CN104246909A - Conductive paste, hardened material, electrode, and electronic device - Google Patents

Conductive paste, hardened material, electrode, and electronic device Download PDF

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Publication number
CN104246909A
CN104246909A CN201380017276.4A CN201380017276A CN104246909A CN 104246909 A CN104246909 A CN 104246909A CN 201380017276 A CN201380017276 A CN 201380017276A CN 104246909 A CN104246909 A CN 104246909A
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composition
electrocondution slurry
particle
electrode
copper
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CN201380017276.4A
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CN104246909B (en
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岩村荣治
相泽贵之
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Arakawa Chemical Industries Ltd
Pelnox Ltd
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Arakawa Chemical Industries Ltd
Pelnox Ltd
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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
    • 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
    • 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
    • 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

This conductive paste comprises a conductive filler (A), a thermosetting phenolic resin (B), an unsaturated fatty acid (C), and an organic solvent (D). More specifically, the conductive filler (A) of the conductive paste has copper or a copper alloy as a core and silver as a shell. The thickness of the shell is 0.02 [mu]m or more. Flat-plate-shaped coated particles (a1) having an aspect ratio of 2 or more are included at 0.1-30 vol%.

Description

Electrocondution slurry, solidfied material, electrode and electronic equipment
Technical field
The present invention relates to a kind of electrocondution slurry, the solidfied material obtained by this electrocondution slurry, the electrode be made up of this solidfied material and electronic equipment.
Background technology
So-called electrocondution slurry typically refers to the conductive composition that the granular conductive filling such as silver (Ag) or copper (Cu), nickel (Ni), tin (Sn), aluminium (Al), carbon black and the thermosetting binder resins such as phenolic resins or epoxy resin are coordinated with organic solvent and made.And electrocondution slurry easily and imperceptibly can form the electrode of various shape by silk screen printing etc., be therefore applied on various electronic equipment or electronic product.
At present, as the conductive filling of excellent electric conductivity, employ copper and silver.But its problem is, copper is widely used because of low price, its reverse side is due to easy oxidation, thus causes the conductivity of electrocondution slurry unstable.On the other hand, even if silver is oxidized also produce similar problem hardly, but expensive.Therefore, in this field, usually use together with Argent grain, or replace, use the composite particles formed by silver-colored covering copper particle.
, with by this kind of composite particles be used as conductive filling electrocondution slurry formed electrode, on this electrode face welding electronic unit time, there is the situation of the wettability difference of the solder metal of melting.Particularly in the solder slurry of lead-free solder powder employing tin-silver-copper etc., this problem is remarkable.Its reason is various, but, it has been generally acknowledged that one of its reason is that the interfacial energy between solder metal-electrode increases, and result is that fusion welding metal does not infiltrate expansion because the tin in fusion welding and the reaction of the composite particles in electrode form alloy.
As solving the method for the wettability difference of solder in the electrocondution slurry of Argent grain or above-mentioned composite particles of employing, as described in patent document 1, which, the known thermoplastic resin of adhesive resin and the glass transition temperature of being used as is the saturated polyester of about 60 ~ 100 DEG C.
At first technical literature
Patent documentation 1: Japanese Unexamined Patent Publication 6-295616 publication.
Summary of the invention
But the present inventor has carried out detailed analysis and discussion based on the new starting point shown below, the present inventor has learnt that the electrocondution slurry utilized using thermoplastic resin as adhesive does not fully eliminate the situation of wettability deficiency.
First, the inside of the electrode obtained by electrocondution slurry is formed by with the phase of the self-existent conductive filler of the form contacted with each other and the substantial continuous phase be made up of the adhesive resin riddling its space.
Then, Fig. 1 is the sectional view based on scanning electron microscopy (SEM) when being coated by existing electrocondution slurry (being equivalent to comparative example 1 described later) on glass baseplate and to make it on the electrode after solidifying and to make the melting of solder slurry.As shown in Figure 1, the pattern that scaling powder (Flux) is expanded in the mode covering the solder alloy after melting (white lug boss) can be confirmed.More specifically, when the electrode be made up of existing electrocondution slurry makes solder slurry (solder paster) melting, the liquid scaling powder oozed out is impregnated into electrode interior in the mode covering solder metal, enters with the state mixed with adhesive resin.
But, when the scaling powder of formation solder slurry excessively enters into electrode interior, the activating agent of the surface oxidation of the solder metal in solder slurry should be suppressed to reduce on surface, namely, run off 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 view of the electrode obtained by existing electrocondution slurry.As shown in Figure 2, known: it is that scaling powder forms independently phase that scaling powder enters into adhesive resin result mutually.This adhesive resin is formed by the thermosetting phenolic resin by being heating and curing, although adhesive resin is the phase of rigid mutually, can not prevent soaking into of scaling powder completely.Its result demonstrates: such as use mylar this kind of by thermoplastic thermoplastic resin as adhesive resin time, scaling powder can not be suppressed all the more to be impregnated into inside.
On the other hand, as shown in the SEM sectional view of Fig. 3, make solder slurry on the electrode obtained by existing electrocondution slurry during melting, the solder metal of melting is also impregnated into electrode interior.But the intensity that being soaked in a certain degree guarantees welded joint is absolutely necessary, and when fusion welding metal too arrives deep, that situation, the fusion weld doses on electrode reduces.
Like that, as shown in Figure 4, on electrode, fusion welding metal may be described as the state (part is with reference to figure (1)) of be ostracised (segregation, segregation), and result is judged as wettability difference.At this moment, due to solder melting at a relatively high temperature, therefore it has been generally acknowledged that when adhesive is by the electrode that thermoplastic resin is formed mutually, it is inner that the solder metal of melting accelerates to be impregnated into softening resin more.On the other hand, when on electrode, fusion welding metal infiltrates and expands, do not occur such repulsion (segregation, segregation) (part is with reference to figure (2)), welding (soldering) is good.
The problem that invention will solve
Tremendous contribution of the present invention is: provide a kind of new electrocondution slurry, the solidfied material obtained by this electrocondution slurry, the electrode be made up of this solidfied material, have the electronic unit of this electrode and possess the electronic equipment of this electronic unit, this new electrocondution slurry, soaks into by effectively suppressing the inside of fusion welding metal and scaling powder thus can form the electrode of welding wettability excellence, the electrode namely formed by electrocondution slurry, electrode with electrical, the mechanical engagement formed by solder metal and excellent electric conductivity on various base material.
Solve the method for problem
The present inventor is concentrated have studied using thermosetting resin (such as phenolic resins) as in the electrocondution slurry of adhesive, how to make scaling powder or fusion welding metal not arrive electrode deep.It found that: the coating particle of given shape avoids scaling powder and/or fusion welding metal soaking in the vertical direction in general horizontal direction, thus can realize suppressing excessive soaking into.Moreover the present inventor also finds simultaneously: when surface seems that the import volume of the coating particle of this useful given shape is too much, on the contrary, band is used as the deterioration of the static state of electrocondution slurry entirety and/or the variation of dynamic viscosity or operability.The present inventor analyzes repeatedly and inquires into, and found that: the coating particle only adding this given shape of proper range amount, contributes to solving above-mentioned various problem.Moreover, also find to adopt specific additive also to contribute to solving above-mentioned various problem.
A kind of electrocondution slurry of the present invention contains conductive filling (A), thermosetting phenolic resin (B), unrighted acid (C) and organic solvent (D).More specifically, the conductive filling (A) of this electrocondution slurry is, tabular containing 0.1 more than volume % 30 volume below % is coated to particle (a1), this tabular be coated to particle with copper or copper alloy be core, take silver as shell, the layer thickness of this shell is that more than 0.02 μm and aspect ratio are for more than 2.
Based on this electrocondution slurry, can prevent or suppress scaling powder and/or fusion welding metal to arrive electrode deep.And, based on this electrocondution slurry, while the variation of the static state and/or dynamic viscosity that can suppress electrocondution slurry entirety, good operability can also be maintained.In addition, as a concrete example of good operability, process, the expansion of slurry on mask of slurry during silk screen printing become easy.And, when the transfer printing of silk screen printing, can suppress or prevent from being attached on impression part (squeegee).
In addition, about above-mentioned electrocondution slurry, optimal way is: the ball that above-mentioned tabular is coated to particle (a1) the average primary particle diameter that converts is more than 0.1 μm less than 50 μm, and the 99% accumulation particle diameter D99 that this tabular is coated to particle (a1) is less than 100 μm.
Moreover, about above-mentioned electrocondution slurry, other optimal way is: above-mentioned conductive filling (A) also containing is core with copper, take silver as the spherical coating particle (a2) of the aspect ratio of shell less than 2 and/or be core with copper alloy, take silver as the spherical coating particle (a3) of the aspect ratio of shell less than 2.
Moreover about above-mentioned electrocondution slurry, other optimal way is: the alloy atom forming the copper alloy of above-mentioned spherical coating particle (a3) is nickel and/or zinc.
Moreover about above-mentioned electrocondution slurry, other optimal way is: the content forming the alloy atom of the copper alloy of above-mentioned spherical coating particle (a3) is 30 below atom %.
Moreover about above-mentioned electrocondution slurry, other optimal way is: above-mentioned thermosetting phenolic resin (B) is resol type (resol type) phenolic resins.
Moreover about above-mentioned electrocondution slurry, other optimal way is: above-mentioned unrighted acid (C) to be carbon number be less than more than 6 20 unrighted acid.
Moreover about above-mentioned electrocondution slurry, other optimal way is: above-mentioned (D) composition is gylcol ether and/or terpene alcohols.
Moreover, about above-mentioned electrocondution slurry, other optimal way is: above-mentioned conductive filling (A) be 100 weight portions (with solid content convert) time, the content of above-mentioned thermosetting phenolic resin (B), above-mentioned unrighted acid (C) and above-mentioned organic solvent (D) as described below:
Above-mentioned thermosetting phenolic resin (B): more than 3 weight portions below 30 weight portions;
Above-mentioned unrighted acid (C): more than 0.01 weight portion below 5 weight portions;
Above-mentioned organic solvent (D): more than 3 weight portions below 50 weight portions.
And optimal way is: also can adopt the solidfied material making above-mentioned electrocondution slurry be heating and curing to obtain or the electrode be made up of this solidfied material.
In addition, as concrete application examples, optimal way is: be placed with the electronic equipment by the electronic unit in the welding of solder slurry on above-mentioned solidfied material or on above-mentioned electrode.
Moreover optimal way is: the solder powder used in above-mentioned solder slurry is tin series lead-free solder powder.
, so-called in the application " tabular is coated to particle ", the part being not limited to this particle surface must have the meaning of plane.Such as, when being no matter the particle of the Surface forming seen by microcosmic but macroscopically seeing, be roughly the situation of plane, or in the cross section of this particle, see the situation of line of general planar, in all involved " tabular is coated to particle " in this application.Moreover so-called in the application " spherical coating particle ", is not limited to the meaning that this particle is the particle of real spherical shape.Such as, if aspect ratio is less than 2, its cross section is the elliptical shape that the line of general planar is seen in elliptical shape or local, is also comprised in " tabular is coated to particle " of the application.
Invention effect
Based on electrocondution slurry of the present invention, can prevent or suppress scaling powder and/or fusion welding metal to be impregnated into electrode interior.Therefore, based on electrocondution slurry of the present invention, the electrode that conductivity wettability that is good and fusion welding is also excellent can be formed on various base material.
Consequently, based on electrocondution slurry of the present invention, the electrode that conductivity wettability that is good and fusion welding is also excellent can be formed on various base material.
Accompanying drawing explanation
Fig. 1 be existing electrocondution slurry (being equivalent to comparative example 1) to be coated on glass substrate and to make it on the electrode after solidifying, also make the melting of solder slurry time the cross-sectional image based on sweep electron microscope (SEM).
Fig. 2 be represent inside that scaling powder is immersed in the electrode obtained by existing electrocondution slurry (being equivalent to comparative example 1), SEM cross-sectional image that the result mixed with adhesive resin is the pattern forming island scaling powder phase.
Fig. 3 represents that the diffusion of fusion welding metal is impregnated into the SEM sectional view of the pattern of the inside of the electrode obtained by existing electrocondution slurry (being equivalent to comparative example 1).
In Fig. 4, photo (1) represents the optical photograph making the pattern creating non-wetting (repelling (segregation, segregation)) during the melting of solder slurry on existing electrocondution slurry (being equivalent to comparative example 1).Moreover photo (2) is the optical photograph representing the pattern of infiltration spread well of fusion welding on the electrode made at the electrocondution slurry (being equivalent to embodiment 1) by present embodiment.
Fig. 5 is the schematic diagram that tabular is coated to the primary particle of particle (a1).
Fig. 6 represents that blocking fusion welding metal (at this moment refering in particular to tin) with being coated to practical physical by the tabular of (a1) composition spreads the SEM sectional view being impregnated into the pattern of the electrode interior formed with the electrocondution slurry of present embodiment.
Fig. 7 is the enlarged drawing of Fig. 6.
Fig. 8 is the enlarged drawing of the particle swarm in generation Ke Kendaer cavity (Kirkendall void) in Fig. 6.
Fig. 9 is by employing using the sectional view of the electrode that copper-nickel-kirsite is core, to take silver as the coating particle of shell make as the electrocondution slurry (corresponding with embodiment 17) of (a3) composition of conductive filler.
Embodiment
The electrocondution slurry of present embodiment is the conductive composition conductive filling (A) (hereinafter also referred to (A) composition) being coated to particle (a1) (hereinafter also referred to (a1) composition) containing the tabular specified, thermosetting phenolic resin (B) (hereinafter also referred to (B) composition) and unrighted acid (C) (hereinafter also referred to (C) composition) are matched with in organic solvent (D) (hereinafter also referred to (D) composition).
The tabular that (A) composition of present embodiment contains 0.1 more than volume % 30 volume below % is coated to particle (a1) (hereinafter also referred to (a1) composition), this tabular be coated to particle (a1) with copper or copper alloy be core, take silver as shell, the layer thickness of this shell is that more than 0.02 μm and aspect ratio are for more than 2.In addition, as the alloy atom forming copper alloy, gold, silver, tin, nickel and zinc etc. are enumerated.Moreover, take copper alloy as (a1) composition of core, be difficult to produce Ke Kendaer cavitation described later.
Fig. 5 is the ideograph (schematic diagram) that tabular is coated to the primary particle 100 of particle (a1).(a1) composition is core 10 with copper or copper alloy, take silver as the coating particle of shell 20.Should (a1) composition because its shape, so in the electrode obtained at the electrocondution slurry by present embodiment, choose the position of its part or all almost parallel relative to the in-plane of base material (at least out of plumb).In addition, the material forming core 10 both can be copper self, also can be the alloy of copper and other metal (such as gold, silver, tin, nickel, zinc etc.).In addition, from the viewpoint preventing from corroding, alloy kind is particularly preferably selected from least one in nickel (Ni) and zinc (Zn).Moreover, (a1) aspect ratio (hereinafter also referred to " AR ") of composition, namely the maximum length that will become in the primary particle of (a1) composition be L, thickness be t time, it is called aspect ratio (Aspect Ratio) than (L/t).
In the electrode that the electrocondution slurry by present embodiment obtains, above-mentioned (a1) composition is arranged on its part or all position almost parallel relative to the in-plane of base material, result is as shown in 6 or Fig. 7, because physically can block solder alloy element (situation of two figure is tin) diffusion is impregnated in the electrode using the electrocondution slurry of present embodiment to be formed, so can prevent or suppress the non-wetting of the fusion welding metal on electrode.More particularly, can confirm: the tabular based on present embodiment is coated to the existence of particle (a1), avoid scaling powder and/or fusion welding metal to soak in the vertical direction in generally horizontal directions, can realize suppressing excessive soaking into.
And, what is interesting is that the present inventor has also found: surface seem useful tabular be coated to the import volume of particle (a1) too much time, bring the deterioration of the static state of electrocondution slurry entirety and/or the variation of dynamic viscosity or operability on the contrary.The result that the present inventor repeatedly analyzes further and inquires into is: also found: conductive filling (A) is coated to particle (a1) containing tabular in the scope of 0.1 more than volume % 30 volume below %, can solve simultaneously above-mentioned scaling powder or fusion welding soak into or the viscosity stability of electrocondution slurry of present embodiment or silk screen printing time the problem of operability etc.
T in Fig. 5 smean the average thickness of the shell formed by silver in (a1) composition, when considering the wettability etc. of the conductivity of the electrocondution slurry of present embodiment or solder metal, preferably more than 0.02 μm, more preferably more than 0.05 μm less than 5 μm.Further the average thickness of preferred shell is more than 0.1 μm less than 1 μm.In addition, even with copper or copper alloy be core, take silver as shell, aspect ratio be more than 2 tabular be coated to particle, if use the material of the thickness of described shell less than 0.02 μm to replace (a1) composition, not preferred in several.Particularly, when adopting the shell of this type of thickness, the resistance of electrode becomes large sometimes.Moreover scaling powder becomes easy to soaking into of this electrode interior, and the wettability of fusion welding metal on this electrode also can be deteriorated.
T in Fig. 5 cmean the thickness of the copper of formation core in (a1) composition or the particle of copper alloy, its value is not particularly limited.But, from the viewpoint of wettability etc. improving the printing of electrocondution slurry of present embodiment, conductivity or solder metal, be preferably more than 0.1 μm less than 10 μm, be more preferably about more than 0.3 μm, about less than 5 μm.And further the thickness of the particle of preferred copper or copper alloy is about more than 0.5 μm about less than about 3 μm.
As mentioned above, the L in Fig. 5 means the maximum length of the primary particle of formation (a1) composition, and t means its maximum ga(u)ge.Herein, on the surface of (a1) composition, the distance of fusion welding metal conduction (diffusion) is longer, more can effectively prevent this fusion welding metal from soaking into the diffusion in electrode deep.According to this viewpoint, L is preferably more than 0.2 μm, is more preferably about more than 0.2 μm, about less than 100 μm.And more preferably L is about more than 2 μm about less than 50 μm.Moreover t is preferably more than 0.1 μm, be more preferably about more than 0.1 μm, about less than 10 μm.And preferably t is about more than 0.9 μm, about less than 5 μm further.
L, t, t of present embodiment sand t ceach value measure respectively by following method.
(1) solidfied material utilizing any method mechanical cutting to be made up of the electrocondution slurry of present embodiment or the electrode using this solidfied material to obtain.
(2) sweep electron microscope (SEM) is utilized to observe this cross section and make a video recording.
(3) based on the cross section of the coating particle of some tabular silver of the formation occurred in the image obtained (a1) composition, at least directly L, t, t is measured in five places sand t c, ask its mean value.
As mentioned above, in the present embodiment, (a1) composition is its aspect ratio is more than 2.By adopting this type of (a1) composition, can effectively suppress or prevent fusion welding metal and/or scaling powder diffusion to be impregnated into the electrode interior be made up of the electrocondution slurry of present embodiment.Based on such viewpoint, the aspect ratio of (a1) composition is preferably about more than 2, about less than 100, is 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 of mechanical cutting present embodiment or electrode, obtain the SEM cross-sectional image (with reference to Fig. 6) of about 500 times.Then, with this image for field range, the therefrom coating particle ((a1) composition) of selected some tabular silver.Then, based on L and t of this (a1) composition, obtain the aspect ratio (AR of this some particle 1).Then, the field range similarly more than different five, is coated to particle for total at least 100 tabulars, obtains its aspect ratio, they are added, obtain mean value, determine the aspect ratio of (a1) composition thus.
The electrocondution slurry of present embodiment contains (a1) composition of the aspect ratio with above-mentioned defined.Therefore, as shown in Fig. 6 and Fig. 7, because fusion welding metal (two figure special secondary schools refer to ashbury metal) diffusion physically can be blocked be impregnated into the electrode interior be made up of this slurry, be improved so the wettability of fusion welding metal on this electrode is bad.
Moreover the content that the tabular in conductive filling (A) ((A) composition) is coated to particle (a1) ((a1) composition) is 0.1 more than volume % 30 volume below %.By adopting such volume ratio, the electrocondution slurry viscosity stability As time goes on (change of viscosity stability) of present embodiment becomes good, restrained effectively fusion welding metal and/or scaling powder is impregnated into the electrode interior obtained by this electrocondution slurry.Consequently the solder wettability of this electrode and conductivity are improved.Based on such viewpoint, the tabular in conductive filling (A) is coated to content preferably 0.3 more than volume %, 30 below the volume % of particle (a1), more preferably 0.5 more than volume % 30 volume below %.
Moreover the granular size of (a1) composition is not particularly limited.But in present embodiment, the viscosity considering electrocondution slurry or the flatness etc. on the surface of solidfied material (film) obtained by this electrocondution slurry, the ball average primary particle diameter that converts is preferably about more than 0.1 μm, about less than 50 μm.And, be more preferably about more than 0.5 μm, about less than 30 μm.And the preferred ball average primary particle diameter that converts is about more than 1.0 μm about less than 20 μm.Moreover the 99% accumulation particle diameter D99 of (a1) composition is preferably less than 100 μm, is more preferably less than 70 μm.And preferred 99% accumulation particle diameter D99 is less than 50 μm.In addition, each particle diameter can use such as laser diffraction/diffuse transmission type distribution of particles determinator (micro-tracking meter (マ イ Network ロ ト ラ Star Network) FRA9220 of such as Leeds & Northrup Inc.) etc. to obtain.
(a1) composition also can use commercial goods, but can use the various known method manufactures such as atomization method (atomize method) or galvanoplastic.When the latter's method, such as, obtain by carrying out following (X), (Y).
(X) by utilizing various machine, the raw copper powder of flat processing cathode copper powder or cathode copper alloy powder, copper reduction end or reduction copper alloy powder and atomized copper powder end or atomization copper alloy powder etc. or raw copper alloy powder, make its primary particle become above-mentioned thickness t cwriting board shape.
(Y) after (X), by electrolytic plating method or non-electrolytic plating method, make the tabular particle that obtains silver-plated.
In addition, by galvanoplastic, the oxide scale film being present in and becoming on the spherical bronze powder of raw material or the surface of copper alloy powder can not only be removed in galvanizing process, and utilize silver more evenly and as one man can be coated on it on the surface.What consequently can obtain copper exposes few coating particle.
Moreover, as other optimal way that can adopt, as required, (A) composition also comprises with copper is core, take silver as the spherical coating particle (a2) of the aspect ratio of shell less than 2 (hereinafter also referred to (a2) composition) and/or be core with copper alloy, take silver as the spherical coating particle (a3) of the aspect ratio of shell less than 2 (hereinafter also referred to (a3) composition).By using (a2) composition and/or (a3) composition, the viscosity of the electrocondution slurry of present embodiment can be allocated, operability etc. when maybe can control silk screen printing.Based on such viewpoint, the aspect ratio of (a2) composition and (a3) composition is all preferably about more than 1 about less than 1.8, is more preferably about more than 1 about less than 1.5.In addition, such aspect ratio can be obtained by the method the same with (a1) composition.
Moreover the content of alloy atom forming the copper alloy of (a3) composition is not particularly limited, but the conductivity of electrocondution slurry in order to ensure present embodiment, the content of alloy atom is preferably 30 below atom %, is more preferably 20 below atom %.The content of preferred alloy atom is 15 below atom % further.
In addition, as the slug particle forming (a3) composition, be preferably selected from any one of copper-nickel alloy particle, copper-admiro particle and copper-nickel-zinc alloy granules.Therefore, from the viewpoint of improving the corrosion resistance of slug particle and suppressing the conductivity based on alloying to worsen, preferably select nickel and/or zinc as alloy atom.
Moreover the content forming the alloy atom of the copper alloy of above-mentioned (a3) composition is not particularly limited.But from the viewpoint of making electric attachment play function thus more can improve good conductivity definitely, preferred alternate manner is: the content forming the alloy atom of the copper alloy of spherical coating particle (a3) is 30 below atom %.
Moreover as an example of (a3) composition, in copper-nickel alloy particle, the weight rate of each atom is not particularly limited.But, from the viewpoint of the viscosity stability of the conductivity of electrocondution slurry of the present invention or this electrocondution slurry and suppress Ke Kendaer cavity described later, copper: nickel preferably adopts about 99: about 1 ~ about 85: the scope of about 15.As an example of (a3) composition, in copper-zinc alloy particle, the weight rate of each atom is not particularly limited.But, the same with nickel, from the viewpoint of conductivity, viscosity stability and suppression cavity, copper: zinc preferably adopts about 99: about 1 ~ about 70: the scope of about 30.Moreover as an example of (a3) composition, in copper-nickel-zinc alloy granules, the weight rate of each atom is not particularly limited.But, from the viewpoint of conductivity, viscosity stability, suppression cavity, copper: (nickel and zinc) preferably adopts about 99: about 1 ~ about 70: the scope of about 30.
Moreover the content of (a2) composition in (A) composition and/or (a3) composition is not particularly limited.But, from the viewpoint of the operability the etc. when viscosity stability of the electrocondution slurry of present embodiment, the solder wettability of electrode obtained by this electrocondution slurry and conductivity and silk screen printing, preferably approximately about 99.9 below the volume % of 70 more than volume %, more preferably about 99.5 below the volume % of about 80 more than volume %.Moreover preferred scope is about 99 below the volume % of about 90 more than volume % further.
(a2) thickness of composition and (a3) composition shell formed by silver is separately not particularly limited.But, from the viewpoint of the operability the etc. when viscosity stability of the electrocondution slurry of present embodiment, the solder wettability of electrode obtained by this electrocondution slurry and conductivity and silk screen printing, preferably approximately more than 0.02 μm about less than 5 μm, more preferably about more than 0.05 μm about less than 3 μm.Moreover preferred scope is about more than 0.1 μm about less than 1 μm further.In addition, such thickness can be obtained by the method same with (a1) composition.
(a2) thickness (diameter) of the thickness (diameter) of the core of composition and the core of (a3) composition is also not particularly limited.But, consider the conductivity of the electrocondution slurry of present embodiment, the fusion welding Metal Phase wettability etc. for the electrode obtained by this electrocondution slurry, all preferably approximately more than 0.1 μm about less than 20 μm, more preferably about more than 0.3 μm about less than 15 μm.
(a2) composition and (a3) composition can use commercial goods, also can with the method manufacture same with (a1) composition.
In addition, (a2) composition is that the silver of slug particle is coated to particle with copper.And, sometimes produce so-called Ke Kendaer cavity at the interface of this silver and copper.Herein so-called Ke Kendaer (Kirkendall) cavity typically refer in the diffusion couple of certain metal with other Metal Contact, result from the former different relative to the former diffusion coefficient with the latter relative to the diffusion coefficient of the latter and this contact interface produce cavity phenomenon.
When this phenomenon is applicable to the electrocondution slurry of present embodiment, on the electrode obtained by this electrocondution slurry, such as, when employing the solder slurry melting of tin class lead-free solder powder, the copper atom reaction of the core of the tin atom in fusion welding and formation (a2) composition, forms alloy.At this moment, because copper atom one side is compared with tin atom, diffusion velocity is fast, so copper atom there occurs more Mass movement to fusion welding metal one side.Its result as shown in Figure 8, produces cavity in the core-shell interfaces of (a2) composition sometimes.
On the other hand, because slug particle is copper alloy, so (a3) composition is difficult to produce Ke Kendaer cavity in core-shell interfaces.Moreover, when using (a3) composition, there is the advantage that the wettability of fusion welding Metal Phase to the electrode that the electrocondution slurry by present embodiment is made is improved.
Fig. 9 is by the microscope enlarged photograph in the cross section employing the electrode that the electrocondution slurry that obtains for core with copper-nickel-zinc alloy granules is made in (a3) composition.As shown in Figure 9, can confirm almost not see Ke Kendaer cavity in core-shell interfaces.
In addition, use the situation of (a2) composition and (a3) composition, the volume ratio of (a2) composition and (a3) composition is not particularly limited simultaneously.But, in the present embodiment, preferably approximately 1: about 9 ~ about 9: about 1, more preferably about 2: about 8 ~ about 8: about 2.Moreover preferred scope is about 3 further: about 7 ~ about 7: about 3.
In addition, as required, can also containing the conductive filling (hereinafter referred to as (a4) composition) except (a1) composition ~ (a3) composition in (A) composition.Particularly, such as enumerate Argent grain, copper particle, carbon granule etc. that copper particle, nickel particle, copper-nickel alloy particle, gold grain, the particle obtained by the alloy of these metals, nickel are coated to copper particle, successively coating silver and nickel.Moreover the content of (a4) composition in (A) composition is also not particularly limited.But, (a1) when composition and (a2) composition and/or (a3) composition are in 100 volume %, from the viewpoint of the conductivity of raising solder metal to the wettability of the electrode that the electrocondution slurry by present embodiment is made, the electrocondution slurry of present embodiment, the corrosion resistance etc. of (A) composition, preferably adopt the scope of about 30 below the volume % of 0 more than volume %.
Moreover, use the object of (B) composition to be, fixing (A) composition in the electrode that the electrocondution slurry by present embodiment obtains, suppress fusion welding and liquid scaling powder to soak into the diffusion of electrode interior simultaneously.As an example of (B) composition, be not particularly limited, various known thermosetting phenolic resin can be used, such as novolac resin or resol type phenol resin etc.In addition, can form solidfied material of the present invention at relatively low temperatures from the viewpoint of suppressing the burn into of (A) composition, making the intensity of this solidfied material suitably and improve the adhesion of this solidfied material and base material, thermosetting phenolic resin (B) is resol type phenol resin preferably.Moreover, routine as of the phenol becoming raw material, enumerate carbolic acid, cresols, amyl phenol, bisphenol-A, butylphenol, octyl phenol, nonyl phenol, dodecyl phenol (dodecylphenol) etc.Moreover, as an example of formaldehydes, enumerate formalin, paraformaldehyde etc.
In addition, together with (B) composition, also can use other thermosetting binder resins (hereinafter referred to as (B ') composition) on a small quantity simultaneously.One example of this kind of (B ') composition has thermosetting epoxy resin, melamine resin (melamine resin, melmac), polyamide-imide resin, polyimide resin etc.
Moreover, as (C) composition, enumerate various known unrighted acid, such as the unrighted acid of ω-3, ω-6, ω-9 etc.As concrete example, enumerate stearic acid, sorbic acid, oleic acid, linoleic acid, 6,10,14-hexadecatrienoic acid (6,10,14-hexadecatrienoic acid, hiragonic acid, the acid of ヒ ラ go), eleostearic acid, punicic acid (プ ニ カ acid, punicic acid), linolenic acid, parinaric acid (モ ロ Network チ acid, moroctic acid), arachidonic acid etc.Wherein, from the view point of the wettability etc. that further can improve fusion welding, the carbon number of unrighted acid (C) carbon of decarboxylate (but except) preferably approximately more than 6 about less than 20, the preferably unrighted acid of less than more than 16 20.Wherein, at least one of oleic acid, linoleic acid and linolenic acid is particularly preferably selected from.In addition, because As time goes on, the viscosity of the electrocondution slurry of present embodiment has the tendency easily increased, thus preferably do not use above-mentioned carbon number be about more than 6 about less than 20 saturated fatty acid (such as stearic acid) replace (C) composition.
In addition, (C) composition is used to improve infiltrating reason and indefinite.But it has been generally acknowledged that, when heating the electrocondution slurry of present embodiment, its unsaturated bond and the effect of (B) composition, the hardness of the continuous phase be made up of (B) composition increases, and result inhibits liquid scaling powder to soak into the diffusion of electrode interior.
Moreover, as (D) composition, such as, enumerate the aliphatic alcohol of ethanol, normal propyl alcohol (n-propanol), isopropyl alcohol, isobutanol etc., the terpenol of tertiary peonol (タ mono-ピ オ ネ mono-Le terpaeonel) etc., carbiphene (diethylene glycol monoethyl ether), diethylene glycol monobutyl ehter (diethylene glycol monobutyl ether), carbiphene acetate (diethylene glycol monoethyl ether acetate ethyl cellosolve acetate), diethylene glycol monobutyl ehter acetate (diethylene glycol monobutyl ether acetate), butyl carbitol (butyl carbitol), glycol ether (glycol ether) class of hexyl Carbitol (hexyl carbitol) etc., the ester class of isopropyl acetate (vinegar acid isopropyl), ethyl propionate (ehyl propionate), benzoic acid butyl ester, diethylene adipate (diethyl adipate) etc., the hydro carbons (hydrocarbon) of n-hexane (n-hexane), dodecane (dodecane), tetradecene (tetradecene) etc.They can be used alone one, or also can combinationally use two or more.Moreover because As time goes on, the electrocondution slurry of present embodiment is difficult to thickening, so particularly preferably use above-mentioned gylcol ether and/or terpene alcohols in (D) composition.Particularly consider that terpene alcohols dissolves the resin of the HMW of (B) composition and (C) composition reaction generation, therefore, restrained effectively the thickening of the electrocondution slurry of present embodiment.
In the electrocondution slurry of present embodiment, the content (i.e. the content of filler composition) of (A) composition is not particularly limited, but consider conductivity or the adhesion (fluid-tight engagement) etc. with base material, using the slurry eliminating (D) composition overall as 1 volume fraction time, be preferably about more than 0.3 about less than 0.7, be more preferably about more than 0.4 about less than 0.65.Preferred scope about more than 0.45 about less than 0.6 further.
Moreover, in the electrocondution slurry of present embodiment, the content (i.e. the content of adhesive composition) of (B) composition and (C) composition is not particularly limited, but, consider conductivity or the adhesion etc. with base material, using the slurry eliminating (D) composition overall as 1 volume fraction time, be preferably about more than 0.7 or about less than 0.3, more preferably about more than 0.65 or about less than 0.4.Preferred scope about more than 0.6 or about less than 0.45 further.
Moreover, the content of (A) composition in the electrocondution slurry of present embodiment ~ (D) composition is not particularly limited, but, be in preferred degree making the action effect of present embodiment, from the viewpoint of the viscosity stability of this slurry and printing adaptability and the conductivity etc. of solidfied material be made up of this slurry, usually preferably: when being 100 weight portions (converting with solid content) with (A) composition, the content of (B) composition, (C) composition and (D) composition as described below.
(B) composition: more than about 3 weight portions below about 30 weight portions, preferably approximately more than 5 weight portions below about 20 weight portions.
(C) composition: more than about 0.01 weight portion below about 5 weight portions, preferably approximately more than 0.03 weight portion below about 2.5 weight portions.
(D) composition: more than about 3 weight portions below about 50 weight portions, preferably approximately more than 5 weight portions below about 30 weight portions.
In addition, as required, the curing accelerator material of composition (removing is equivalent to (C)) of (B) composition, the additive of thixotropic agent (thixo), fire retardant, viscosity modifier, smoothing agent, antioxidant, plasticizer, activating agent, coupling agent etc. can be coordinated in the electrocondution slurry of present embodiment.Such as the purpose of the adhesion of the electrocondution slurry and base material that improve present embodiment, coupling agent can be utilized.As the example of coupling agent, enumerate silane system coupling agent, titanium system coupling agent, zirconium system coupling agent, aluminium system coupling agent, chromium system coupling agent etc.
Utilizing gyratory shaker or the known utensil such as planetary stirring machine, three-high mill, the electrocondution slurry of present embodiment can be obtained by being uniformly mixed above-mentioned each composition.Moreover the viscosity of the slurry obtained is not particularly limited.But, based on the value of the 10rpm (25 DEG C) of Brookfield rotary viscosimeter, preferably adopt the scope of about below the 300Pas of about more than 0.1Pas.
The electrocondution slurry of present embodiment is coated on various base material and is also made the volatilization of (D) composition obtain in a heated condition by the solidfied material of present embodiment.Heating condition is not particularly limited.But heating-up temperature preferably approximately more than 130 DEG C about less than 200 DEG C, preferably approximately more than 0.2 hour heating time is about less than 2 hours.
The kind of base material is not particularly limited.Because the electrocondution slurry of present embodiment is the material of non-sintered type, so the electrode of ceramic electronic components as chip capacitor (chip condenser, superminiature capacitor) etc., can not only apply ceramic material as base material, and the electrocondution slurry of present embodiment also can be applied to the base material of glass etc. or the resin base material etc. of glass epoxy resin, polyamide, polyimide resin, mylar etc.
Coating process is also not particularly limited.The purposes of electrocondution slurry according to the present embodiment or its viscosity etc., can adopt the various coating means such as such as silk screen printing or distributor (dispenser).In addition, by being repeatedly coated with, the electrocondution slurry thick-film of present embodiment also can be made.
The shape of the solidfied material obtained by the electrocondution slurry of present embodiment is also not particularly limited.Such as, this solidfied material can be arbitrary shape of plane (round shape, polygon-shaped etc.), wire.As an example of the solidfied material of wire, enumerate the wired circuit etc. formed to wire on printed circuit board.
And, the electrocondution slurry of above-mentioned execution mode, useful mainly as direct applied electrode on electronic unit.The electronic equipment of present embodiment is placed with on above-mentioned solidfied material or on above-mentioned electrode by the various electronic units in the welding of solder slurry.
The solder metal used in solder slurry can be contain plumbous solder and any one of lead-free solder.As lead-free solder, such as, can use the lead powder end of Sn-Pb system [Sn-35Pb etc.], Sn-Ag system [Sn-3.5Ag etc.], Sn-Cu system [Sn-0.7Cu etc.], Sn-Ag-Cu system [Sn-3Ag-0.5Cu etc.].That is, from the viewpoint of protection of the environment, the solder powder used in solder slurry preferred tin series lead-free solder powder.In addition, these solder powders also can contain the metallic element of In, Bi, Ge etc.
< embodiment >
Below, specifically describe present embodiment by each embodiment, but be not clearly utilize these embodiments to limit the scope of above-mentioned execution mode.In addition, table 1 is the list of each condition of following embodiment and comparative example.
Table 1
The allotment of < (A) composition makes >
Embodiment 1
As shown in table 1, by mixing following (a1) composition 20 volume %, (a2) composition 80 volume %, allotment makes (A) composition.
(a1) composition: the coating copper powders of commercially available tabular silver (trade name " HP0420M1 ", happiness star metal, about 0.28 μm of silver-colored shell thickness, ball convert about 8 μm of average primary particle diameter, about 40 μm of 99% accumulation particle diameter D99).
(a2) composition: spherical silver is coated to copper powders (trade name " 1400Y ", Mitsui Metal Co., Ltd.'s mining industry (strain) are made, ball converts about 6 μm of average primary particle diameter, about 12 μm of 99% accumulation particle diameter D99).
Then, planet strrier is utilized will to be somebody's turn to do (A) composition 85 parts (wherein (a1) composition 17 parts and (a2) composition 68 parts), the commercially available resol type phenol resin (trade name " BRL-275 ", Showa macromolecule (strain) are made) 8.91 parts as (B) composition, the oleic acid as (C) composition (pharmaceutical worker industry (strain) system pure with light) 0.09 part and carbiphene acetate (hereinafter referred to as DEGA) the 6 parts fully mixing as (D) composition.Then, also with three-high mill mixing, allotment makes electrocondution slurry.In addition, as shown in table 1, the volume % of (A) composition during removing (D) composition in this electrocondution slurry is 50.9%.Moreover the volume % of (B) composition and (C) composition is 49.1%.
Embodiment 2
Except the oleic acid replaced in embodiment 1 except using linoleic acid, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Embodiment 3
Except the oleic acid replaced in embodiment 1 except using leukotrienes, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Embodiment 4
In embodiment 1, except use relative to the thickness of the shell of core be 0.15 μm, ball convert about 8 μm of average primary particle diameter, about 40 μm of 99% accumulation particle diameter D99 the coating copper particle of tabular silver as except (a1) composition, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Embodiment 5
In embodiment 1, except use relative to the thickness of the shell of core be 0.5 μm, ball convert about 9 μm of average primary particle diameter, about 41 μm of 99% accumulation particle diameter D99 the coating copper particle of tabular silver as except (a1) composition, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Embodiment 6
In embodiment 1, except use relative to the thickness of the shell of core be 0.75 μm, ball convert about 9 μm of average primary particle diameter, about 41 μm of 99% accumulation particle diameter D99 the coating copper particle of tabular silver as except (a1) composition, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Embodiment 7 ~ 8
In embodiment 1, except the number of change as shown in table 1 (B) composition and (C) composition, other in the same manner as in Example 1, allotment makes electrocondution slurry.
Embodiment 9
In embodiment 1, except use relative to the thickness of the shell of core be 0.02 μm, ball conversion particle diameter is 7 μm, D99 is tabular particle 25 parts of conduct (a1) compositions of 40 μm, uses except above-mentioned " 1400Y " 60 parts of conduct (a2) compositions, other is the same, and allotment makes electrocondution slurry.
Embodiment 10 ~ 12
In embodiment 1, except (A) composition that change as shown in table 1 uses, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Embodiment 13
In embodiment 1, by mixing following (a1) composition 10 volume %, (a3) composition 90 volume %, allotment makes (A) composition.
(a1) composition: the commercially available coating copper powders (trade name " HP0420M1 ") of tabular silver.
(a3) composition: be that the spherical silver of core is coated to particle (the nickel content in about 0.12 μm of the thickness of outer shell, copper alloy is 14 atom %, ball converts about 2 μm of average primary particle diameter, about 8 μm of 99% accumulation particle diameter D99) with copper-nickel alloy.
Then, planet strrier is utilized fully to mix this (A) composition 85 parts (wherein (a1) composition 8.5 parts and (a3) composition 76.5 parts), as " BRL-275 (trade name) " 8.91 parts of (B) composition, as the oleic acid 0.09 part of (C) composition and the DEGA6 part as (D) composition.Thereafter further with three-high mill mixing, allotment makes electrocondution slurry.
Embodiment 14
In embodiment 13, be that the spherical silver of core is coated to particle (content of the nickel in about 0.12 μm of the thickness of outer shell, copper alloy is 6 atom %, ball converts about 2 μm of average primary particle diameter, about 8 μm of 99% accumulation particle diameter D99) as except (a3) composition with copper-nickel alloy except using, other is the same with embodiment 13, and allotment makes electrocondution slurry.
Embodiment 15
In embodiment 13, be that the spherical silver of core is coated to particle (content of the nickel in about 0.12 μm of the thickness of outer shell, copper alloy is 1.3 atom %, ball converts about 2 μm of average primary particle diameter, about 8 μm of 99% accumulation particle diameter D99) as except (a3) composition with copper-nickel alloy except using, other is the same with embodiment 13, and allotment makes electrocondution slurry.
Embodiment 16
In embodiment 13, be that the spherical silver of core is coated to particle (content of the zinc in about 0.12 μm of the thickness of outer shell, copper alloy is 5.3 atom %, ball converts about 2 μm of average primary particle diameter, about 10 μm of 99% accumulation particle diameter D99) as except (a3) composition with copper-zinc alloy except using, other is the same with embodiment 13, and allotment makes electrocondution slurry.
Embodiment 17
In embodiment 13, particle (nickel in about 0.12 μm of the thickness of outer shell, copper alloy and zinc content is respectively 7.7 atom %, 6.9 atom %, ball converts about 3 μm of average primary particle diameter, about 9 μm of 99% accumulation particle diameter D99) is coated to except (a3) composition using the spherical silver that copper-nickel-kirsite is core except using, other is the same with embodiment 13, and allotment makes electrocondution slurry.
Embodiment 18 ~ 19
After adopting (a3) composition shown in embodiment 13, add (a2) composition shown in embodiment 1, adjust them respectively with the ratio shown in table 1, in addition, other is the same with embodiment 13, and allotment makes electrocondution slurry.
Embodiment 20
Adopt (a3) composition shown in embodiment 13, add commercially available Argent grain (trade name: AGC-239, FUKUDA METAL's paper tinsel powder industry (strain) system, average about 8 μm of primary particle diameter, about 40 μm of D99) as (a4) composition, afterwards, them are adjusted respectively with the ratio shown in table 1, in addition, other is the same with embodiment 13, and allotment makes electrocondution slurry.
Embodiment 21
Adopt (a3) composition shown in embodiment 13, add above-mentioned " AGC-239 " conduct (a4) composition and add DEGA6 part and tertiary peonol 2 parts of conduct (D) compositions, afterwards, them are adjusted respectively with the ratio shown in table 1, in addition, other is the same with embodiment 13, and allotment makes electrocondution slurry.
Comparative example 1
In embodiment 1, replace (a1) composition and (a2) composition two kinds and use commercially available Argent grain (trade name: 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 expressed as in table 1), in addition, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Comparative example 2
In embodiment 1, by the quantitative change of (B) composition more 9 parts and do not use (C) composition, in addition, other in the same manner as in Example 1, allotment makes electrocondution slurry.
Comparative example 3
In embodiment 1, replace (a1) composition and use silver-colored shell thickness to be the coating copper particle of commercially available tabular silver (ball convert about 8 μm of average primary particle diameter, about 40 μm of D99) of 0.009 μm, in addition, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Comparative example 4
In embodiment 1, replace the resol type phenol resin as (B) composition and use commercially available epoxy resin (trade name " jER828 ", Mitsubishi's resin (strain) are made), in addition, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Comparative example 5 ~ 7
In embodiment 1, except the use amount of change as shown in table 1 (a1) composition, (a2) composition, (B) composition, (C) composition and (D) composition, other is allocated and makes electrocondution slurry in the same manner as in Example 1.
Comparative example 8
In embodiment 1, planet strrier is utilized fully to mix (A) composition 85 parts (wherein (a1) composition 0.05 part and (a2) composition 84.95 parts), " BRL-275 " 50.9 parts as (B) composition, the oleic acid 0.09 part as (C) composition and the DEGA6 part as (D) composition.Then, also with three-high mill mixing, allotment makes electrocondution slurry.In addition, the volume % of (A) composition in this electrocondution slurry during removing (D) composition is 50.9%.Moreover the volume % of (B) composition and (C) composition is 49.1%.
The evaluation > of the viscosity stability of < electrocondution slurry
About the various electrocondution slurries of each embodiment with each comparative example, utilize commercially available Brookfield rotary viscosimeter (model HBT), measure the viscosity after just having allocated making respectively and in the thermostat of 25 DEG C, be incubated the viscosity after 24 hours, based on calculating formula shown below, following calculating formula is utilized to calculate the rate of viscosity increase of this electrocondution slurry.In addition, mensuration is at room temperature carried out.
< calculating formula >
Rate of viscosity increase=[(25 DEG C, the viscosity-electrocondution slurry under 10rpm of insulation after 168 hours just allocate making after the viscosity under 10rpm) ÷ (electrocondution slurry just allocate making after the viscosity under 10rpm)] × 100
Think in addition: above-mentioned heat-retaining condition is with the heat-retaining condition of temperature accelerated test for intention, and the rate of viscosity increase in this test takes care of the rate of viscosity increase after about six months under probably having reproduced the environment of less than 10 DEG C more than 0 DEG C.Moreover rate of viscosity increase carries out evaluating based on following index.
◎ (fabulous): rate of viscosity increase is less than 20%
Zero (well): 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, the viscosity stability confirming the electrocondution slurry of the embodiment 21 containing tertiary peonol is extremely excellent, is worth in this respect mentioning especially.
The making > of < electrode
Use hollowed-out mask (stencill mask) (the about 0.2mm of the about 22mm × thickness of the about 35mm × width of length), on glass substrate (the about 1.5mm of the about 27mm × thickness of the about 77mm × width of length), print the electrocondution slurry of each embodiment and each comparative example respectively.The glass substrate obtained by this process being put into thermostat, heats 30 minutes at 150 DEG C, while making solvent evaporates, by making adhesive resin solidify, making solidfied material (electrode).
The evaluation > of the conductivity of < electrode
About the various solidfied materials of each embodiment with each comparative example, utilize four terminals (probe) method, measure resistivity at room temperature.Numerical value is less, means that the conductivity of electrode is better.
< weldability, infiltrating evaluation >
Central authorities are used to have the hollow metal mask (length 25 × width 20 × thickness 0.2mm) in the hole of 6.5mm, on the electrode formed with the electrocondution slurry of embodiment 1, the solder slurry (trade name " VAPY LF219 ", waste river chemical industry (strain) system) of printing Sn-3Ag-0.5Cu alloy.Then, in an atmosphere, at 150 DEG C, prepare heating 90 seconds, then at 240 DEG C, after formally heating makes the complete melting of solder, naturally cool.Then, the pattern of the infiltration expansion of solder metal is observed with magnifying glass (10 ~ 20 times) or digital microscope (100 ~ 200 times), by following standard evaluation wettability.About other embodiment and the electrode of comparative example, weld too, evaluate their " wettability ".In addition, " wettability " is evaluated based on following index.
Zero (well): solder slurry is according to the shape melting after hollowed printing.
△ (level that can use in limited purposes): solder surface produces concavo-convex, poor flatness.
× (poor): on electrode, solder condenses and forms the state repelling (segregation, segregation).
The evaluation > that < fusion welding metal and scaling powder soak into
Observe the glass substrate after welding of each embodiment and each comparative example from above, visualization fusion welding metal and solder soldering fluid are impregnated into the state (diffusion is soaked into) of electrode.Moreover, each glass substrate is cut off by Cross section polishing (cross-sectional polishing) method, utilize scanning electron microscope (multiplying power 300 ~ 10000) to observe, confirm that fusion welding metal and solder soldering fluid are impregnated into the state of electrode.In addition, " impregnability " is evaluated based on following index.
Zero (well): solder metal, solder soldering fluid do not soak into the reverse side arriving glass substrate.
△ (level that can use in limited purposes): solder metal soaks into the reverse side arriving glass substrate.
× (poor): solder metal and solder soldering fluid soak into the reverse side arriving glass substrate.
Moreover, based on the image of the multiplying power 500 times of above-mentioned scanning electron microscope, according to the method specified in specification of the present invention, utilize the cross-sectional image of each electrode of embodiment and comparative example, obtain the aspect ratio of (a1) composition, (a2) composition and (a3) composition.
The evaluation > in the cavity in < (a3) composition
Based on the image of the multiplying power 5000 times of above-mentioned scanning electron microscope, according to the method specified in specification of the present invention, utilize the cross-sectional image of each electrode of embodiment and comparative example, observe the cavity in (a3) composition.In addition, should " cavity " be carry out evaluating based on following index.
◎ (fabulous): in cross-sectional SEM image, at the periphery of the core be made up of copper alloy particle, does not have or almost can not confirm cavity.
Zero (well): in section S EM photo, at the periphery of the core be made up of copper alloy particle, makes out little cavity.
Disclosing for illustration of this execution mode or embodiment and recording of above-mentioned execution mode or embodiment is not record to limit the present invention.And the variation be present in scope of the invention of other combination containing above-mentioned execution mode or embodiment is also comprised in the scope of invention request protection.
Industrial applicibility
The electrocondution slurry of above-mentioned execution mode and each embodiment is mainly used as the electrode of the electrode of electronic unit or the wiring of printed circuit board etc.Moreover, in addition, the various uses of slug type and non-sintered electrocondution slurry also can be applicable to.The electrocondution slurry of such as present embodiment can be applicable to the welding conducting portion etc. of capacitor outer electrode, solar cell conducting channel, ito glass electrode, TO glass electrode, printed circuit.
Moreover, possess the solidfied material of the electrocondution slurry of each execution mode above-mentioned, electronic unit or electronic equipment the same with the electrocondution slurry of each above-mentioned execution mode, also can be applicable to the purposes of wide scope.

Claims (13)

1. an electrocondution slurry, is characterized in that, contains:
Conductive filling (A), the tabular that this conductive filling contains 0.1 more than volume % 30 volume below % is coated to particle (a1), this tabular be coated to particle (a1) with copper or copper alloy be core, take silver as shell, the layer thickness of this shell is that more than 0.02 μm and aspect ratio are for more than 2;
Thermosetting phenolic resin (B);
Unrighted acid (C); And
Organic solvent (D).
2. electrocondution slurry as claimed in claim 1, is characterized in that,
The ball that described tabular is coated to particle (a1) the average primary particle diameter that converts is more than 0.1 μm less than 50 μm, and the 99% accumulation particle diameter D99 that described tabular is coated to particle (a1) is less than 100 μm.
3. electrocondution slurry as described in claim 1 or 2, is characterized in that,
Described conductive filling (A) also containing is core with copper, take silver as the spherical coating particle (a2) of the aspect ratio of shell less than 2 and/or be core with copper alloy, take silver as the spherical coating particle (a3) of the aspect ratio of shell less than 2.
4. electrocondution slurry as claimed in claim 3, is characterized in that,
The alloy atom forming the copper alloy of described spherical coating particle (a3) is nickel and/or zinc.
5. the electrocondution slurry as described in claim 3 or 4, is characterized in that,
The content forming the alloy atom of the copper alloy of described spherical coating particle (a3) is 30 below atom %.
6. the electrocondution slurry according to any one of Claims 1 to 5, is characterized in that,
Described thermosetting phenolic resin (B) is resol type phenol resin.
7. the electrocondution slurry according to any one of claim 1 ~ 6, is characterized in that,
Described unrighted acid (C) to be carbon number be less than more than 6 20 unrighted acid.
8. the electrocondution slurry according to any one of claim 1 ~ 7, is characterized in that,
(D) composition is gylcol ether and/or terpene alcohols.
9. the electrocondution slurry according to any one of claim 1 ~ 8, is characterized in that,
Described conductive filling (A) be 100 weight portions (with solid content convert) time, the content of described thermosetting phenolic resin (B), described unrighted acid (C) and described organic solvent (D) as shown below:
Described thermosetting phenolic resin (B): more than 3 weight portions below 30 weight portions;
Described unrighted acid (C): more than 0.01 weight portion below 5 weight portions;
Described organic solvent (D): more than 3 weight portions below 50 weight portions.
10. a solidfied material, is characterized in that,
By heating claim 1 ~ 9 according to any one of electrocondution slurry and make this electrocondution slurry solidify and obtain.
11. 1 kinds of electrodes, is characterized in that,
Be made up of solidfied material according to claim 10.
12. 1 kinds of electronic equipments, is characterized in that,
Be placed with by the electronic unit in the welding of solder slurry on the described solidfied material that claim 10 is recorded or on the described electrode of claim 11 record.
13. electronic equipments as claimed in claim 12, is characterized in that,
The solder powder used in described solder slurry is tin series lead-free solder powder.
CN201380017276.4A 2012-03-30 2013-03-29 Electrocondution slurry, solidfied material, electrode and electronic equipment Active CN104246909B (en)

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