JP6130209B2 - Conductive film - Google Patents

Description

  The present invention relates to a conductive film containing flaky copper powder.

Conductive paste made by dispersing copper powder in resin is used to bond conductive circuits to insulating substrates and to apply external electrodes to chip components. Recently, the external electrode of multilayer ceramic capacitors has been used. It has also been applied to formation.
In the external electrode of the multilayer ceramic capacitor, the conductive paste is usually attached to the external electrode forming portion of the ceramic body and then heat-treated, and the vehicle component in the conductive paste is evaporated or decomposed and removed during the heating. The external electrodes are formed by sintering the copper powder together.

  In the case of the external electrode of such a multilayer ceramic capacitor, in order to maintain the external shape of the electrode, smooth the surface, accelerate the evaporation or decomposition of the vehicle, and improve the sintered density when firing the conductive paste, It is said that the powder is preferably flat (flaky) rather than spherical. In particular, a flaky copper powder having a uniform particle size and thickness is suitable for having a stable viscosity as a conductive paste and providing an appropriate coating property to the ceramic body. In order to have excellent electrical conductivity as an electrode, it is desirable that the amount of impurities in the flaky copper powder is small. Furthermore, in order to control the sinterability and adhesive strength of the conductive paste and eliminate these fluctuations, flaky copper powder having a uniform particle size and thickness is indispensable.

The present applicant has proposed to improve the particle size distribution of the flaky copper powder for the purpose of producing the flaky copper powder having such characteristics with high accuracy and reproducibility (see Patent Document 1). ).
However, even if the particle size distribution of the flaky copper powder is improved, sufficient conductivity may not be obtained unless the planar density of the flaky copper powder is sufficiently high. There exists a subject that electroconductivity will fall, when using it, mixing with powder.

Japanese Patent Laid-Open No. 2005-200734

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a conductive film in which the flake-like copper powder has a high planar density and does not deteriorate in conductivity even when used in combination with other conductive powder.

The conductive film of the present invention as a means for solving the above problems contains flaky copper powder and a resin,
The metal area ratio [(B / A) × 100], which is the ratio of the area B of the flaky copper powder to the effective total area A of the cross-sectional photographic image of the conductive film by a scanning electron microscope, is 60% or more.

  According to the present invention, the conventional problems can be solved and the object can be achieved, and the planar density of the flake-like copper powder is high, especially when mixed with other conductive powders. A conductive film whose conductivity is not reduced can be provided.

1A is a cross-sectional SEM photograph (magnified 3000 times) of the conductive film of Example 1. FIG. 1B is a cross-sectional SEM photograph (10,000 magnifications) of the conductive film of Example 1. FIG. FIG. 2A is a cross-sectional SEM photograph (3,000 times) of the conductive film of Comparative Example 1. 2B is a cross-sectional SEM photograph (10,000 times) of the conductive film of Comparative Example 1. FIG. 3A is a cross-sectional SEM photograph (magnified 3000 times) of the conductive film of Comparative Example 2. FIG. 3B is a cross-sectional SEM photograph (10,000 times) of the conductive film of Comparative Example 2. FIG.

(Conductive film)
The electrically conductive film of this invention contains a flaky copper powder and resin at least, and also contains another component as needed.

In the present invention, the metal area ratio [(B / A) × 100] which is the ratio of the area B of the flaky copper powder to the effective total area A of the cross-sectional photographic image of the conductive film by a scanning electron microscope is 60%. Above, 60% to 90% is preferable.
When the metal area ratio is less than 60%, the density of the flaky copper powder is deteriorated, and the conductivity may be affected. On the other hand, when the metal area ratio is 90% or more, the viscosity of the conductive paste increases and the conductive film may not be formed.

Here, the metal area ratio is determined by cutting a cross section of the conductive film formed on the alumina substrate with an ion milling apparatus, observing the SEM cross section with a field emission scanning electron microscope, and using the scanning electron microscope of each conductive film. The metal area ratio [(B / A) × 100], which is the ratio of the area B of the flaky copper powder to the effective total area A of the SEM cross-sectional photograph, can be obtained.
The total area means the total area of the SEM cross-sectional photograph, and can be measured by image analysis type particle size distribution measurement software (Mac-View Ver4, manufactured by Mountec Co., Ltd.).
The effective total area A means an area obtained by removing an excluded area from the total area. The said exclusion area means the part by the defect of a bubble and a cross-section cutout, and can measure it with image analysis type | formula particle size distribution measurement software (The product made by Mountec, Mac-View Ver4).
The area B of the flaky copper powder means the area occupied by the copper powder in the SEM cross-sectional photograph, and can be measured by image analysis type particle size distribution measurement software (Mac-View Ver4, manufactured by Mountec Co., Ltd.).

<Flake copper powder>
When the flake copper powder is contained in the conductive film, the particles are overlapped with each other with a large contact area. Therefore, the spherical copper powder is obtained from the viewpoint of conductivity, surface smoothness, and shape retention. Has no unique effect.
The flaky copper powder is not particularly limited as long as it is flaky, but the cumulative 50% particle size (D50) in the volume-based particle size distribution by the laser diffraction particle size distribution measurement method is preferably 0.1 μm to 30 μm. 1 μm to 10 μm is more preferable.
The average thickness D of the flaky copper powder is preferably 0.1 μm to 30 μm.
The average thickness D of the flaky copper powder was determined by randomly selecting 100 particles from a scanning electron microscope (SEM) image of the cross section of the conductive film, and using image analysis type particle size distribution measurement software (Mac-View Ver4, manufactured by Mountec Co., Ltd.). ) To measure.
1-100 are preferable and, as for the aspect-ratio (D50 / D) of the said flaky copper powder, 1-10 are more preferable.
As for content in the said electrically conductive film of the said flaky copper powder, 85 mass%-95 mass% are preferable. When the content is less than 85% by mass, sufficient conductivity of the conductive film may not be obtained, and when it exceeds 95% by mass, the viscosity of the conductive paste increases and the conductive film cannot be formed. There is.

The flaky copper powder is not particularly limited and may be appropriately selected depending on the intended purpose. However, the flaky copper powder can be produced by subjecting spherical copper powder produced by a wet reduction method to flake processing.
As the wet reduction method, a primary reduction step of adding a primary reducing agent to a suspension obtained by reacting an aqueous copper salt solution and an alkali agent to precipitate copper hydroxide to reduce to cuprous oxide,
It is preferable to include a secondary reduction step of adding a secondary reducing agent to the cuprous oxide suspension to reduce it to metallic copper in a liquid, and further including other steps as necessary.
Examples of the primary reducing agent include glucose.
Examples of the secondary reducing agent include hydrazine (hydrated hydrazine).

  The secondary reduction step includes a first addition stage in which a part of the secondary reducing agent is added and a second addition stage in which the other part of the secondary reducing agent is added. In the first addition stage, Preferably, the amount of secondary reducing agent added is greater than the amount of secondary reducing agent added in the second addition stage, and the amount of secondary reducing agent added in the first addition stage is More preferably, it is more than twice as much as the amount of the secondary reducing agent added in the step of adding 2. Thereby, reduction | restoration can be strengthened at the initial stage of reaction, and a fine copper powder with a fine particle diameter can be manufactured.

In the flake processing, after adding a lubricant to the obtained spherical copper powder, it is preferable to use a ball mill or a vibration mill to perform drawing or stretching by the mechanical energy of the media loaded in the mill.
The flake processing may be either a wet process or a dry process, but a dry process that does not require a dry process is preferred because it is simple.
The processing time of the flake processing is preferably 10 minutes to 4 hours.
When the flake processing is performed in a non-oxidizing atmosphere such as nitrogen gas or argon gas, it is possible to prevent oxidation of the copper powder surface, and a flaky copper powder having a low oxygen concentration can be obtained.

The medium is not limited to materials such as ceramics, glass, metal, etc., but ceramics are preferable because they have strength and do not become an impurity source due to destruction and wear in the pulverization process, and materials are zirconia from the viewpoint of strength and cost. More preferred.
The diameter of the media is preferably 1 mm to 5 mm.
The lubricant is added to suppress aggregation and coagulation growth between copper powders during flake processing, and examples of the lubricant include oleic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. , Etc.
The addition amount of the lubricant is preferably 0.1% by mass to 2.0% by mass with respect to the mass of copper.

<Resin>
The resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, epoxy resin, acrylic resin, polyester resin, polyimide resin, polyurethane resin, phenoxy resin, silicone resin, ethyl cellulose, nitrocellulose, and the like Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a solvent, a hardening | curing agent, a dispersing agent, a viscosity modifier, etc. are mentioned.

The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, methyl ethyl ketone, methyl isobutyl ketone, tetradecane, tetralin, propyl alcohol, isopropyl alcohol, terpineol, ethyl carbitol, butyl carbitol , Ethyl carbitol acetate, butyl carbitol acetate, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, and the like. These may be used individually by 1 type and may use 2 or more types together.
The solvent is used for viscosity adjustment and volatilizes and disappears when the conductive film is cured.

  Examples of the curing agent include an epoxy resin curing agent when an epoxy resin is used as the resin.

<Method for producing conductive film>
There is no restriction | limiting in particular as a manufacturing method of the said electrically conductive film, According to the objective, it can select suitably, The said electrically conductive paste is apply | coated on a board | substrate and it obtains by hardening a coating film.
The conductive paste is, for example, the flaky copper powder, the resin, and other components as necessary, for example, ultrasonic dispersion, disperser, three-roll mill, ball mill, bead mill, biaxial kneader, self-revolving type It can produce by mixing using a stirrer etc.

There is no restriction | limiting in particular in the said application | coating, According to the objective, it can select suitably, For example, a screen printing method, a gravure printing method, a wire bar coating method, a doctor blade coating method, a roll coating method etc. are mentioned. Among these, the screen printing method is preferable.
There is no restriction | limiting in particular in the curing temperature of the said coating film, Although it can select suitably according to the objective, For example, 100 to 300 degreeC is preferable.
The curing time of the coating film varies depending on the curing temperature and cannot be generally defined, but is preferably 10 minutes to 60 minutes.

  The conductive film of the present invention is suitably used for applications such as bonding of various conductive circuits, formation of wiring, formation of external electrodes of chip components, formation of external electrodes of multilayer ceramic capacitors, and the like.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

Example 1
<Preparation of conductive film>
-Synthesis of cuprous oxide slurry-
A copper sulfate aqueous solution A prepared by dissolving 5.0 kg of CuSO ₄ .5H ₂ O in 11.9 kg of pure water was prepared.
As the alkaline aqueous solution B, 4.1 kg of 48.5% NaOH aqueous solution was prepared.
First, the entire amount of the alkaline aqueous solution B maintained at a temperature of 35 ° C. was added to the copper sulfate aqueous solution A maintained at a temperature of 30 ° C. and stirred. The suspension in which copper hydroxide was precipitated in this liquid was kept at 60 ° C. The copper sulfate aqueous solution A and the alkaline aqueous solution B were mixed so that the equivalent ratio of caustic soda to copper was 1.24.
Next, a glucose solution in which 2.2 kg of glucose is dissolved in 3.4 kg of pure water is added to the total amount of the obtained copper hydroxide suspension, and the temperature of the solution is adjusted to 70.5 within 10 minutes after the addition. After raising the temperature to 0 ° C., it was held for 50 minutes. All the processing operations so far were performed in a nitrogen atmosphere.

Next, air was bubbled through the copper hydroxide suspension for 135 minutes at a flow rate of 3.4 liters / minute.
Next, the copper hydroxide suspension was allowed to stand in a nitrogen atmosphere, and then the supernatant was removed to obtain 4.32 kg of suspension.
The obtained 4.32 kg suspension was divided into 2.16 kg each, and 1.92 kg of pure water was added to each to prepare two 4.08 kg suspensions.

-Synthesis of copper powder-
The 4.08 kg suspension obtained in the synthesis of the cuprous oxide slurry was placed in a reaction vessel and maintained at 45.1 ° C. with stirring, and 80% hydrazine hydrate was added for 0 minutes to 10 minutes. 1.4 equivalents were added. Thereafter, the temperature was raised to 84.1 ° C. at a rate of 0.56 ° C./min during 10 to 80 minutes.
Then, 0.2 equivalents of hydrazine hydrate was added during 80 to 100 minutes and held until all the cuprous oxide was reduced to metallic copper.
Here, the hydrazine equivalent is a ratio with respect to the stoichiometric amount when the stoichiometric amount required to reduce all of cuprous oxide to metallic copper is 1 equivalent, and is held for 0 to 10 minutes. The amount of water hydrazine added is 1.4 equivalent means that the stoichiometric amount of 14/10 hydrazine required to reduce all the cuprous oxide to metallic copper in a stoichiometric amount of 0 to 10 minutes. Means added.
The suspension after completion of the reaction was separated into solid and liquid, sufficiently washed with pure water, and dried to obtain copper powder.

-Flake processing-
15.6 kg of the obtained copper powder was prepared.
Stearic acid as a lubricant of 1.0% by mass with respect to the mass of the copper powder is mixed, together with 192.4 kg of zirconia balls having a diameter of 2.3 mm (the zirconia ball filling amount is 80 vol% with respect to a 65 L pot capacity). It put into the vibration mill (Chuo Processing Machine Co., Ltd. make, FVR-20), and the pressure-stretching process by a ball was performed continuously for 30 minutes. Thus, the flaky copper powder of Example 1 was produced.
The cumulative 50% particle diameter (D50) of the obtained flaky copper powder of Example 1 was 1.72 μm, and the aspect ratio (D50 / average thickness D) was 1.98. The cumulative 50% particle size (D50) was measured with a laser diffraction particle size distribution device (manufactured by SYMPATEC, HEROS particle size distribution measurement device, HELOS & RODOS).
The average thickness D of the flaky copper powder was determined by randomly selecting 100 particles from a scanning electron microscope (SEM) image of the cross section of the conductive film, and using image analysis type particle size distribution measurement software (Mac-View Ver4, manufactured by Mountec Co., Ltd.). ) And measured.

-Production of conductive paste-
90 parts by mass of the obtained flaky copper powder, 8 parts by mass of a bisphenol F type epoxy resin (manufactured by ADEKA, Adeka Resin EP-4901E) as a thermosetting resin, and a curing agent (Amicure MY-24, Ajinomoto Fine Techno Co., Ltd.) After mixing 2 parts by mass (made by company) and an appropriate amount of butyl carbitol acetate as a solvent with a kneading deaerator, a conductive paste was prepared by passing three rolls five times and uniformly dispersing.

-Production of conductive film-
The obtained conductive paste was printed on an alumina substrate by a screen printing method in a pattern of 13 mm × 13 mm and thickness 50 μm, and then baked and cured in the atmosphere at 200 ° C. for 40 minutes to form a conductive film. .

(Comparative Example 1)
-Synthesis of cuprous oxide slurry-
In the same manner as in Example 1, 4.08 kg of suspension was obtained.

-Synthesis of copper powder-
As a method for synthesizing copper powder, in Example 1, 0.1 equivalent of hydrazine hydrate was added to a suspension in which the temperature and equivalent of hydrazine hydrate addition were maintained at 45.1 ° C., and 0 minutes to 10 minutes after addition. The temperature was raised to 49.1 ° C. during the minute.
Thereafter, 0.3 equivalent of hydrazine hydrate was added during 10 to 30 minutes, and the temperature was raised to 84.1 ° C. at a rate of 0.56 ° C./minute during 30 to 100 minutes.
Next, 0.33 equivalent of hydrazine hydrate was added during 100 minutes to 110 minutes, 0.94 equivalent of hydrazine hydrate was added during 110 minutes to 190 minutes, and all the cuprous oxide was reduced to metallic copper. A copper powder was prepared in the same manner as in Example 1 except that it was held until it was done.

-Flake processing-
15.6 kg of the obtained copper powder was prepared.
As a lubricant, 1.0% by mass of stearic acid is mixed with respect to the mass of copper powder, and 216.5 kg of zirconia balls having a diameter of 2.3 mm (with a zirconia ball filling amount of 90 vol% with respect to a pot volume of 65 L). At the same time, it was put into a vibration mill, and the pressure-stretching treatment with the balls was continuously carried out for 200 minutes to obtain a flaky copper powder of Comparative Example 1.
The cumulative 50% particle diameter (D50) of the obtained flaky copper powder of Comparative Example 1 was 3.92 μm, and the aspect ratio (D50 / average thickness D) was 5.49.

  Next, using the obtained flaky copper powder of Comparative Example 1, a conductive paste and a conductive film were produced in the same manner as in Example 1.

(Comparative Example 2)
In Example 1, spherical copper powder was obtained in the same manner as in Example 1 except that the flake processing was not performed.
The cumulative 50% particle diameter (D50) of the obtained spherical copper powder of Comparative Example 2 was 1.67 μm.
Next, using the obtained spherical copper powder of Comparative Example 2, a conductive paste and a conductive film were produced in the same manner as in Example 1.

  Next, the metal area ratio was measured for the produced conductive films of Example 1 and Comparative Examples 1 and 2 as follows. The results are shown in Table 1.

<Measurement of metal area ratio>
A cross section of the conductive film formed on the alumina substrate was cut out with an ion milling device (E-3500 type with high-rate ion gun, manufactured by Hitachi High-Technologies Corporation), and a field emission scanning electron microscope (FE-SEM) (Hitachi Corporation). SEM cross-section observation was performed using S-4700 manufactured by Seisakusho. 1A (3,000 times) and FIG. 1B (10,000 times) SEM cross-sectional photographs of Example 1, and SEM cross-sectional photographs of Comparative Example 1 are FIG. 2A (3,000 times) and FIG. 2B (10,000 times). ) And SEM cross-sectional photographs of Comparative Example 2 are shown in FIG. 3A (3,000 times) and FIG. 3B (10,000 times), respectively.
Next, the metal area ratio [(B / A) × 100], which is the ratio of the area B of the copper powder to the effective total area A of the SEM cross-sectional photograph of each conductive film by a scanning electron microscope, was determined.
The said total area means the total area of a SEM cross-sectional photograph, and it measured with the image analysis type | formula particle size distribution measurement software (The product made in a mount tech company, Mac-View Ver4).
The effective total area A means an area obtained by removing an excluded area from the total area. The said exclusion area means the part by the defect of a bubble and a cross-section cutout, and it measured with the image analysis type | formula particle size distribution measurement software (The product made by Mountec, Mac-View Ver4).
The area B of the copper powder means the area occupied by the copper powder in the SEM cross-sectional photograph, and was measured by image analysis type particle size distribution measurement software (Mac-View Ver4, manufactured by Mountec Co., Ltd.).

From the result of Table 1, since Example 1 has a higher metal area ratio than Comparative Examples 1 and 2 and the planar density of the copper powder is high, it is conductive when used by mixing with other conductive powder. It is considered that the decrease in sex can be suppressed.

As an aspect of this invention, it is as follows, for example.
<1> A conductive film containing at least a flaky copper powder and a resin,
The metal area ratio [(B / A) × 100], which is the ratio of the area B of the flaky copper powder to the effective total area A of the cross-sectional photographic image of the conductive film by a scanning electron microscope, is 60% or more. It is the electrically conductive film characterized.
<2> The conductive film according to <1>, wherein the metal area ratio [(B / A) × 100] is 60% to 90%.
<3> The conductive film according to any one of <1> to <2>, wherein the content of the flaky copper powder is 85% by mass to 95% by mass.
<4> Flaked copper powder
A primary reduction step of adding a primary reducing agent to the suspension obtained by reacting an aqueous copper salt solution with an alkali agent to precipitate copper hydroxide and reducing the suspension to cuprous oxide;
A secondary reduction step in which a secondary reducing agent is added to the cuprous oxide suspension to reduce it to metallic copper in a liquid;
Manufactured by a method for producing a flaky copper powder, including a flake processing step of flake processing the obtained copper powder,
The secondary reduction step includes a first addition stage in which a part of the secondary reducing agent is added and a second addition stage in which the other part of the secondary reducing agent is added. In the first addition stage, The conductive film according to any one of <1> to <3>, wherein the addition amount of the secondary reducing agent is larger than the addition amount of the secondary reducing agent in the second addition stage.
<5> The conductive film according to <4>, wherein the addition amount of the secondary reducing agent in the first addition stage is twice or more larger than the addition amount of the secondary reducing agent in the second addition stage. .
<6> The conductive film according to any one of <4> to <5>, wherein the secondary reducing agent is hydrazine.

Claims (4)

A conductive film containing at least flaky copper powder and a resin,
The metal area ratio [(B / A) × 100], which is the ratio of the area B of the flaky copper powder to the effective area A of the cross-sectional photographic image of the conductive film by a scanning electron microscope, is 60% or more. A conductive film.   The conductive film according to claim 1, wherein the metal area ratio [(B / A) × 100] is 60% to 90%.   The conductive film according to claim 1, wherein the content of the flaky copper powder is 85% by mass to 95% by mass. A conductive film containing at least flaky copper powder and a resin,
The metal area ratio [(B / A) × 100], which is the ratio of the area B of the flaky copper powder to the effective area A of the cross-sectional photographic image of the conductive film by a scanning electron microscope, is 60% or more,
Content of the said flaky copper powder is 85 mass%-95 mass%, The electrically conductive film characterized by the above-mentioned.
that's all