JP2001207088A - Silver ink and its manufacturing method, and method for manufacturing electronic part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver ink which can be used as an electrode material for electronic parts, and to provide a method for manufacturing the same and a method for manufacturing electronic parts. SOLUTION: The silver ink is obtained by mixing at least one of a solvent, a metallic powder, a ceramic powder, glass powder, an organometallic compound, and a resin with a sliver soap.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a square chip resistor,
The present invention relates to a silver ink used for various electronic components such as a high frequency component filter and a noise component, a method for manufacturing the same, and a method for manufacturing an electronic component.

[0002]

2. Description of the Related Art Conventionally, metal salts other than alkali metals are collectively called metal soaps, and hundreds of thousands of tons are produced or consumed in Japan every year. As such metal soaps, for example, calcium stearate, zinc stearate, aluminum stearate, magnesium stearate, and barium stearate have been proposed. Actually, in the plastic and cement, pharmaceutical industries, etc., lubricants, dispersants, water repellents, etc. It is added as an agent, release agent, catalyst, stabilizer, and bactericide. Further, a method for producing such metal soap is disclosed in Japanese Patent Publication No. 58-12267.

[0003] Conventionally, silver ink has a particle size of 0.1.
A silver ink obtained by dispersing a silver powder of about 20 μm to about 20 μm in a resin solution has been commercially available. However, in the case of such a silver ink, the ink is expensive because fine silver powder having a particle size of 1 μm to several tens μm is used. The silver ink is used not only for wiring of electronic components such as coils, but also for a part of end electrodes of various chip components. For example, in Japanese Patent Application Laid-Open No. 8-37127, the particle size is from 10 ° to 500 °.
A method of manufacturing an electronic component using the metal fine powder of the item (2) is disclosed. However, such ultrafine silver powder having a particle size of 10 ° to 500 ° is very expensive and has been difficult to put to practical use.

[0004]

Conventional silver electrodes widely used as external electrodes and internal electrodes of multilayer ceramic capacitors, square chip resistors, various coils and noise components are made by dispersing fine silver powder in a resin solution or the like. Silver ink
It was manufactured by printing or coating at a predetermined position. However, such a conventional silver ink has a problem that silver needs to be highly pulverized and is expensive.

The present invention solves the above-mentioned conventional problems and provides a silver ink which can be used as an electrode material for an electronic component while providing a silver ink at a low price, a method for manufacturing the same, and a method for manufacturing an electronic component. It is intended to do so.

[0006]

In order to achieve the above-mentioned object, the present invention provides a silver soap, a solvent and a metal powder which are at least one of ceramic powder, glass powder, organic metal and resin. Are mixed.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention comprises oleic acid, linoleic acid, linolenic acid, erucic acid,
Ricinoleic acid, stearic acid, palmitic acid, lauric acid, behenic acid, octanoic acid, naphthenic acid, tall oil, myristic acid, palmitic acid, carboxylic acid, or aliphatic carboxylic acid having 6 to 22 carbon atoms, tall oil fatty acid Or a mixture of silver soap obtained by reacting at least one of its derivatives with silver and at least one of a solvent, a metal powder, a ceramic powder, a glass powder, an organic metal, and a resin in the silver soap. Thus, it is possible to provide an inexpensive and stable silver ink.

The invention according to claim 2 is characterized in that oleic acid, carboxylic acid, linoleic acid, linolenic acid, erucic acid, ricinoleic acid, stearic acid, palmitic acid, lauric acid, behenic acid, octanoic acid, naphthenic acid, tall oil Silver soap prepared by reacting at least one kind of fatty acid or its derivative with silver oxide or hydroxide, and a solvent, metal powder, ceramic powder, glass powder, organic metal, resin for the silver soap. It is a mixture of at least one of the above, and since conduction can be obtained even after firing, in addition to the use of electronic parts, including ceramics, lubricants, dispersants, and repellents that used conventional metal soaps It can be used for liquid agents, germicides, etc., and has the effect of being able to provide silver ink stably at low cost.

[0009] The invention according to claim 3 includes at least one kind of metal element of potassium, sodium, calcium, magnesium, aluminum, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead and copper. A mixture of silver soap produced by reacting an organic acid or metal soap with a water-soluble silver salt, and a mixture of at least one of a solvent, metal powder, ceramic powder, glass powder, organic metal, and resin with the silver soap. In addition, since conductivity can be obtained even after firing, it can be used not only for electronic parts but also for ceramics, lubricants, dispersants, water repellents, disinfectants, etc. where conventional metal soap was used, This has the effect that silver ink can be stably provided at low cost.

According to a fourth aspect of the present invention, there is provided the silver soap according to any one of the first to third aspects, wherein the silver soap is contained in an amount of 0.01 to 100% by weight. It has the effect of being able to form.

[0011] The invention according to claim 5 is characterized in that at least one of lauric acid, myristic acid, lauric acid, stearic acid, palmitic acid, oleic acid, carboxylic acid or aliphatic carboxylic acid having 6 to 22 carbon atoms. Silver soap formed by reacting one kind with silver is liquefied or dispersed or dissolved in a solvent, and the particle size is 0.001 μm or more and 50 μm or more.
m, metal powder, ceramic powder, or glass powder is added, and silver soap is used as a kind of additive or dispersant in fine particle ink of metal, ceramic, etc. In addition to promoting sintering, the sintering density can be increased and the performance of various electronic components can be improved.

According to a sixth aspect of the present invention, a silver ink containing at least 0.01% by weight or more and 100% by weight or less of silver soap is formed on a substrate of an electronic component so as to have conductivity. , Silver ink containing silver soap,
By giving conductivity by firing on the substrate,
It has an effect that various electronic components such as a square chip resistor, a multilayer ceramic capacitor, a high frequency filter, and a noise filter can be manufactured at low cost.

(Embodiment 1) Hereinafter, a silver ink according to Embodiment 1 of the present invention will be described.

First, sodium hydroxide is dissolved in water to prepare a sodium hydroxide solution.

Next, oleic acid is added to the sodium hydroxide solution, and the mixture is sufficiently stirred using a stirrer to form sodium oleate as a white precipitate in the solution.
Note that, if the stirring is excessively performed during the stirring, sodium oleate foams, and the formed foam is difficult to disappear. Therefore, the stirring is performed while being careful not to foam.

Next, the sodium oleate prepared in the previous step is added to a silver nitrate solution in which silver nitrate is dissolved in water,
The mixture is stirred using a stirrer to replace the sodium of sodium oleate with the silver of silver nitrate to produce silver soap, silver oleate. In this reaction, sodium nitrate is synthesized as a by-product, but by supplying sufficient water, water-soluble sodium nitrate can be dissolved in water and separated from silver oleate. Sodium oleate and silver oleate both form precipitates,
Since silver oleate is closer to pure white than sodium oleate, it can be distinguished from each other by the whiteness of the precipitate. After synthesizing silver oleate as a precipitate in this manner, the precipitate is filtered and sufficiently washed with pure water to remove sodium nitrate as a by-product to obtain high-purity silver oleate.

Next, the silver oleate is dried at a low temperature to obtain silver oleate. In this way, a water-soluble salt of silver is reacted with an alkali soap in an aqueous solution to obtain a precipitate of silver soap unnecessary for water.
In addition, by reacting in a solvent such as alcohol if necessary, hydrolysis of alkali soap can be prevented,
Higher purity silver oleate can be obtained. The silver oleate thus obtained can be dissolved in solvents such as mineral spirits, aromatic hydrocarbons and chlorinated hydrocarbons.

After drying the silver oleate, it is heated at about 100 ° C. using a hot plate or the like,
The silver oleate, which is initially a white solid, gradually dissolves, and a blue-green paste-like liquid silver oleate is obtained. Even if this liquid silver oleate is returned to room temperature, it remains in its paste state (liquid state). Thus, impurities can be removed by further filtering the liquid silver oleate. In addition, the use can be expanded by liquefying silver oleate itself.

In the above description, silver soap using oleic acid has been described. However, linoleic acid, linolenic acid, erucic acid, ricinoleic acid, stearic acid, parsic acid, lauric acid, behenic acid, octanoic acid, naphthenic acid, A similar silver soap can be produced by using tollic acid, myristic acid, palmitic acid, carboxylic acid, or an aliphatic carboxylic acid having 6 to 22 carbon atoms.

The silver soap prepared here can be liquefied by dissolving it in an organic solvent such as α-terpineol, aromatic hydrocarbon, chlorinated hydrocarbon, vegetable oil, mineral oil or wax, benzene, alcohol, pyridine and the like. In addition, by using an emulsifier, an emulsifier, and a dispersant, it can be dispersed in an emulsion state (or a colloidal state or a micelle state) in water or alcohol, and an aqueous silver soap solution can be prepared.
The silver soap thus formed forms a silver film when heated to 200 ° C. or higher, and can be used as a wiring material for various electronic components.

The silver soap is made by adding at least one of a metal powder, a ceramic powder, a glass powder, an organic metal, a resin, and the like to a silver ink to increase or decrease the resistance value or to adhere to the substrate. Since the force can be improved and the strength and hardness of the coating film can be changed, it can be adjusted to the characteristics of the desired electronic component. In particular, by adding a compound such as bismuth, lead, or zinc to the silver ink, even when a silver thin film is formed by baking on an alumina substrate or the like, the adhesion to the alumina substrate or the like can be improved. Enhanced. Further, by containing this silver soap in an amount of 0.1% by weight or more and 100% by weight or less, the silver ink proposed in the present invention can be produced. This silver ink is printed or coated on an alumina substrate or the like, and then fired, whereby electrical conduction is obtained. In addition,
If the silver ink contains no more than 0.05% by weight of silver soap, electrical conduction may not be obtained after firing. In addition, the silver soap of the present embodiment is used for coloring of porcelain, or other metal soap, in addition to the production of electronic components, such as lubricants, dispersants, water repellents, release agents, desiccants, and catalysts. It can also be used as a stabilizer, a bactericide and the like.

A method for confirming the silver soap of the prepared silver ink as described above will be described. First, hydrochloric acid is added to silver oleate, which is silver soap, and separated into water and ether.
Next, potassium hydroxide is added to the extracted ether, centrifuged, and further separated into water and ether. Infrared spectroscopy (FR-IR), nuclear magnetic resonance absorption analysis (NMR), X-ray microanalyzer (X
MA). When the IR spectrum is obtained, W
AVENUMBER 1528.542 and 1997.94
At position 25, the presence of the carboxylate can be detected. The presence of silver can be confirmed by performing XMA analysis of the water-soluble matter. Thus, it is confirmed that silver oleate is present in the silver ink. Next, only the silver salt is separated from the other salts using an alcohol. Further, even when only the silver salt is taken out in this way and the IR spectrum is similarly obtained, even if the wavevenmber is 152.568 or 139.
At position 7.628, the presence of the carboxylate can be detected. By determining the XMA spectrum, the presence of silver can be confirmed. In this way, even when other metallic soap is mixed in the silver soap of the present invention, the presence or absence of silver soap can be confirmed. Further, the carboxylic acid can be specified by releasing the carboxylic acid of the silver salt and measuring the IR spectrum or 13 C-NMR spectrum of the released carboxylic acid. In order to determine the alkyl chain length of the metal soap of the present invention, a methyl ester of a fatty acid may be prepared with a boron trifluoride-methanol reagent, and gas chromatography may be used.

(Embodiment 2) Hereinafter, a silver ink according to Embodiment 2 of the present invention will be described.

Here, the only difference from the silver ink of the first embodiment is the method for producing silver soap. Therefore, only this point will be described.

First, 1 g of silver powder is added to 10 g of oleic acid and left as it is for a long time. Then, in a few months, silver is reduced by about several percent, and silver soap corresponding to the reduced amount is formed. In addition to oleic acid, at least one of linoleic acid, linolenic acid, erucic acid, ricinoleic acid, stearic acid, palmitic acid, lauric acid, behenic acid, octanoic acid, naphthenic acid, tall oil fatty acid and derivatives thereof Even if used, silver soap can be produced similarly.

(Embodiment 3) Hereinafter, a silver ink according to Embodiment 3 of the present invention will be described.

Here, the only difference from the silver ink of the first embodiment is the method for producing silver soap. Therefore, only this point will be described.

First, silver is reacted with ozone to produce black silver oxide.

Next, silver soap is produced by reacting the silver oxide with oleic acid. In addition to oleic acid, carboxylic acid, linoleic acid, linolenic acid, erucic acid, ricinoleic acid, stearic acid, palmitic acid, lauric acid, behenic acid, octanoic acid, naphthenic acid, tall oil fatty acid or a derivative thereof may be used. You can create silver soap, as well.

In the present embodiment, silver has been described as an oxide. However, silver soap can be similarly produced by using a hydroxide instead of an oxide.

(Embodiment 4) Hereinafter, a silver ink according to Embodiment 4 of the present invention will be described.

In the present embodiment, a method for producing fatty acid silver by reacting a water-soluble silver salt with an organic acid or metallic soap will be described. As the water-soluble silver salt, in addition to the silver nitrate described in Embodiment 1, fluoride, chlorate,
Perchlorates and the like can be used. Silver soap can be produced by reacting such a water-soluble silver salt with an organic acid or a metal soap other than silver. In addition, as the organic acid or the metal soap, potassium, sodium,
Calcium, magnesium, aluminum, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead,
It is desirable to include any metal element of copper. Since such a metal element has a higher ionization tendency than silver, it easily replaces silver and generates silver soap. In the case of using a metal soap of a metal element having a higher ionization tendency than silver, at least oleic acid, linoleic acid, linolenic acid, erucic acid, ricinoleic acid, stearic acid, palmitic acid, lauric acid, behenic acid, octane It is desirable to include acids, naphthenic acid tall oil fatty acids. By using the difference in the ionization tendency of silver, an inexpensive silver ink can be provided.

[0033]

As described above, according to the present invention, silver soap, which can be made conductive by sintering, which cannot be obtained with conventional metal soap, is used in plastics, cement, the pharmaceutical industry, and the like. , Water repellent, release agent,
The present invention has an effect of providing a silver ink which can be used not only as a catalyst, a stabilizer and a bactericide but also enables wiring of electronic components and the like, and a method for producing the same.

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Claims (6)

[Claims] 1. Oleic acid, linoleic acid, linolenic acid,
Erucic acid, ricinoleic acid, stearic acid, palmitic acid, lauric acid, behenic acid, octanoic acid, naphthenic acid,
Tall oil, myristic acid, palmitic acid, carboxylic acid, or an aliphatic carboxylic acid having 6 to 22 carbon atoms, tall oil fatty acid or a silver soap obtained by reacting at least one kind of a derivative thereof with silver, A silver ink obtained by mixing at least one of a solvent, a metal powder, a ceramic powder, a glass powder, an organic metal, and a resin with the silver soap. 2. Oleic acid, carboxylic acid, linoleic acid,
Linolenic acid, erucic acid, ricinoleic acid, stearic acid,
Silver soap obtained by reacting at least one kind of palmitic acid, lauric acid, behenic acid, octanoic acid, naphthenic acid, tall oil fatty acid or a derivative thereof with a silver oxide or hydroxide, and a solvent for the silver soap Silver ink made by mixing any one of metal powder, ceramic powder, glass powder, organic metal, and resin. 3. An organic acid or metal soap containing at least one metal element of potassium, sodium, calcium, magnesium, aluminum, zinc, chromium, iron, cadmium, cobalt, nickel, tin, lead, and copper, and water-soluble. Silver soap produced by the reaction of a neutral silver salt, and a solvent, metal powder, ceramic powder, glass powder,
A silver ink obtained by mixing at least one of an organic metal and a resin. 4. The silver ink according to claim 1, wherein silver soap is contained in an amount of 0.01 to 100% by weight. 5. Silver reacts with at least one of lauric acid, myristic acid, lauric acid, stearic acid, palmitic acid, oleic acid, carboxylic acid, or aliphatic carboxylic acid having 6 to 22 carbon atoms. Silver soap obtained by liquefaction or dispersing or dissolving in a solvent, metal particles having a particle size of 0.001 μm or more and 50 μm or less,
A method for producing a silver ink to which one of ceramic powder and glass powder is added. 6. At least 0.01% by weight of silver soap
A method for producing an electronic component in which silver ink containing not less than 100% by weight or less is formed on an electronic component substrate by coating or printing into a predetermined shape to impart conductivity.