WO2013147235A1

WO2013147235A1 - Conductive paste, hardened material, electrode, and electronic device

Info

Publication number: WO2013147235A1
Application number: PCT/JP2013/059698
Authority: WO
Inventors: 岩村　栄治; 相澤　貴之
Original assignee: 荒川化学工業株式会社; ペルノックス株式会社
Priority date: 2012-03-30
Filing date: 2013-03-29
Publication date: 2013-10-03
Also published as: JP5462984B1; CN104246909B; JPWO2013147235A1; CN104246909A

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 µm or more. Flat-plate-shaped coated particles (a1) having an aspect ratio of 2 or more are included at 0.1-30 vol%.

Description

Conductive paste, cured product, electrode, and electronic device

The present invention relates to a conductive paste, a cured product obtained from the conductive paste, an electrode made of the cured product, and an electronic device.

In general, the conductive paste is a particulate conductive filler such as silver (Ag), copper (Cu), nickel (Ni), tin (Sn), aluminum (Al), or carbon black, and a phenol resin or epoxy. An electrically conductive composition obtained by blending a thermosetting binder resin such as a resin with an organic solvent. The conductive paste is used in various electronic devices and electronic products because electrodes of various shapes can be easily and finely formed by screen printing or the like.

Conventionally, copper and silver have been used as conductive fillers having excellent electrical conductivity. However, copper is inexpensive and general-purpose, but is easily oxidized, and there is a problem of destabilizing the electrical conductivity of the conductive paste. On the other hand, silver is not expensive, but it is expensive. Therefore, in general, composite particles in which copper particles are coated with silver may be used together with or instead of silver particles in this field.

However, when an electrode is formed with a conductive paste using such composite particles as a conductive filler and an electronic component is to be soldered thereon, defective wetting of the molten solder metal may occur. This problem is particularly noticeable in solder paste using lead-free solder powder such as tin-silver-copper. There are various reasons for this, but one of the reasons is that the tin in the molten solder and the composite particles in the electrode react to form an alloy, resulting in an increase in the interfacial energy between the solder metal and the electrode. This is thought to be because the solder metal does not spread out.

As a method for eliminating solder wettability in a conductive paste using silver particles or the above composite particles, as described in Patent Document 1, a thermoplastic resin as a binder resin and a glass transition temperature of 60 to 100 ° C. It is known to use a degree of saturated polyester.

JP-A-6-295616

However, the present inventors have found that the lack of wetting is not sufficiently solved by the conductive paste using a thermoplastic resin as a binder, based on the detailed analysis and examination by the present inventors based on the following new viewpoints.

First, the inside of the electrode obtained from the conductive paste is composed of a phase of a conductive filler that exists independently in contact with each other and a substantially continuous phase made of a binder resin that fills the voids.

FIG. 1 shows a scanning electron microscope when a conventional conductive paste (corresponding to Comparative Example 1 to be described later) is applied on a glass substrate and the solder paste is further melted on the cured electrode. It is a cross-sectional image by (SEM). As shown in FIG. 1, it can be confirmed that the flux spreads so as to cover the solder alloy (white portion) after melting. More specifically, when the solder paste is melted on an electrode made of a conventional conductive paste, the liquid flux that has exuded so as to cover the solder metal penetrates into the electrode and is compatible with the binder resin. Is incorporated in a manner to

However, if the flux constituting the solder paste is excessively taken into the inside of the electrode, the activator that is originally on the surface and should suppress the surface oxidation of the solder metal in the solder paste is reduced. Since it will be washed away from the peripheral area, the molten solder metal may be insufficiently wet.

FIG. 2 is an SEM cross-sectional view of an electrode obtained from a conventional conductive paste. As shown in FIG. 2, as a result of the flux being taken into the binder resin phase, it can be seen that the flux forms an independent phase. The binder resin phase is formed from a thermosetting phenol resin that is cured by heating, but the penetration of the flux cannot be prevented even though the binder resin phase is a strong and hard phase. This result indicates that, for example, when a thermoplastic resin that is softened by heat, such as a polyester resin, is used as the binder resin, the internal penetration of the flux cannot be further suppressed.

On the other hand, as shown in the SEM sectional view of FIG. 3, when the solder paste is melted on the electrode obtained from the conventional conductive paste, the molten solder metal also penetrates into the electrode. However, a certain amount of penetration is essential to ensure the strength of the solder joint, but if the molten solder metal reaches too deep, the amount of molten solder on the electrode will probably decrease. End up.

Then, as shown in FIG. 4, the molten solder metal is in a state of being so-called ridden on the electrode (see the partial diagram (1)), and as a result, it is determined that the wet defect is poor. At this time, since the solder melts at a relatively high temperature, in the case of an electrode in which the binder phase is composed of a thermoplastic resin, the penetration of the molten solder metal into the softened resin is further accelerated. It is thought that it is done. On the other hand, when the molten solder metal spreads wet on the electrode, such repelling does not occur (see the partial view (2)), and the soldering is good.

The present invention effectively suppresses the internal penetration of the molten solder metal and the flux, thereby improving the solder wettability, that is, the electrical and mechanical bondability and the electrical property formed by the electrode formed of the conductive paste and the solder metal. A novel conductive paste capable of forming an electrode having excellent conductivity on various substrates, a cured product obtained from the conductive paste, an electrode made of the cured product, an electronic component having the electrode, and the electronic component This greatly contributes to the provision of electronic devices.

The present inventor has conducted earnest research on how to prevent flux and molten solder metal from reaching the deep part of the electrode in a conductive paste using a thermosetting resin (for example, phenol resin) as a binder. As a result, it has been found that the coated particles having a specific shape can prevent the penetration of flux and / or molten solder metal in the vertical direction in a substantially horizontal direction and suppress excessive penetration. In addition, when the amount of the coated particles of the specific shape that seem to be useful at first glance is too large, the present inventors, on the contrary, lead to static and / or dynamic viscosity fluctuations and deterioration of workability as a whole conductive paste. I also learned that. As a result of further analysis and examination by the present inventors, it has been found that the addition of coated particles having a specific shape in an appropriate range contributes to the solution of the above problems. It has also been found that adopting specific additives also contributes to solving the above problems.

One conductive paste of the present invention contains a conductive filler (A), a thermosetting phenol resin (B), an unsaturated fatty acid (C), and an organic solvent (D). More specifically, the conductive filler (A) of this conductive paste has copper or a copper alloy as a core, silver as a shell, the shell has a layer thickness of 0.02 μm or more, and an aspect ratio of 2 or more. The flat coated particles (a1) are contained in an amount of 0.1% by volume to 30% by volume.

According to this conductive paste, it is possible to prevent or suppress the flux and / or molten solder metal from reaching the deep part of the electrode. In addition, according to this conductive paste, static and / or dynamic viscosity fluctuations as a whole of the conductive paste are suppressed, and good workability can be maintained. As a specific example of good workability, handling of the paste at the time of screen printing and development of the paste on the mask plate are facilitated. Further, adhesion to the squeegee can be suppressed or prevented during screen printing transfer.

In the conductive paste described above, the sphere-converted average primary particle diameter of the tabular coated particles (a1) is 0.1 μm or more and 50 μm or less, and the 99% cumulative particle size of the tabular coated particles (a1). It is a preferable embodiment that D99 is 100 μm or less.

In the conductive paste described above, the conductive filler (A) described above further includes spherical coated particles (a2) having an aspect ratio of less than 2 having copper as a core and silver as a shell and / or a copper alloy as a core and silver. It is also another preferred embodiment to contain spherical coated particles (a3) having an aspect ratio of less than 2 in which A is a shell.

Moreover, in the above-described conductive paste, it is another preferable aspect that the alloy atoms forming the copper alloy of the above-described spherical coated particles (a3) are nickel and / or zinc.

Moreover, in the above-described conductive paste, the content of the alloy atoms forming the copper alloy of the above-described spherical coated particles (a3) is another preferable embodiment.

Further, in the above-described conductive paste, it is another preferable embodiment that the thermosetting phenol resin (B) is a resol type phenol resin.

In the conductive paste, the unsaturated fatty acid (C) is another unsaturated fatty acid having 6 to 20 carbon atoms.

Further, in the above-described conductive paste, it is another preferable aspect that the above-described component (D) is a glycol ether and / or a terpenol.

Moreover, in the above-described conductive paste, when the conductive filler (A) is 100 parts by weight (in terms of solid content), the thermosetting phenol resin (B), the unsaturated fatty acid (C), and the Another preferred embodiment is that the content of the organic solvent (D) is as follows.
The above-mentioned thermosetting phenol resin (B): 3 to 30 parts by weight The above-mentioned unsaturated fatty acid (C): 0.01 to 5 parts by weight The above-mentioned organic solvent (D): 3 parts by weight or more 50 parts by weight or less

Furthermore, a cured product obtained by heat-curing the above-described conductive paste, or an electrode made of the cured product is also a preferred embodiment.

In addition, an electronic device in which an electronic component soldered with a solder paste is placed on the above-described cured product or the above-described electrode is also a preferable embodiment as a specific application example.

In addition, it is another preferable aspect that the solder powder used in the above-described solder paste is a tin-based lead-free solder powder.

By the way, in the present application, the term “tabular coated particle” is not limited to the meaning that a part of the particle surface necessarily has a flat surface. For example, even if the particle is formed only by a curved surface when viewed microscopically, it can be said that the particle is substantially flat when viewed macroscopically, or a substantially flat line is seen in the cross section of the particle. The case is also included in the “tabular coated particle” in the present application. Further, in the present application, the “spherical coated particle” is not limited to the meaning that the particle is a true spherical particle. For example, if the aspect ratio is less than 2, an elliptical shape in the cross section or an elliptical shape in which a substantially flat line can be seen in part is included in the “tabular coated particles” in the present application.

The conductive paste of the present invention can prevent or suppress the penetration of flux and / or molten solder metal into the electrode. Therefore, according to the conductive paste of the present invention, an electrode having good electrical conductivity and excellent wettability of molten solder can be formed on various substrates.

As a result, according to the conductive paste of the present invention, an electrode having good electrical conductivity and excellent wettability of molten solder can be formed on various substrates.

It is a cross-sectional image by a scanning electron microscope (SEM) when solder paste is further melted on an electrode obtained by applying and curing a conventional conductive paste (corresponding to Comparative Example 1) on a glass substrate. It is a SEM cross-sectional image which shows a mode that the island-like flux phase is formed as a result of flux infiltrating the inside of the electrode consisting of the conventional electrically conductive paste (equivalent to the comparative example 1), and being compatible with binder resin. It is a SEM cross-sectional image which shows a mode that the molten solder metal is diffusing and osmose | permeating inside the electrode consisting of the conventional electrically conductive paste (equivalent to the comparative example 1). In FIG. 4, a photograph (1) is an optical photograph showing a state in which wetting failure (repellency) occurs when the solder paste is melted with a conventional conductive paste (corresponding to Comparative Example 1). Moreover, the photograph (2) is an optical photograph showing a state where the molten solder is wet and spread cleanly on the electrode made of the conductive paste of this embodiment (corresponding to Example 1). It is a schematic diagram of the primary particle of a flat covering particle | grain (a1). A state in which the diffusion and penetration of molten solder metal (in this case, exclusively tin) into the electrode formed of the conductive paste according to the present embodiment is physically blocked by the flat coated particles as the component (a1). FIG. FIG. 7 is an enlarged view of FIG. 6. FIG. 7 is an enlarged view of a particle group in which Kirkendall voids are generated in FIG. 6. FIG. 5 is a cross-sectional view of an electrode made of a conductive paste (corresponding to Example 17) using coated particles having a copper-nickel-zinc alloy core and silver shell as the component (a3) which is a conductive filler.

The conductive paste of this embodiment includes a conductive filler (A) (hereinafter also referred to as (A) component) containing predetermined tabular coated particles (a1) (hereinafter also referred to as (a1) component), thermosetting. -Based phenolic resin (B) (hereinafter also referred to as component (B)) and unsaturated fatty acid (C) (hereinafter also referred to as component (C)) are referred to as organic solvent (D) (hereinafter also referred to as component (D)). .)) Is an electrically conductive composition.

The component (A) of the present embodiment is a tabular coated particle (a1) in which copper or a copper alloy is used as a core, silver is used as a shell, the thickness of the shell is 0.02 μm or more, and the aspect ratio is 2 or more. (Hereinafter referred to as component (a1)) is contained in an amount of 0.1% by volume to 30% by volume. In addition, as an alloy atom which makes a copper alloy, gold | metal | money, silver, tin, nickel, zinc, etc. are mentioned. In addition, the (a1) component having a copper alloy as a core is less likely to cause the Kirkendall void phenomenon described later.

FIG. 5 is a schematic diagram of the primary particles 100 of the tabular coated particles (a1). The component (a1) is coated particles having copper or a copper alloy as the core 10 and silver as the shell 20. This component (a1) has a shape in which, in the electrode obtained from the conductive paste of the present embodiment, a part or all of the (a1) component is substantially parallel (at least not perpendicular) to the plane direction of the substrate. Take. The material constituting the core 10 may be copper itself or an alloy of copper and other metals (for example, gold, silver, tin, nickel, zinc, etc.). In terms of preventing corrosion, the alloy type is particularly preferably at least one selected from the group of nickel (Ni) and zinc (Zn). Further, the aspect ratio (hereinafter also referred to as “AR”) of the component (a1), that is, the ratio (L / t) when the maximum length of the primary particles constituting the component (a1) is L and the thickness is t. Is called the aspect ratio.

In the electrode obtained from the conductive paste of the present embodiment, the above-described component (a1) is partially or entirely provided at a position substantially parallel to the planar direction of the base material. As shown, the diffusion and penetration of the solder alloy element (tin in the case of both figures) into the electrode formed using the conductive paste of this embodiment can be physically blocked, so that the molten solder metal on the electrode It becomes possible to prevent or suppress the poor wetting. More specifically, the presence of the flat coated particles (a1) of the present embodiment prevents the flux and / or molten solder metal from penetrating in the vertical direction in a substantially horizontal direction and suppressing excessive penetration. It was confirmed that can be realized.

Furthermore, it is interesting that the present inventor found that the introduction amount of the tabular coated particles (a1) that seemed to be useful is too large, on the contrary, the static and / or dynamic viscosity fluctuations and work of the entire conductive paste. It has also been found that it causes sexual deterioration. As a result of further analysis and examination by the inventor, the conductive filler (A) contains tabular coated particles (a1) in the range of 0.1% by volume to 30% by volume. It has also been found that problems such as penetration of the flux or molten solder, viscosity stability of the conductive paste of the present embodiment, and workability during screen printing can be solved simultaneously.

T _s in Figure 5, (a1) in the component, it is meant an average thickness of the shell made of silver, in consideration of the wettability of the electrical conductivity and solder metal conductive paste of the present embodiment Then, it is preferable that it is 0.02 micrometer or more, and it is more preferable that it is 0.05 micrometer or more and 5 micrometers or less. A more preferable average layer thickness of the shell is 0.1 μm or more and 1 μm or less. In addition, even in the case of tabular coated particles having copper or a copper alloy as a core, silver as a shell, and an aspect ratio of 2 or more, the shell having a layer thickness of less than 0.02 μm is replaced with the component (a1). If used, it is not preferable in several aspects. Specifically, when a shell having such a layer thickness is employed, the electrical resistance of the electrode may increase. In addition, the flux can easily penetrate into the electrode, and the wettability of the molten solder metal on the electrode can be deteriorated.

T _{c in} FIG. 5 means the thickness of the copper or copper alloy particles forming the core in the component (a1), and the value is not particularly limited. However, from the viewpoint of improving the printability, electrical conductivity, solder metal wettability, etc. of the conductive paste of this embodiment, it is preferably 0.1 μm or more and 10 μm or less, and is about 0.3 μm or more and about 5 μm or less. It is more preferable that In addition, a more preferable layer of copper or copper alloy particles is about 0.5 μm or more and about 3 μm or less.

As described above, L in FIG. 5 means the maximum length of the primary particles constituting the component (a1), and t means the maximum thickness. Here, the longer the distance that the molten solder metal travels on the surface of the component (a1), the more effectively the diffusion and penetration of the molten solder metal into the electrode deep portion can be prevented. From this viewpoint, L is preferably 0.2 μm or more, and more preferably about 0.2 μm or more and about 100 μm or less. In addition, more preferable L is about 2 μm or more and about 50 μm or less. Further, t is preferably 0.1 μm or more, and more preferably about 0.1 μm or more and about 10 μm or less. In addition, more preferable t is about 0.9 μm μm or more and about 5 μm or less.

Each value of the present embodiment L, t, t _s, and t _c is measured by the following method.
(1) A cured product made of the conductive paste of the present embodiment or an electrode obtained using the cured product is mechanically cut by some method.
(2) The cross section is observed and photographed with a scanning electron microscope (SEM).
(3) have appeared on the obtained image, constituting the component (a1), from the cross-sectional area of a single tabular silver-coated particles, L, t, and t _s and t _c measured at least 5 points directly Find the average value.

As described above, in this embodiment, the component (a1) has an aspect ratio of 2 or more. By adopting such a component (a1), it becomes possible to effectively suppress or prevent the diffusion and penetration of the molten solder metal and / or flux into the electrode made of the conductive paste of the present embodiment. From this viewpoint, the aspect ratio of the component (a1) is preferably about 2 or more and about 100 or less, more preferably about 2.2 or more and about 20 or less.

Here, the aspect ratio of the representative component (a1) of the present embodiment can be obtained as follows.

First, the cured product or electrode according to this embodiment is mechanically cut to obtain an SEM cross-sectional image of about 500 times (see FIG. 6). Next, using the image as a field of view, one tabular silver-coated particle (component (a1)) is specified. Thereafter, the aspect ratio (AR ₁ ) of the certain one particle is obtained from L and t of the component (a1). Next, in the same manner, the aspect ratio of the (a1) component is determined by determining the aspect ratio and the arithmetic average of at least 100 tabular coated grains in total in five or more different fields of view.

The conductive paste of this embodiment includes the component (a1) having the predetermined aspect ratio described above. Therefore, as shown in FIG. 6 and FIG. 7, it becomes possible to physically block the diffusion and penetration of the molten solder metal (in the case of both figures, tin alloy exclusively) into the electrode made of the paste, The poor wetting of the molten solder metal on the electrode is improved.

Further, the content of the flat coated particles (a1) ((a1) component) in the conductive filler (A) (component (A)) is 0.1% by volume or more and 30% by volume or less. By adopting such a volume ratio, the viscosity stability over time of the conductive paste of this embodiment is improved, and the penetration of molten solder metal and / or flux into the electrode obtained from the conductive paste is effective. Will be suppressed. As a result, the solder wettability and electrical conductivity of the electrode are enhanced. From this viewpoint, the content of the tabular coated particles (a1) in the conductive filler (A) is preferably 0.3% by volume or more and 30% by volume or less, and more preferably 0.5% by volume or more and 30% by volume or less. It is as follows.

Further, the particle diameter of the component (a1) is not particularly limited. However, in this embodiment, considering the viscosity of the conductive paste, the smoothness of the surface of the cured product (coating film) obtained from this, the sphere-converted average primary particle diameter is about 0.1 μm or more and about 50 μm or less. It is preferably 0.5 μm or more and 30 μm or less. In addition, a more preferable spherical equivalent average primary particle size is about 1.0 μm or more and about 20 μm or less. Further, the 99% cumulative particle diameter D99 of the component (a1) is preferably 100 μm or less, and more preferably 70 μm or less. In addition, a more preferable 99% cumulative particle diameter D99 is 50 μm or less. Each particle size can be determined using, for example, a laser diffraction / scattering particle size distribution analyzer (for example, Microtrac FRA 9220 manufactured by Lees & Northrup).

Although a commercial item may be used for (a1) component, it can manufacture by various well-known methods, such as an atomizing method and a plating method. In the case of the latter method, for example, it can be obtained by performing the following (X) and (Y).
(X) Raw copper powder or raw copper alloy powder such as electrolytic copper powder or electrolytic copper alloy powder, reduced copper powder or reduced copper alloy powder, and atomized copper powder or atomized copper alloy powder, the primary particles of which are the thickness t _c Is flattened by various devices so as to obtain a flat plate shape.
(Y) After (X), the obtained tabular particles are silver-plated by an electrolytic plating method or an electroless plating method.
In addition, according to the plating method, not only the oxide film existing on the surface of the spherical copper powder or copper alloy powder as a raw material can be removed during the plating process, but also the surface is covered with silver relatively uniformly and uniformly. it can. As a result, it is possible to obtain coated particles with less copper exposure.

In addition, the component (A) includes, as necessary, spherical coated particles (a2) (hereinafter also referred to as the component (a2)) and / or a copper alloy having an aspect ratio of less than 2 with copper as a core and silver as a shell. The inclusion of spherical coated particles (a3) (hereinafter also referred to as component (a3)) having an aspect ratio of less than 2 and having a core as silver and a shell is another preferred embodiment that can be employed. By using the component (a2) and / or the component (a3), it is possible to adjust the viscosity of the conductive paste of the present embodiment and to control workability during screen printing. From this viewpoint, the aspect ratio of the component (a2) and the component (a3) is preferably about 1 or more and about 1.8 or less, and more preferably about 1 or more and about 1.5 or less. The aspect ratio can be obtained by the same method as that for the component (a1).

Further, the content of the alloy atoms forming the copper alloy of the component (a3) is not particularly limited, but for the purpose of ensuring the electrical conductivity of the conductive paste of the present embodiment, the content of the alloy atoms is 30 atomic% or less. It is preferable that it is 20 atomic% or less. A more preferable alloy atom content is 15 atomic% or less.

The core particles constituting the component (a3) are preferably one type selected from the group consisting of copper-nickel alloy particles, copper-zinc nickel alloy particles, and copper-nickel-zinc alloy particles. Therefore, the selection of nickel and / or zinc as the alloy atoms is preferable from the viewpoint of enhancing the corrosion resistance of the core particles and suppressing the deterioration of conductivity due to alloying.

Further, the content of the alloy atoms constituting the copper alloy of the component (a3) is not particularly limited. However, the content of alloy atoms forming the copper alloy of the spherical coated particles (a3) is 30 atomic% or less, which is preferable from the viewpoint of functioning as an electrical joining member and obtaining good conductivity with higher accuracy. It is another one aspect | mode.

Further, the weight ratio of each atom in the copper-nickel alloy particles, which is an example of the component (a3), is not particularly limited. However, adopting a range in which copper: nickel is about 99: about 1 to about 85: about 15 means that the conductivity of the conductive paste of the present invention, the viscosity stability of the paste, and the Kirkendal described later This is preferable from the viewpoint of suppressing voids. Further, the weight ratio of each atom in the copper-zinc alloy particles, which is an example of the component (a3), is not particularly limited. However, it is preferable to adopt a range in which copper: zinc is about 99: about 1 to about 70:30 about from the viewpoints of conductivity, viscosity stability, and void suppression, like nickel. Further, the weight ratio of each atom in the copper-nickel-zinc alloy particles, which is an example of the component (a3), is not particularly limited. However, it is preferable from the viewpoint of conductivity, viscosity stability, and void suppression that copper: (nickel and zinc) is in a range of about 99: about 1 to about 70:30.

Further, the content of the component (a2) and / or the component (a3) in the component (A) is not particularly limited. However, from the viewpoint of viscosity stability of the conductive paste of the present embodiment, solder wettability and electrical conductivity of an electrode obtained from the conductive paste, workability during screen printing, and the like, about 70% by volume or more and about 99.9%. The volume is preferably not more than volume%, more preferably not less than about 80 volume% and not more than about 99.5 volume%. Further, a more preferable range is from about 90% by volume to about 99% by volume.

The layer thickness of the shell made of silver in each of the components (a2) and (a3) is not particularly limited. However, from the viewpoint of viscosity stability of the conductive paste of the present embodiment, solder wettability and electrical conductivity of an electrode obtained from the conductive paste, workability at the time of screen printing, etc., about 0.02 μm or more and about 5 μm or less. It is preferably about 0.05 μm or more and about 3 μm or less. Further, a more preferable range is from about 0.1 μm to about 1 μm. Such a layer thickness can be determined by the same method as that for the component (a1).

The layer thickness (diameter) of the core of the component (a2) and the layer thickness (diameter) of the core of the component (a3) are not particularly limited. However, in consideration of the electrical conductivity of the conductive paste of the present embodiment and the wettability of the molten solder metal with respect to the electrode made of the paste, it is preferable that both be about 0.1 μm or more and about 20 μm or less. More preferably, it is 3 μm or more and about 15 μm or less.

Commercially available products may be used for the (a2) component and the (a3) component, but they can be produced by the same method as the (a1) component.

The component (a2) is silver-coated particles having copper as core particles. And so-called Kirkendall voids may occur at the silver-copper interface. Here, Kirkendall void is generally due to the difference between the diffusion coefficient of the former and the latter in the diffusion pair where a metal and another metal are in contact. The phenomenon that voids are generated at the contact interface.

When this is applied to the conductive paste of this embodiment, when a solder paste using, for example, a tin-based lead-free solder powder is melted on the electrode obtained from the paste, the tin atom in the molten solder and the component (a2) Reacts with the copper atoms that form the core to form an alloy. At this time, since the diffusion rate of the copper atom is larger than that of the tin atom, the copper atom moves more in mass toward the molten solder metal. As a result, as shown in FIG. 8, voids may occur at the core-shell interface of the component (a2).

On the other hand, in the component (a3), since the core particles are a copper alloy, Kirkendall voids hardly occur at the core-shell interface. Further, when the component (a3) is used, there is an advantage that the wettability of the molten solder metal with respect to the electrode made of the conductive paste of this embodiment is increased.

FIG. 9 is an enlarged micrograph of a cross section of an electrode made of a conductive paste using the component (a3) having copper-nickel-zinc alloy particles as a core. As shown in FIG. 9, it can be confirmed that almost no Kirkendall void is observed at the core-shell interface.

In addition, when using together (a2) component and (a3) component, the volume ratio of (a2) component and (a3) component is not specifically limited. However, in this embodiment, it is preferably about 1: about 9 to about 9: about 1, more preferably about 2: about 8 to about 8: about 2. A more preferred range is from about 3: about 7 to about 7: about 3.

The component (A) may further contain a conductive filler other than the components (a1) to (a3) (hereinafter referred to as the component (a4)) as necessary. Specifically, for example, silver particles, copper particles, nickel particles, copper-nickel alloy particles, gold particles, particles made of an alloy of these metals, nickel-coated copper particles, copper particles coated with silver and nickel in this order, carbon particles Etc. Further, the content of the component (a4) in the component (A) is not particularly limited. However, when the component (a1) and the component (a2) and / or the component (a3) are 100% by volume, it is possible to adopt a range of 0% by volume to about 30% by volume. It is preferable from the viewpoint of improving the wettability of the solder metal to the electrode made of the conductive paste, the conductivity of the conductive paste of the present embodiment, the corrosion resistance of the component (A), and the like.

The component (B) is used for the purpose of suppressing diffusion and penetration of molten solder and liquefied flux into the electrode while fixing the component (A) in the electrode obtained from the conductive paste of the present embodiment. . As an example of the component (B), various known thermosetting phenol resins, such as novolac type phenol resins and resol type phenol resins, can be used without particular limitation. The thermosetting phenolic resin (B) is a resol type phenolic resin, which suppresses corrosion of the component (A) and can form a cured product according to the present invention at a relatively low temperature. Is preferable from the viewpoint of improving the adhesion between the cured product and the substrate. Moreover, as an example of the phenols used as a raw material, there can be mentioned coalic acid, cresol, amylphenol, bisphenol A, butylphenol, octylphenol, nonylphenol, dodecylphenol, and the like. Examples of formaldehydes include formalin and paraformaldehyde.

A small amount of other thermosetting binder resin (hereinafter referred to as “component (B ′)”) may be used in combination with the component (B). An example of such a component (B ′) is a thermosetting epoxy resin, a melamine resin, a polyamideimide resin, a polyimide resin, or the like.

In addition, as the component (C), various known unsaturated fatty acids, for example, unsaturated fatty acids such as ω-3, ω-6, ω-9 and the like can be mentioned. Specific examples include stearic acid, sorbic acid, oleic acid, linoleic acid, hiragoic acid, eleostearic acid, punicic acid, linolenic acid, moloctic acid, arachidonic acid, and the like. Among these, from the viewpoint of further improving the wettability and the like of the molten solder, the number of carbon atoms of the unsaturated fatty acid (C) (excluding the carbon of the carboxyl group) is preferably from about 6 to about 20; 16 to 20 unsaturated fatty acids are preferred. Among these, at least one selected from the group consisting of oleic acid, linoleic acid and linolenic acid is particularly preferable. In addition, it is easy to increase the viscosity of the electrically conductive paste which concerns on this embodiment over time that it replaces with (C) component and uses the above-mentioned saturated fatty acid (for example, stearic acid) about 6-20 carbon atoms. This is not preferable.

The reason why the wettability is improved by using the component (C) is not clear. However, when the conductive paste of this embodiment is heated, the unsaturated bond acts on the component (B), and the hardness of the continuous phase composed of the component (B) is increased. As a result, the liquefied flux into the electrode is reduced. This may be because diffusion and penetration can be suppressed.

Examples of the component (D) include aliphatic alcohols such as ethanol, n-propanol, isopropanol, and isobutanol; terpenols such as terpionol; diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether acetate, Glycol ethers such as diethylene glycol monobutyl ether acetate, butyl carbitol and hexyl carbitol; esters such as isopropyl acetate, ethyl propionate, butyl benzoate and diethyl adipate; hydrocarbons such as n-hexane, dodecane and tetradecene Is mentioned. These can be used alone or in combination of two or more. Moreover, it is preferable to use the above-mentioned glycol ethers and / or terpenols among the component (D) because the conductive paste according to the present embodiment is difficult to thicken with time. In particular, since terpenols are considered to dissolve a high molecular weight resin produced by the reaction between the component (B) and the component (C), they are effective in suppressing the thickening of the conductive paste according to this embodiment.

The content of the component (A) in the conductive paste of the present embodiment (that is, the content of the filler component) is not particularly limited, but considering the electrical conductivity and adhesion to the substrate, the component (D) When the whole paste is taken as one volume fraction, it is preferably about 0.3 or more and about 0.7 or less, more preferably about 0.4 or more and about 0.65 or less. A more preferable range is about 0.45 or more and about 0.6 or less.

Moreover, the content of the component (B) and the component (C) in the conductive paste of the present embodiment (that is, the content of the binder component) is not particularly limited. However, in consideration of electrical conductivity, adhesion to the base material, etc., when the whole paste excluding the component (D) is defined as one volume fraction, it may be about 0.7 or more and about 0.3 or less. Preferably, it is about 0.65 or more and about 0.4 or less. A more preferable range is about 0.6 or more and about 0.45 or less.

Further, the content of the component (A) to the component (D) in the conductive paste of the present embodiment is not particularly limited. However, in order to obtain the effect of the present embodiment to a preferable level, the component (A) is usually added in an amount of 100% by weight. Parts (B), (C) component, and (D) component content is as follows, the viscosity stability and printability of the paste, and the paste This is preferable from the viewpoint of the conductivity of the cured product.
Component (B): about 3 to about 30 parts by weight, preferably about 5 to about 20 parts by weight (C) Component: about 0.01 to about 5 parts by weight, preferably about 0 0.03 to about 2.5 parts by weight Component (D): about 3 to about 50 parts by weight, preferably about 5 to about 30 parts by weight

In addition, in the conductive paste of this embodiment, the curing accelerator (excluding the component corresponding to the component (C)), a thixotropic agent, a flame retardant, a viscosity modifier, Additives such as leveling agents, antioxidants, plasticizers, activators, and coupling agents can be blended. For example, the coupling agent can be used for the purpose of improving the adhesion between the conductive paste of this embodiment and the substrate. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, and a chromium coupling.

The conductive paste of the present embodiment can be obtained by kneading and mixing the above components with a known apparatus such as a rotary stirrer, a planetary kneader, or a three roll. Moreover, the viscosity of the paste obtained is not specifically limited. However, it is preferable that a range in which the value at 10 rpm (25 ° C.) by the Brookfield viscometer is about 0.1 Pa · s to about 300 Pa · s is adopted.

The cured product of the present embodiment is obtained by applying the conductive paste of the present embodiment to various base materials and volatilizing the component (D) under heating. The heating conditions are not particularly limited. However, the heating temperature is preferably from about 130 to about 200 ° C., and the heating time is preferably from about 0.2 hours to about 2 hours.

The type of base material is not particularly limited. Since the conductive paste of the present embodiment is of a non-sintered type, not only can a ceramic substrate be used as a base material as an electrode for a ceramic electronic component such as a chip capacitor, but also a base material such as glass or a glass epoxy resin The conductive paste of this embodiment can also be applied to resin base materials such as polyamide resin, polyimide resin, and polyester resin.

The coating method is not particularly limited. Various coating means such as screen printing and dispenser can be employed depending on the use of the conductive paste of the present embodiment, its viscosity, and the like. Note that the conductive paste of this embodiment can be thickened by recoating.

The shape of the cured product obtained from the conductive paste of the present embodiment is not particularly limited. For example, the cured product may be planar (circular, polygonal, etc.) or linear. Examples of the linear cured product include a wiring circuit formed linearly on a printed wiring board.

In addition, the conductive paste of the above-described embodiment is useful mainly as an electrode applied directly to an electronic component. In the electronic device of the present embodiment, various electronic components soldered with a solder paste are placed on the above-described cured product or the above-described electrode.

Any of solder metal, lead-containing solder, and lead-free solder used in the solder paste may be used. Examples of lead-free solder include Sn—Pb (Sn-35Pb, etc.), Sn—Ag (Sn—3.5Ag, etc.), Sn—Cu (Sn—0.7Cu, etc.), Sn—Ag—Cu. Lead powder of the system [Sn-3Ag-0.5Cu etc.] can be used. That is, it is a preferred embodiment from the viewpoint of environmental protection that the solder powder used for the solder paste is a tin-based lead-free solder powder. Note that these solder powders may contain metal elements such as In, Bi, and Ge.
<Example>

Hereinafter, the present embodiment will be specifically described through each example, but needless to say, the scope of the above-described embodiment is not limited by these. Table 1 is a list of conditions for the following examples and comparative examples.

<Preparation of component (A)>
Example 1
As shown in Table 1, component (A) was prepared by mixing 20% by volume of component (a1) below and 80% by volume of component (a2).
Component (a1): Commercially available tabular silver-coated copper powder (trade name “HP0420M1”, manufactured by Kisei Metals, silver shell layer thickness of about 0.28 μm, sphere-converted average primary particle size of about 8 μm, 99% cumulative particle size of about D99 40μm)
Component (a2): Spherical silver-coated copper powder (trade name “1400Y”, manufactured by Mitsui Mining & Smelting Co., Ltd .; sphere equivalent average primary particle size of about 6 μm, 99% cumulative particle size D99 of about 12 μm)

Next, 85 parts (of which 17 parts of (a1) component and 68 parts of (a2) component) are included as the component (A), and a commercially available resol type phenol resin (trade name “BRL-275”, Molecules Co., Ltd.)) 8.91 parts, (C) component oleic acid (Wako Pure Chemical Industries, Ltd.) 0.09 parts, and (D) component diethylene glycol monoethyl ether acetate (hereinafter referred to as “C” component) , DEGA) was mixed well in a planetary kneader. Then, the electrically conductive paste was prepared by knead | mixing with 3 rolls further. In addition, as shown in Table 1, the volume% of the component (A) when the component (D) was excluded in the conductive paste was 50.9%. Moreover, the volume% of (B) component and (C) component was 49.1.

Example 2
A conductive paste was prepared in the same manner as in Example 1 except that linoleic acid was used instead of oleic acid in Example 1.

Example 3
A conductive paste was prepared in the same manner as in Example 1 except that linolenic acid was used in place of oleic acid in Example 1.

Example 4
In Example 1, as the component (a1), the thickness of the shell relative to the core is 0.15 μm, the sphere-converted average primary particle diameter is about 8 μm, and the 99% cumulative particle diameter D99 is about 40 μm. A conductive paste was prepared in the same manner as in Example 1 except that the particles were used.

Example 5
In Example 1, as the component (a1), a plate-like silver coating having a shell thickness with respect to the core of 0.5 μm, a sphere-converted average primary particle size of about 9 μm, and a 99% cumulative particle size D99 of about 41 μm A conductive paste was prepared in the same manner as in Example 1 except that copper particles were used.

Example 6
In Example 1, as the component (a1), a plate-like silver coating having a shell thickness with respect to the core of 0.75 μm, a sphere-converted average primary particle size of about 9 μm, and a 99% cumulative particle size D99 of about 41 μm A conductive paste was prepared in the same manner as in Example 1 except that copper particles were used.

Examples 7-8
A conductive paste was prepared in the same manner as in Example 1 except that the number of parts (B) and (C) was changed as shown in Table 1 in Example 1.

Example 9
In Example 1, as the component (a1), the thickness of the shell relative to the core is 0.02 μm, the spherical particle system is 7 μm, and the tabular grains having D99 of 40 μm are 25 parts. A conductive paste was prepared in the same manner except that 60 parts of “1400Y” was used.

Examples 10-12
A conductive paste was prepared in the same manner as in Example 1, except that the component (A) used in Example 1 was changed to that shown in Table 1.

Example 13
In Example 1, the following component (a1) is 10% by volume, and component (a3) is 90% by volume.
(A) component was prepared by mixing so that it might become.
Component (a1): Commercially available flat silver-coated copper powder (trade name “HP0420M1”)
Component (a3): Spherical silver-coated particles having a copper-nickel alloy core (shell layer thickness of about 0.12 μm, content of nickel in the copper alloy is 14 atomic%, sphere-converted average primary particle size of about 2 μm, (99% cumulative particle size D99 approx. 8μm)
Next, 85 parts of the component (A) (of which 8.5 parts of the (a1) component and 76.5 parts of the (a3) component are included), and 8 parts of “BRL-275 (trade name)” are used as the (B) component. 91 parts, 0.09 part of oleic acid as component (C) and 6 parts of DEGA as component (D) were mixed well in a planetary kneader. Then, the electrically conductive paste was prepared by knead | mixing with 3 rolls further.

Example 14
In Example 13, spherical silver-coated particles having a copper-nickel alloy core as the component (a3) (shell layer thickness of about 0.12 μm, nickel content in the copper alloy of 6 atomic%, sphere-converted average primary A conductive paste was prepared in the same manner as in Example 13 except that the particle size was about 2 μm and the 99% cumulative particle size D99 was about 8 μm.

Example 15
In Example 13, spherical silver-coated particles having a copper-nickel alloy core as the component (a3) (shell layer thickness of about 0.12 μm, nickel content in the copper alloy is 1.3 atomic%, sphere equivalent) A conductive paste was prepared in the same manner as in Example 13, except that the average primary particle size was about 2 μm and the 99% cumulative particle size D99 was about 8 μm.

Example 16
In Example 13, spherical silver-coated particles having a copper-zinc alloy core as the component (a3) (shell layer thickness of about 0.12 μm, zinc content in the copper alloy is 5.3 atomic%, sphere equivalent) A conductive paste was prepared in the same manner as in Example 13 except that the average primary particle size was about 2 μm and the 99% cumulative particle size D99 was about 10 μm.

Example 17
In Example 13, spherical silver-coated particles having a copper-nickel-zinc alloy core as the component (a3) (shell layer thickness of about 0.12 μm, and the contents of nickel and zinc in the copper alloy were 7.7 respectively) A conductive paste was prepared in the same manner as in Example 13 except that atomic percent, 6.9 atomic percent, sphere-converted average primary particle size of about 3 μm, and 99% cumulative particle size D99 of about 9 μm were used.

Examples 18-19
In the same manner as in Example 13, except that the component (a3) shown in Example 13 was adopted, the component (a2) shown in Example 1 was added, and the ratio was adjusted to the values shown in Table 1, respectively. Prepared.

Example 20
The component (a3) shown in Example 13 was employed, and as the component (a4), commercially available silver particles (trade name: AGC-239, manufactured by Fukuda Metal Foil Powder Co., Ltd., average primary particle size: about 8 μm, D99: 40 μm) was added, and the conductive paste was prepared in the same manner as in Example 13 except that the ratio was adjusted to the ratio shown in Table 1.

Example 21
The component (a3) shown in Example 13 was employed, the above-mentioned “AGC-239” was added as the component (a4), and 6 parts of DEGA and 2 parts of terpionol were added as the component (D), and the results are shown in Table 1. A conductive paste was prepared in the same manner as in Example 13 except that the ratio was adjusted.

Comparative Example 1
In Example 1, instead of both the component (a1) and the component (a2), commercially available silver particles (trade name: AGC-239, manufactured by Fukuda Metal Foil Powder Co., Ltd., average primary particle size of about 8 μm, D99) About 40 μm A conductive paste was prepared in the same manner as in Example 1 except that (shown as component (a4) in Table 1) was used.

Comparative Example 2
In Example 1, the electrically conductive paste was prepared like Example 1 except having changed the quantity of (B) component into 9 parts and not using (C) component.

Comparative Example 3
In Example 1, instead of the component (a1), commercially available tabular silver-coated copper particles having a silver shell layer thickness of 0.009 μm (sphere-converted average primary particle diameter of about 8 μm, D99 of about 40 μm) were used. Prepared a conductive paste in the same manner as in Example 1.

Comparative Example 4
In Example 1, it replaced with the resol type phenol resin which is (B) component, and replaced with the commercially available epoxy resin (Brand name "jER828", Mitsubishi Resin Co., Ltd. product). A conductive paste was prepared.

Comparative Examples 5-7
Example 1 was the same as Example 1 except that the amounts used of component (a1), component (a2), component (B), component (C) and component (D) were changed as shown in Table 1. A conductive paste was prepared.

Comparative Example 8
In Example 1, 85 parts of component (A) (of which 0.05 part of component (a1) and 84.95 parts of component (a2)) and 50.9 parts of “BRL-275” as component (B) Then, 0.09 part of oleic acid as component (C) and 6 parts of DEGA as component (D) were mixed well in a planetary kneader. Then, the electrically conductive paste was prepared by knead | mixing with 3 rolls further. In addition, the volume% of (A) component at the time of remove | excluding (D) component in the said electrically conductive paste was 50.9%. Moreover, the volume% of (B) component and (C) component was 49.1%.

<Evaluation of viscosity stability of conductive paste>
About each electrically conductive paste of each Example and each comparative example, the viscosity immediately after preparation and the viscosity after being kept in a constant temperature bath at 25 ° C. for 24 hours are measured with a commercially available Brookfield viscometer (model HBT), respectively. And based on the formula shown below, the thickening rate of the said electrically conductive paste was computed with the following formula | equation. The measurement was performed at room temperature.

<Calculation formula>
Thickening rate = [(viscosity at 10 rpm after incubation at 25 ° C. for 168 hours−viscosity at 10 rpm immediately after preparation of the conductive paste) ÷ (viscosity at 10 rpm immediately after preparation of the conductive paste)] × 100

The above-mentioned heat retention conditions are intended for a temperature acceleration test, and the thickening rate in this test generally reproduces the thickening rate after storage for about 6 months in an environment of 0 ° C or higher and 10 ° C or lower. It is thought that. Moreover, the thickening rate was evaluated based on the following indicators.
◎ (Very good): Thickening rate is less than 20%. ○ (Good): Thickening rate is 20% or more and 50% or less. △ (Poor): Thickening rate is over 50%. It is worthy of special mention that the conductive paste of Example 21 contained was confirmed to be extremely excellent in viscosity stability.

<Production of electrode>
The conductive paste of each example and each comparative example was placed on a glass substrate (length: about 77 mm × width: about 27 mm × thickness: about 1.5 mm), and stencil mask (length: about 35 mm × width: about 22 mm × thickness: about 0). .2 mm). The glass substrate obtained by this treatment was placed in a thermostatic bath and heated at 150 ° C. for 30 minutes to volatilize the solvent and cure the binder resin to produce a cured product (electrode).

<Evaluation of electrode electrical conductivity>
For each cured product of each example and each comparative example, the specific resistance at room temperature was measured by a four-terminal (probe) method. The smaller the value, the better the electrical conductivity of the electrode.

<Soldering, wettability evaluation>
A Sn-3Ag-0.5Cu alloy solder paste (trade name “VAPY LF219”, manufactured by Arakawa Chemical Industries, Ltd.) was placed on the electrode formed of the conductive paste according to Example 1 at a center of 6.5 mm. Printing was performed using a metal stencil mask with a hole (length 25 × width 20 × thickness 0.2 mm). Next, the solder was preheated at 150 ° C. for 90 seconds in the air, and further heated at 240 ° C. to completely melt the solder, and then naturally cooled. Thereafter, the wetting and spreading of the solder metal was observed with a magnifier (10 to 20 times) or a digital microscope (100 to 200 times), and the wettability was evaluated according to the following criteria. The electrodes of other examples and comparative examples were also soldered in the same manner, and their “wetability” was evaluated. “Wettability” was evaluated based on the following indicators.
○ (Good): Solder paste melted according to the stencil-printed shape.
Δ (a level that can be used in limited applications): The solder surface has irregularities, resulting in poor leveling.
X (defect): Solder aggregated on the electrode, and it was in a state of being removed.

<Evaluation of penetration of molten solder metal and flux>
The glass substrate after soldering of each Example and each Comparative Example was observed from the upper surface, and the penetration state (diffusion penetration) of the molten solder metal and the solder flux into the electrode was visually observed. Each glass substrate was cut by a cross sectional polishing method and observed with a scanning electron microscope (magnification: 300 to 10,000) to confirm the penetration state of molten solder metal and solder flux into the electrode. The “penetration” was evaluated based on the following indicators.
○ (Good): No penetration of solder metal and solder flux reaching the back side of the glass substrate △ (Available level for limited applications): Permeation of solder metal reaching the back side of the glass substrate × (Bad): Back side of the glass substrate Penetration of solder metal and solder flux leading to

In addition, based on the above-mentioned scanning electron microscope image at a magnification of 500 times, according to the method defined in this specification, from the cross-sectional images of the respective electrodes according to the example and the comparative example, (a1) component, (a2) component And the aspect ratio of (a3) component was calculated | required.

<Evaluation of Void in Component (a3)>
Based on the above-mentioned image of the scanning electron microscope with a magnification of 5000, voids in the component (a3) were observed from the cross-sectional images of the electrodes according to the example and the comparative example according to the method defined in this specification. . This “void” was evaluated based on the following indicators.
◎ (Very good): In the cross-sectional SEM image, no void is present or hardly visible in the peripheral portion of the core made of copper alloy particles. ○ (Good): In the cross-sectional SEM photograph, a void is formed in the peripheral portion of the core made of copper alloy particles. Is slightly visible

The disclosure of the above-described embodiment or example is described for explaining the embodiment or example, and is not described for limiting the present invention. In addition, modifications within the scope of the present invention including other combinations of the above-described embodiments or examples are also included in the scope of the claims.

The conductive paste of the above-described embodiment and each example is mainly useful as an electrode for an electronic component or a wiring for a printed wiring board. In addition, the present invention can be applied to various uses of baking type and non-baking type conductive pastes. For example, the conductive paste of this embodiment can be applied to a capacitor external electrode, a solar cell conductive circuit, an ITO glass electrode, a TO glass electrode, a soldered conductive portion of a printed circuit, and the like.

Also, a cured product, an electronic component, or an electronic device provided with the conductive paste of each of the above-described embodiments can be applied to a wide range of uses, like the conductive paste of each of the above-described embodiments.

Claims

Plate-shaped coated particles (a1) having copper or a copper alloy as a core, silver as a shell, a shell layer thickness of 0.02 μm or more, and an aspect ratio of 2 or more are contained in an amount of 0.1% by volume to 30%. A conductive filler (A) containing at most vol%,
A thermosetting phenolic resin (B);
An unsaturated fatty acid (C);
An organic solvent (D),
Conductive paste.
The sphere-converted average primary particle diameter of the tabular coated particles (a1) is 0.1 μm or more and 50 μm or less, and the 99% cumulative particle diameter D99 of the tabular coated particles (a1) is 100 μm or less.
The conductive paste according to claim 1.
The conductive filler (A) further has a spherical coated particle (a2) having an aspect ratio of less than 2 with copper as a core and silver as a shell and / or an aspect ratio with a copper alloy as a core and silver as a shell of less than 2. Containing spherical coated particles (a3)
The electrically conductive paste of Claim 1 or Claim 2.
The alloy atoms forming the copper alloy of the spherical coated particles (a3) are nickel and / or zinc.
The conductive paste according to claim 3.
The content of alloy atoms constituting the copper alloy of the spherical coated particles (a3) is 30 atomic% or less.
The electrically conductive paste of Claim 3 or Claim 4.
The thermosetting phenol resin (B) is a resol type phenol resin.
The electrically conductive paste of any one of Claim 1 thru | or 5.
The unsaturated fatty acid (C) is an unsaturated fatty acid having 6 to 20 carbon atoms,
The electrically conductive paste of any one of Claim 1 thru | or 6.
(D) component is glycol ethers and / or terpenols,
The electrically conductive paste of any one of Claim 1 thru | or 7.
In the case where the conductive filler (A) is 100 parts by weight (in terms of solid content), the content of the thermosetting phenol resin (B), the unsaturated fatty acid (C), and the organic solvent (D) is The conductive paste according to any one of claims 1 to 8, which is as follows.
The thermosetting phenol resin (B): 3 to 30 parts by weight The unsaturated fatty acid (C): 0.01 to 5 parts by weight The organic solvent (D): 3 to 50 parts by weight Less than
It is obtained by heat-curing the conductive paste according to any one of claims 1 to 9.
Cured product.
The cured product according to claim 10,
electrode.
An electronic component soldered with a solder paste is placed on the cured product according to claim 10 or on the electrode according to claim 11.
Electronic devices.
The solder powder used for the solder paste is a tin-based lead-free solder powder.
The electronic device according to claim 12.