscope (multiplying power 300~10000), confirms molten
Melt solder metal and solder soldering fluid is impregnated into the state of electrode.In addition, " impregnability " is evaluated based on following index.
Zero (good)：Solder metal, solder soldering fluid are not impregnated into the reverse side up to glass substrate.
△ (level that can be used in limited purposes)：Solder metal is impregnated into the reverse side up to glass substrate.
× (poor)：Solder metal and solder soldering fluid are impregnated into the reverse side up to glass substrate.
Furthermore, the image of 500 times of the multiplying power based on above-mentioned scanning electron microscope is provided according in description of the invention
Method, using the cross-sectional image of each electrode of embodiment and comparative example, obtain (a1) composition, (a2) composition and (a3) composition
Aspect ratio.
<(a3) the empty evaluation in composition>
The image of 5000 times of the multiplying power based on above-mentioned scanning electron microscope, the side according to specified in description of the invention
Method, using the cross-sectional image of each electrode of embodiment and comparative example, observes the cavity in (a3) composition.In addition, being somebody's turn to do " cavity "
It is to be evaluated based on following index.
◎ (fabulous)：In cross-sectional SEM image, in the periphery for the core being made up of copper alloy particle, do not exist or
Cavity can hardly be confirmed.
Zero (good)：In the SEM photograph of section, in the periphery for the core being made up of copper alloy particle, make out seldom
Cavity.
Above-mentioned embodiment or the disclosure of embodiment is recorded for illustrating the embodiment or embodiment,
It is not intended to the restriction present invention and records.Moreover, being present in other combinations containing above-mentioned embodiment or embodiment
The scope of the invention in variation be also contained in the range of invention is claimed.
Industrial applicibility
Above-mentioned embodiment and the electrocondution slurry of each embodiment are mainly used as electrode or the printed wiring of electronic unit
The electrode of the wiring of substrate etc..Furthermore, in addition, can also be applied to each of slug type and non-sintered electrocondution slurry
Plant purposes.The electrocondution slurry of such as present embodiment can be applied to capacitor outer electrode, solar cell conducting channel,
Ito glass electrode, TO glass electrodes, welding conducting portion of printed circuit etc..
Furthermore, possess the solidfied material, electronic unit or electronic equipment of the electrocondution slurry of each above-mentioned embodiment with it is upper
The electrocondution slurry for each embodiment stated is the same, can also be applied to the purposes of wide scope.
Claims (13)
1. a kind of electrocondution slurry, it is characterised in that contain：
Conductive filling (A), the conductive filling contains coated of tabular more than 0.1 volume % below 30 volume %
Grain (a1), the tabular is coated to particle (a1) using copper or copper alloy as core, using silver as shell, and the thickness degree of the shell is 0.02
More than μm and aspect ratio be more than 2；
Thermosetting phenolic resin (B)；
Unrighted acid (C)；And
Organic solvent (D),
Wherein, the electrocondution slurry be by the conductive filling (A), the thermosetting phenolic resin (B) and it is described not
Saturated fatty acid (C) is matched with electrocondution slurry obtained from the organic solvent (D).
2. electrocondution slurry as claimed in claim 1, it is characterised in that
The tabular is coated to average a diameter of less than more than 0.1 μm 50 μm of the primary particle of the ball of particle (a1) conversion, moreover, institute
State tabular and be coated to 99% accumulation particle diameter D99 of particle (a1) for less than 100 μm.
3. electrocondution slurry as described in claim 1 or 2, it is characterised in that
The conductive filling (A) is also containing spherical coated particle of the aspect ratio less than 2 using copper as core, using silver as shell
And/or spherical coated particle (a3) of the aspect ratio using copper alloy as core, using silver as shell less than 2 (a2).
4. electrocondution slurry as claimed in claim 3, it is characterised in that
The alloy atom for forming the copper alloy of the spherical coated particle (a3) is nickel and/or zinc.
5. electrocondution slurry as claimed in claim 3, it is characterised in that
The content for forming the alloy atom of the copper alloy of the spherical coated particle (a3) is below 30 atom %.
6. electrocondution slurry as described in claim 1 or 2, it is characterised in that
The thermosetting phenolic resin (B) is resol type phenol resin.
7. electrocondution slurry as described in claim 1 or 2, it is characterised in that
The unrighted acid (C) is the unrighted acid that carbon number is less than more than 6 20.
8. electrocondution slurry as described in claim 1 or 2, it is characterised in that
(D) composition is gylcol ether and/or terpene alcohols.
9. electrocondution slurry as described in claim 1 or 2, it is characterised in that
When the conductive filling (A) is 100 parts by weight (being converted with solid content), the thermosetting phenolic resin (B), institute
State the content of unrighted acid (C) and the organic solvent (D) as shown below：
The thermosetting phenolic resin (B)：More than 3 parts by weight below 30 parts by weight；
The unrighted acid (C)：More than 0.01 parts by weight below 5 parts by weight；
The organic solvent (D)：More than 3 parts by weight below 50 parts by weight.
10. a kind of solidfied material, it is characterised in that
Obtained by heating electrocondution slurry according to any one of claims 1 to 9 and solidifying the electrocondution slurry.
11. a kind of electrode, it is characterised in that
It is made up of the solidfied material described in claim 10.
12. a kind of electronic equipment, it is characterised in that
It is placed with the solidfied material that claim 10 is recorded or on the electrode of claim 11 record by weldering
Electronic unit in the welding of slurry material.
13. electronic equipment as claimed in claim 12, it is characterised in that
The solder powder used in the solder slurry is tin series lead-free solder powder.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012082076 | 2012-03-30 | ||
| JP2012-082076 | 2012-03-30 | ||
| PCT/JP2013/059698 WO2013147235A1 (en) | 2012-03-30 | 2013-03-29 | Conductive paste, hardened material, electrode, and electronic device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104246909A CN104246909A (en) | 2014-12-24 |
| CN104246909B true CN104246909B (en) | 2017-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380017276.4A Active CN104246909B (en) | 2012-03-30 | 2013-03-29 | Electrocondution slurry, solidfied material, electrode and electronic equipment |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5462984B1 (en) |
| CN (1) | CN104246909B (en) |
| WO (1) | WO2013147235A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2014098036A1 (en) * | 2012-12-21 | 2017-01-12 | ペルノックス株式会社 | Conductive paste |
| JP6187226B2 (en) * | 2013-12-16 | 2017-08-30 | 富士通株式会社 | Manufacturing method of electronic device |
| WO2015122345A1 (en) * | 2014-02-12 | 2015-08-20 | 東レ株式会社 | Conductive paste, method for producing pattern, method for producing conductive pattern, and sensor |
| JP2016004659A (en) * | 2014-06-16 | 2016-01-12 | 株式会社村田製作所 | Conductive resin paste and ceramic electronic part |
| KR102417311B1 (en) | 2014-07-22 | 2022-07-07 | 알파 어셈블리 솔루션스 인크. | Stretchable interconnects for flexible electronic surfaces |
| JP5941588B2 (en) * | 2014-09-01 | 2016-06-29 | Ｄｏｗａエレクトロニクス株式会社 | Bonding material and bonding method using the same |
| CN109509568B (en) * | 2017-12-29 | 2021-06-08 | 太原氦舶新材料有限责任公司 | High-performance conductive silver paste |
| JP2020004524A (en) * | 2018-06-26 | 2020-01-09 | ナミックス株式会社 | Conductive paste for vacuum printing |
| KR102600380B1 (en) | 2018-12-05 | 2023-11-09 | 상라오 징코 솔라 테크놀러지 디벨롭먼트 컴퍼니, 리미티드 | Solar cell and method for manufacturing the same, and solar cell panel |
| JP7491246B2 (en) | 2021-03-12 | 2024-05-28 | 株式会社村田製作所 | Conductive paste and ceramic electronic components |
| JP2023000704A (en) | 2021-06-18 | 2023-01-04 | パナソニックＩｐマネジメント株式会社 | Conductive paste and conductive film formed using the same |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2558013B2 (en) * | 1990-11-30 | 1996-11-27 | 株式会社トクヤマ | Conductive copper paste composition and method for producing the same |
| JPH08311304A (en) * | 1995-05-16 | 1996-11-26 | Mitsui Kinzoku Toryo Kagaku Kk | Copper-based electroconductive composition |
| US6322620B1 (en) * | 2000-11-16 | 2001-11-27 | National Starch And Chemical Investment Holding Corporation | Conductive ink composition |
| JP4224771B2 (en) * | 2002-05-15 | 2009-02-18 | 日立化成工業株式会社 | Conductive paste |
| JP4389148B2 (en) * | 2002-05-17 | 2009-12-24 | 日立化成工業株式会社 | Conductive paste |
| US20090211626A1 (en) * | 2008-02-26 | 2009-08-27 | Hideki Akimoto | Conductive paste and grid electrode for silicon solar cells |
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2013
- 2013-03-29 WO PCT/JP2013/059698 patent/WO2013147235A1/en active Application Filing
- 2013-03-29 CN CN201380017276.4A patent/CN104246909B/en active Active
- 2013-03-29 JP JP2013534524A patent/JP5462984B1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013147235A1 (en) | 2013-10-03 |
| CN104246909A (en) | 2014-12-24 |
| JPWO2013147235A1 (en) | 2015-12-14 |
| JP5462984B1 (en) | 2014-04-02 |
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