JP2000331534A - Electrode ink for electronic component, its manufacture, and manufacture of electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably print by ink jet even in electrode ink for an electronic component having high concentration easy to generate a precipitating body or a aggregate by dispersing a specified amount of plural metal powders made of the same element having different specified particle size or less in water or an organic solvent so as to become specified viscosity or less and filtering with a filter. SOLUTION: Plural metal powders made of the same element having different particle size of 10 μm or less are dispersed in water or an organic solvent in a ratio of 1 wt.% or more but 80 wt.% or less and so as to have a viscosity of 2 poises or less, and they are filtered with a filter. For example, nickel powder having a particle size of 0.4 μm and nickel powder having a particle size of 0.04 μm and an additive or resin are dispersed in an organic solvent or water. As the organic solvent, alcohols, ketones, and esters are listed. The mixture is dispersed by using zirconia beads having a diameter of 0.05 mm for 3 hours, filtered with a membrane filter having a pore size of 5 μm, and viscosity is adjusted to 2 poises to prepare an organic solvent base electrode ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for an electronic component which is mainly used for manufacturing ceramic electronic components such as multilayer ceramic capacitors, LC filters, composite high frequency components and the like which are widely used in various electronic devices by an ink jet method. The present invention relates to an ink, a method for manufacturing the same, and a method for manufacturing an electronic component.

[0002]

2. Description of the Related Art Conventionally, ceramic electronic components have often been manufactured by a printing method using a plate such as screen printing or gravure printing. However, such a method is suitable for mass production, but it has been difficult to make small turns in recent years in the production of small lots and many varieties. Therefore, as a new printing method, it has been proposed to use an ink jet for manufacturing a ceramic electronic component.

First, a general ink jet ink will be described. Common ink jet inks are
Dye-type and pigment-type materials, which are volatilized or deteriorated by firing, cannot be used as electrode materials, dielectric materials, or magnetic materials. For example, U.S. Pat. No. 3,889,270 proposes an ink jet ink for printing on paper.
U.S. Pat. No. 4,150,997 proposes a water-based fluorescent ink for an ink jet and a method for producing the same, but since these are used for coloring, they cannot be applied to electronic components. U.S. Pat. No. 4,894,092 proposes heat-resistant pigments, but these are for coloring and cannot be applied to electronic components. U.S. Pat.
59,247 describes an electrochromic coating and a method for producing the same, but these cannot be applied to electronic components. US Patent 5,034,
In the specification of Japanese Patent No. 244, a method of forming a heat-resistant pattern for glass using an inorganic ceramic pigment is introduced.
Electronic components cannot be manufactured with such pigment-based inks.

Next, an ink jet ink used for coloring a ceramic substrate will be described. US Patent 5,
No. 273,575 is for coloring a ceramic substrate.
Ink jet inks prepared by dissolving various metal salts in a solvent instead of pigments (for example, black, brown, green, and brilliant blue) have been proposed. Further, U.S. Pat. No. 5,407,474 proposes an ink for coloring a ceramic substrate, which has a limited particle diameter of an inorganic pigment. No. 5,714,23
No. 6 proposes an ink for coloring a ceramic substrate prepared by mixing various metal salts with a combustible material serving as an oxygen supply substance.

[0005] However, such an ink for ink jet can be used as an internal electrode, a dielectric material or a magnetic material, for example, even though coloring and printing such as marking of ceramic electronic parts are possible. Japanese Patent Publication No. 5-77474 and Japanese Patent Application Laid-Open No. 63-283981 propose a firing type decorating method for a ceramic base material using a chelate. Japanese Patent Publication No. 6-21255 proposes a firing type marking ink comprising a silicone resin, an inorganic color pigment and a solvent. In addition, Japanese Patent Laid-Open No.
No. 26 proposes a marking ink for a ceramic substrate using a soluble metal salt. Japanese Patent Laid-Open No. 5-26
No. 2,583 proposes a marking method in which an acidic aqueous solution in which a soluble metal liquid is dissolved is applied on a ceramic base material, and then an alkaline aqueous solution is applied so as to neutralize the metal salt, followed by firing. Japanese Patent Application Laid-Open No. 7-330473
In Japanese Patent Application Laid-Open Publication No. H11-157, a marking method is proposed in which an ink composed of a metal ion aqueous solution is printed in a predetermined shape on a ceramic substrate by an ink jet and then fired. Also, JP-A-8-1
No. 27747 proposes a marking ink for coloring a ceramic substrate containing a metal pigment. However, electronic parts cannot be manufactured with such ceramic coloring inks.

Next, a description will be given of how an etching resist used for manufacturing an electronic component or the like is formed by an ink jet method. U.S. Pat. No. 5,567,328 proposes that a resist pattern serving as an etching resist be produced by an ink jet method when a circuit board is manufactured. Similarly, Japanese Patent Application Laid-Open No. Sho 60-175050 proposes that a resist pattern to be an etching resist be formed three-dimensionally on a metal film on a substrate by an ink jet method. However, the use of such an etching resist increases the production cost of electronic components. As described above, with such an ink jet method or ink for an ink jet, electronic components cannot be used at low cost.

Next, a proposal for manufacturing various electronic parts by the ink jet method will be described. Conventionally, it has been proposed to use an ink jet device for manufacturing electronic components. JP-A-58-50795 has proposed a method of forming a conductor and a resistor on an unfired ceramic substrate by ink jet. As described in this proposal, in the case of forming an electronic circuit on a substrate by the conventional ink jet method, an ink for forming an electronic circuit is required to be printed on a substrate in order to solve a problem that the ink easily flows or spreads on the substrate. Using a fired ceramic raw sheet, an ink containing a powder such as a conductor or a resistor is formed in an ink jet in an organic dispersion medium that is easily absorbed by the ceramic raw sheet of the ink, and the obtained substrate is fired. To form an electronic circuit. In this technique, the organic solvent in the ink attached to the substrate is absorbed by the green ceramic sheet, thereby preventing the flow of the ink and the spread of the line width.

[0008] In addition, there has been proposed a method of manufacturing an electronic component by ink jet. For example, JP-A-8-22247
Japanese Patent Application Laid-Open No. 5 (1999) -2005 proposes a method of manufacturing a thick-film electronic component in which an ink for a thick film is applied to an internal electrode pattern using an ink-jet apparatus, and is laminated and fired. In this case, conductive ink or resistive film ink is applied to the surface of the ceramic raw sheet in a predetermined pattern shape by an ink jet device. JP-A-59-82793 proposes forming a conductive adhesive or a low-temperature firing conductor paste at a predetermined connection position on a printed circuit board by an ink jet method. Japanese Patent Application Laid-Open No. 56-94719 proposes that in order to eliminate a step due to the thickness of an internal electrode in a multilayer ceramic capacitor, ceramic ink is sprayed by spraying to produce a reverse pattern of the internal electrode.

[0009] Similarly, in Japanese Patent Application Laid-Open No. 9-219339, in order to eliminate a step due to the thickness of an internal electrode in a multilayer ceramic capacitor, a ceramic ink is applied to the surface of a ceramic green sheet by an ink jet, and if necessary, It has been proposed to form the electrode ink by ink jet. In this proposal, a multilayer ceramic electronic component is manufactured while continuously guiding a continuously formed long green ceramic sheet formed on a carrier film to an internal electrode application station, a ceramic ink application station, and a punching station. Will be. In order to absorb the thickness of the internal electrodes in this manner, printing ceramic ink on a portion of the ceramic green sheet on which the internal electrodes are printed, on which the internal electrodes are not formed, is disclosed in Japanese Patent Application Laid-Open No. 52-135051. But it has been proposed.

[0010] Further, in Japanese Patent Application Laid-Open No. 9-232174,
Similarly, it has been proposed that a functional material paste such as a conductive paste or a resistance paste is jetted together with a ceramic paste by an ink jet method to manufacture an electronic component such as a laminated inductor. As a method of manufacturing such a laminated inductor without using a via hole, US Pat.
No. 22,698 proposes a method of manufacturing a laminated coil while alternately forming insulating layers so that a part of a coil pattern is exposed to each other. Also, JP-A-48-8
Japanese Patent No. 1057 proposes a method of laminating coils through via holes formed in a ceramic raw sheet.

In Japanese Patent Application Laid-Open No. 2-65112,
It has been proposed to improve the characteristics of a semiconductor capacitor by uniformly injecting a required amount of a dopant solution in the form of a droplet onto a surface of an element by ink jet at the time of manufacturing a semiconductor capacitor. In this case, in order to dissolve the ionizable salts of the metal, the ink for ink jet is prepared by dissolving it in ethanol or an acid for adjusting pH. When the electronic component forming member is dissolved in the ink as described above, no precipitate or aggregate is generated in the ink. Japanese Patent Application Laid-Open No. 7-330473 discloses a method for forming a predetermined image or coloring the surface of the ceramic instead of the electronic circuit on the surface of the ceramic.
JP-A-63-283981 proposes using an organic metal chelate compound, JP-B-5-69145 proposes to add water glass, and JP-B-6-21255 proposes to add a silicone resin. Have been. However, these proposals are images and cannot form an electronic circuit as proposed by the present invention.

[0012] However, although a method for manufacturing various electronic parts by a conventional ink jet has been proposed as described above, no ink for electronic parts practically used in the method has been proposed. This has a problem that ink containing powder of a metal or the like required for manufacturing such electronic components easily aggregates and easily clogs a jet port of an ink jet apparatus.

Next, as a conventional example, an electrode ink for electronic parts (Ni screen ink for an internal electrode of a multilayer ceramic capacitor) is diluted with butyl acetate to lower the viscosity.
An example of whether the ink can be used as an ink jet ink will be described with reference to FIG. FIG. 4 is a diagram showing a state in which the electrode ink is jetted onto the raw ceramic sheet by an ink jet.

In FIG. 4, a ceramic raw sheet 2 is formed on a base film 1. This raw ceramic sheet 2 was prepared by dissolving butyral resin in butyl acetate, dispersing barium titanate therein, further adding a phthalic acid-based organic solvent as a plasticizer, and drying the base film on the base film with a coating machine to a thickness of 30 μm. What was formed so that it might become. Reference numeral 3 denotes an ink jet device, and an electrode ink 5 built in from a nozzle 4 formed at the tip of the ink jet device.
Are ejected as needed to form ink droplets 6. The ejected ink droplets 6 adhere to the ceramic raw sheet 2 to form the electrode pattern 7. Arrows 8 show how the solvent component permeates from the electrode pattern 7 into the ceramic green sheet 2.

Thus, on the ceramic green sheet 2,
When the solvent-based electrode ink 5 is printed, the electrode ink 5
Solvent component contained in the ceramic raw sheet 2
The cause of a short circuit has been higher than before.
No. 1 is pointed out. Reference numeral 9 denotes aggregates generated in the electrode ink 5, and such aggregates 9 precipitate in the electrode ink 5 and clog the nozzles 4.

As described above, even if the electrode ink 5 is produced as a trial for ink jet printing, the nozzle 4 is clogged due to the aggregates 9 in the electrode ink 5, so that there is a problem that stable printing quality cannot be obtained. . Almost all commercially available electrode inks for electronic parts are also diluted with an organic solvent. Therefore, when printed on a ceramic raw sheet 2 having a thickness of 20 μm or less, the solvent component dissolves the ceramic raw sheet 2, The problem of causing defects such as short circuits has also been pointed out.

[0017]

As described above, inks using dyes or metal salts have been conventionally proposed. However, electronic parts printing which can stably print inks for electronic parts which are liable to cause precipitation and aggregates. No ink jet device has been proposed. Even if such an ink for electronic parts is filtered through a high-precision filtration equipment after production, it precipitates or re-aggregates in the ink jet apparatus. Therefore, in the conventionally proposed ink jet apparatus, the print head for the ink jet and the ink ejection port are easily packed, and stable printing is difficult. Ink for electronic components for ink jets that can be printed stably uses dyes or metal salts for the purpose of coloring, etc., and cannot be used for the production of electronic components such as LC filters and high-frequency components. Was. In the case of manufacturing a multilayer ceramic electronic component, or when printing an electrode ink or the like on a ceramic raw sheet having a thickness of 20 μm or less without using the ink jet method, a solvent component in the electrode ink permeates the ceramic raw sheet, In some cases, this could be the cause of defects such as short circuits.

It is an object of the present invention to propose an ink for electronic parts which cannot be conventionally printed by using the ink jet apparatus for printing electronic parts proposed in the present invention, and a method for producing the same. Also, in the present invention, by proposing a new water-soluble electrode ink, the green sheet can be printed directly on a green sheet having a thickness of 20 μm or less by a printing method such as a screen or gravure as well as an ink jet. Does not swell or redissolve. Therefore, short-circuiting does not occur even in a thin green sheet having a thickness of 20 μm or less, which is short-circuited with the conventional electrode ink. Thus, according to the present invention, a multilayer ceramic electronic component can be manufactured with a high yield regardless of the printing method. Further, by using the present water-soluble electrode ink, not only the prevention of fire but also the printing work environment can be greatly improved.

[0019]

In order to solve the above-mentioned problems, the electrode ink for electronic parts of the present invention is provided by directly proposing a new water-soluble electrode ink on a ceramic raw sheet having a thickness of 20 μm or less. Is printed by a printing method such as ink jet, screen, gravure, etc., without expanding or re-dissolving the green ceramic sheet. Therefore, short-circuiting does not occur even for a thin ceramic sheet having a thickness of 15 μm or less, which is short-circuited with the conventional electrode ink. Thus, according to the present invention, a multilayer ceramic electronic component can be manufactured with a high yield regardless of the printing method. Further, by using the present water-soluble electrode ink for electronic parts, not only the prevention of fire but also the printing work environment can be greatly improved.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention is characterized in that a plurality of metal powders of the same element having different particle diameters of 10 μm or less are contained in water or an organic solvent in an amount of 1% by weight or more.
An electrode ink for electronic parts that is dispersed at a concentration of 0% by weight or less and a viscosity of 2 poises or less. By using metal powders having different particle diameters, it has the effect of improving the ink stability and reducing the cost of the ink. .

According to a second aspect of the present invention, there is provided
This is a method for producing an electrode ink for electronic parts, in which metal powder is dispersed in water or an organic solvent to have a viscosity of 1 to 80% by weight and a viscosity of 2 poise or less using beads having a diameter of 10 mm or less and then filtering through a filter. By dispersing the metal powder with beads, there is an effect of producing a high-yield, high-concentration, low-viscosity electrode ink for ink jet with high yield.

According to a third aspect of the present invention, a plurality of metal powders of the same element having different particle diameters of 10 μm or less are dispersed in water or an organic solvent to have a viscosity of 1% to 80% by weight and a viscosity of 2 poises or less. After the formed electrode ink for electronic parts is formed in a predetermined pattern on a ceramic raw sheet or ceramic substrate using an ink jet device,
After lamination or firing, it is a method of manufacturing electronic components to separate and attach external electrodes, by improving the printing stability with ink jet by mixing metal powder of different particle size,
An effect is to provide various electronic components to the market at a short delivery date and at low cost.

An embodiment of the present invention will be described below with reference to FIGS.

(Embodiment 1) In the electrode ink for electronic parts according to Embodiment 1, a plurality of metal powders of the same element having different particle diameters of 10 μm or less are contained in water or an organic solvent in an amount of 1% by weight to 80% by weight. % Or less and a viscosity of 2 poise or less.

The electrode ink for electronic parts is prepared by first preparing 100 g of Ni powder having a particle size of 0.4 μm and N 2 having a particle size of 0.04 μm.
1 g of an additive or resin is added to 20 g of i-powder, and 150 g of an organic solvent or water is added. Here, silver palladium, platinum, palladium, nickel or the like is added as the metal powder. As an additive, a phthalic acid-based solvent such as butyl phthalate or polyethylene oxide is added. By adding a cellulose-based resin, a vinyl-based resin, a petroleum-based resin, or the like as the resin, it is possible to improve the binding force of the printed coating film and to increase the strength of the dried ink. As organic solvents, ethyl alcohol,
Alcohols such as isopropyl alcohol, acetone,
A ketone such as methyl ethyl ketone, an ester such as butyl acetate, or a hydrocarbon such as naphtha is added. If necessary, fatty acid esters, polyhydric alcohol fatty acid esters, alkyl glycer ethers and their fatty acids, various lecithin derivatives, propylene glycol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, and sorbitan fatty acid esters may be used as dispersants. By adding a polyoxyethylene alkyl ether or the like, the dispersibility of the powder becomes good, and precipitation due to reagglomeration of the powder can be prevented.

Next, dispersion is performed for 3 hours using zirconia beads having a diameter of 0.5 mm. Thereafter, the solution is filtered using a membrane filter having a pore diameter of 5 μm to prepare an organic solvent-based electrode ink having a viscosity of 2 poise.

Here, a plurality of metal powders of the same element having different particle diameters of 10 μm or less include, for example, nickel metal powder having an average particle diameter of 0.4 μm and an average powder of 0.04 μm.
m means a metal powder mixed with nickel metal powder. Thus, by making the average particle size of the metal powder different,
In addition to increasing the stability of the ink, the density of the electrode coating can be increased and the cost of the electrode ink can be reduced.

FIG. 1 is a measurement example of the particle size distribution of an electrode ink for electronic parts composed of a plurality of metal powders of the same element having different particle diameters of 10 μm or less. In FIG. 1, the X axis is the particle diameter, and the Y axis is the relative particle amount. In FIG. 1, a particle size distribution having a plurality of peaks at positions A and B is obtained. By providing a plurality of peaks in this way, even when the ink concentration is 20% by weight or more and 80% by weight, the ink viscosity is 2 poises or less (often 0.0%).
(Within 1 poise to 1 poise) while maintaining a stable dispersion state.

The peak of the smaller particle diameter (corresponding to peak A) preferably has a particle diameter of 0.001 μm or more and 1 μm or less. Further, the particle diameter of the peak having a larger particle diameter (corresponding to peak B) is preferably 0.01 μm or more and 10 μm or less. In addition, by setting the ink formation so that the height of the peak B is higher than that of the peak A, it is possible to further increase the density and viscosity of the electrode ink for electronic parts, and to use the ink jet printing apparatus. It can be used as a usable electrode ink for electronic parts. Note that, depending on the particle size distribution meter, measurement accuracy may not be obtained, and a plurality of peaks as shown in FIG. 1 may not be measured. In such a case, replace the ink coating with SE
By observing with an M (scanning electron microscope) or the like and using a commercially available image analyzing device (or a powder shape evaluation device) as necessary, it is possible to confirm whether or not the particles have different powder diameters.

FIG. 2 is a diagram comparing the printing stability of the electrode ink for electronic parts according to the first embodiment with the conventional electrode ink for electronic parts. In FIG. 2, the X axis represents the number of continuous prints, and the Y axis represents the amount of ink applied. In FIG. 2, white circles are conventional electrode inks for ink jets prepared by diluting a commercially available electrode ink with a dedicated solvent, and black circles are electrode inks for electronic components described in the first embodiment. In the case of ink jet printing using the conventional electrode ink, the amount of ink applied rapidly decreases with an increase in the number of printed sheets, and the fifth sheet cannot be printed because the ink ejection portion is clogged. on the other hand,
In the case of the electrode ink for electronic parts made by using a plurality of metal powders of the same element having different particle diameters of 10 μm or less according to the first embodiment shown in black circles, printing can be stably performed even when the number exceeds 150 sheets. When the sedimentation rate of these inks was examined, sedimentation of the conventional electrode ink started immediately,
On the other hand, it was found that the electrode ink was easily precipitated. On the other hand, the electrode ink of Embodiment 1 prepared using a plurality of metal powders of the same element having different particle diameters of 10 μm or less hardly precipitated.

(Embodiment 2) In Embodiment 2, an electrode ink for electronic parts composed of a plurality of metal powders of the same element having different particle diameters of 10 μm or less described in Embodiment 1 is used. And how various electronic components are manufactured. FIGS. 3A and 3B show how various electronic components are manufactured by ink jet using the electrode ink for electronic components. In FIG. 3A, reference numeral 10 denotes a base film;
On the surface of the base film 10, a ceramic raw sheet 11 is formed. Reference numeral 12 denotes an electrode ink for electronic parts of the present invention proposed in the first embodiment, which is filled in an ink jet head 13. Reference numeral 14 denotes an element which is formed inside the ink jet head 13 and generates local heat and a piezoelectric effect. By the function of the element 14, the ink droplets 15a are ejected from the ink jet head 13 as needed. The ink pattern 1a on the upper surface of the ceramic raw sheet 11
6a is formed. In FIG. 3B, reference numeral 17 denotes a ceramic substrate, on which a break line 18 for dividing into individual pieces is formed. In FIG. 3B, an ink droplet 15b is placed on a ceramic substrate 17 by an ink jet apparatus.
By spraying (not shown in FIG. 3B), a predetermined ink pattern 16b can be formed.

First, the manner of manufacturing an electronic component using the ceramic raw sheet 11 will be described with reference to FIG.
0.5 μm particle size with X7R characteristics according to EIAJ standard
The dielectric powder mainly composed of barium titanate is dispersed together with a butyral resin, a phthalic acid-based plasticizer and an organic solvent to form a dielectric slurry. After the slurry is filtered with a 10 μm filter, the slurry is placed on the base film 10. Then, an organic ceramic raw sheet 11 having a thickness of 10 μm is applied.

Next, as shown in FIG. 3 (A), an internal electrode is formed from the upper surface of the ceramic raw sheet 11 from an ink jetting portion of an ink jet device described below with a print quality of 720 dpi. First, the electronic component electrode ink 12 described in the above-described first embodiment is provided with the built-in element 14.
It is ejected in a droplet form on demand as needed. The ejected ink droplets 15a adhere to the surface of the ceramic raw sheet 11 to form an ink pattern 16a. By arranging several to several hundred elements 14 (not shown) regularly, a large number of ink droplets 15a are ejected at the same time, and the printing speed can be increased.

Next, while peeling the base film 10 from the ceramic raw sheet 11 having the ink pattern 16a in the previous step, dozens to hundreds of the ceramic raw sheets 11 are formed on the uppermost and lowermost surfaces as necessary. Is pressed from above by a press device to form a ceramic green laminate.

Finally, the ceramic green laminate is cut into desired dimensions and singulated, and external electrodes are formed to be electrically connected to the ink pattern 16a, which is an internal electrode, to produce a multilayer ceramic electronic component. Things. Thus, the organic ceramic green sheet 1 having a thickness of 20 μm or less
On top of 1, the electrode ink does not seep into the ceramic raw sheet 11 by using the aqueous electrode ink. Therefore, a short circuit included in the electrode pattern 7 as shown in FIG. 4 does not occur.

It is to be noted that various multilayer ceramic capacitors for TC (temperature compensation) can be manufactured using the present technology. For example, CH type (0 ± 60 ppm / ° C), PH
Type (-150 ± 60ppm / ° C), RH type (-
Capacitors for temperature compensation of 220 ± 60 ppm / ° C.) can be provided to the market with shorter delivery time and lower cost by forming the internal electrodes by ink jet because of the small number and variety of capacitors.

(Embodiment 3) Next, the manner of manufacturing an electronic component using a ceramic substrate will be described with reference to FIG. Here, a square chip resistor will be described as an example. First,
The adhesion to the ceramic substrate 11 and the like was improved by further adding glass powder to an electrode ink for electronic parts having a plurality of metal powders of the same element having different particle diameters of 10 μm or less. Here, as the glass powder, Pb-SiO
Can be added ₂ -B ₂ O _3. Alternatively, bismuth oxide, copper oxide, aluminum oxide, titanium oxide, zinc oxide, magnesium oxide, manganese oxide, or the like may be added. An example of a method for manufacturing a square chip resistor using the silver electrode thus created will be described.

First, as shown in FIG. 3 (B), which has split grooves in the vertical and horizontal directions, an ink pattern 16b is formed on the ceramic substrate 17 near the vertical and horizontal break lines 18 by an ink jet apparatus. Next, a resistor is formed so as to be proud of the ink pattern 16b on the upper surface. Finally, a protective layer is formed of glass or resin so as to cover the resistor. Finally, it is divided into individual pieces, and a plating layer is formed so as to cover the side electrodes as necessary, whereby a square chip resistor can be manufactured. Here, the resistor, glass,
The resin may also be formed by ink jet.

Here, the reason why the particle size of the metal powder is 0.001 μm or more is that if it is less than 0.001 μm, it does not easily exist as a metal in a normal state. In particular, when powders of base metals such as nickel, copper, silver, aluminum, and zinc or alloys thereof are analyzed using a surface analyzer by ESCA, not only the surface layer but also the inside of the powders are transformed into oxide or hydroxide ceramic. I was The reason why it is 10 μm or less is that when it is larger than 10 μm, the metal powder tends to precipitate in the ink. The reason why the metal powder is 1% by weight or more is that if it is less than 1% by weight, electrical conduction may not be obtained after firing the ink. The reason why the content is 80% by weight or less is that when the content is 85% by weight or more, the ink tends to precipitate. In addition, the reason why the viscosity is set to 2 poises or less is that if the viscosity is too high, it is difficult to jet ink stably from the ink jetting part, and even if the ink is jetted, the ink runs out poorly and the printing accuracy deteriorates. It is.

(Embodiment 4) Although the electrode ink for electronic parts of Embodiment 1 is an organic solvent-based electrode ink, it may be an aqueous electrode-based electrode ink for electronic parts. 100 g of Ni powder having a particle size of 0.4 μm, 20 g of Ni powder having a particle size of 0.04 μm, 1 g of an additive or a resin, and 15 g of water or an aqueous (or aqueous) organic solvent.
Add 0 g. Next, dispersion is performed for 3 hours using zirconia beads having a diameter of 0.5 mm.

Thereafter, the mixture is filtered using a membrane filter having a pore diameter of 5 μm to prepare a water-based electrode ink for electronic parts having a viscosity of 2 poise.

Here, as the aqueous (or aqueous) organic solvent, ethylene glycol, glycerin, ethylene glycol or the like is added. As the resin, by adding a water-soluble resin such as a cellulose resin such as methylcellulose and carboxymethylcellulose, a vinyl resin such as polyvinyl alcohol, and a latex resin such as styrene-butadiene rubber, the binding force of the printed coating film is improved. After drying, the strength of the ink can be increased. Examples of dispersants include various lecithin derivatives, propylene glycol fatty acid esters, glycerin fatty acid esters, polyexethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbit fatty acid esters, and polyethylene glycol. By adding a fatty acid ester, polyoxyethylene alkyl ether, polycarboxylic acid or various soaps, the dispersibility of the powder can be improved, and precipitation due to reagglomeration of the powder can be prevented.

When various electrode inks (mainly for screen printing) such as Ni, silver, and palladium are obtained and diluted with a special solvent, the sedimentation speed is high, and the ink is actually set in a commercially available ink jet apparatus and printed. An experiment was attempted, but stable printing was not obtained.

The continuous printing property and stability of the electrode ink for electronic parts proposed in the present invention can be further improved by increasing the surface potential (zeta potential) of the metal powder. For this purpose, the following additives may be added in addition to the above-mentioned dispersants. By increasing the absolute value of the zeta potential of the metal powder to 50 mV or more in this manner, an electrode ink for electronic parts that is less likely to precipitate and has excellent continuous printability can be manufactured.

Examples of the phosphate include sodium hexametaphosphate, polyoxyethylene-added linear alcohol phosphate, polyoxyethylene-added alkylphenol phosphate, and alkyl phosphate. Examples of the anionic surfactant include a carboxylic acid salt such as a linear aliphatic salt, a coconut oil fatty acid salt, a tall oil fatty acid salt, an amine salt, N-lauroylsaccosin, and an acylated polypeptide. Linear sulfonates such as linear alkylbenzene sulfonates, triethanolamine salts, isopropylamine salts, labile sulfonates, higher alkylbenzene sulfonates, benzene, toluene, xylene, cumene sulfonates, lignin sulfonates, and petroleum Sulfonate, N-acylalkyl taurine, n-paraffin sulfonate, α-olefin sulfonate, sulfosuccinate, alkylphthalene sulfonate, isethionate and the like. Examples of the sulfate include a linear primary alcohol sulfate (AS), a polyoxyethylene-added linear alcohol sulfate (AES), and a sulfated salt (sulfonated oil).

Examples of the cationic surfactant include linear amines, linear diamines, linear polyamines, linear quaternary ammonium salts (eg, tetraalkylammonium salts and N-alkyltrimethylammonium chloride), and polyoxyethylene. Addition linear amine, polyoxyethylene addition linear quaternary ammonium salt, amine oxide (for example, N-
Cetyldimethylamine oxide or the like can be used as the alkyldimethylamine oxide. Examples of the nonionic surfactant include a polyoxyethylene-added nonionic surfactant, an ethylene oxide adduct of an alkylphenol (APE), an ethylene oxide adduct of a linear alcohol (AE), a polyoxyethylene adduct of a polyoxypropylene glycol, Polyoxyethylene adducts of linear mercaptans, linear aliphatic esters, glyceryl of natural fatty acids, polyglyceryl esters, propylene glycol, sorbitol, fatty acid esters of polyoxyethylene added sorbitol, polyoxyethylene glycol esters, polyoxyethylene added fatty acids ( Tall oil), alkanolamine-fatty acid condensate, alkanolamide, acetylene tertiary glycol, polyoxyethylene-added silicone, N-alkylpyrrolidone, alkyl Rigurikoshido like there.

As amphoteric surfactants, β-N-alkylaminopropionic acid, N-alkyl-β-iminodipropionic acid,
There are isodazoline carboxysan, N-alkyl betaine, and amine oxide, and sulfobetaine, saltin, and the like can be used as a pH-insensitive surfactant.

When the electrode ink for electronic parts is manufactured by using a bead mill, a diameter of 0.01 μmφ to 10 mm
It is desirable to use beads of φ or less. 0.005μ
With beads of m or less, it is difficult to remove the beads after dispersion. In the case of beads having a diameter of 15 mmφ or more, the dispersion efficiency is deteriorated and the metal powder may be deformed. When such beads are used, a commercially available electric type vertical or horizontal bead mill, or a ball mill used by being set on a rotating frame or the like can be used. The rotation speed of such a mill is desirably from 10 rpm to 2,000 rpm. If the bead mill is at 5 rpm or less, the dispersion efficiency is reduced, which is not practical. On the other hand, in a high-speed bead mill exceeding 3000 rpm, collision between beads becomes severe, dispersing efficiency is reduced, bead life is shortened, and impurities easily enter the ink.

[0049]

As described above, according to the present invention, it is possible to stably print with an ink jet even with a high-concentration electrode ink for electronic parts in which precipitates and aggregates are easily generated. Therefore, when not only multilayer ceramic electronic components such as multilayer ceramic capacitors, but also electronic components such as high frequency components, optical components, LC filters, three-dimensional composite electronic components, and composite devices with various semiconductors are required. In addition to being able to manufacture in as short a time as possible, it is possible to reduce the cost, increase the yield, and increase the reliability of the product.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a measurement example of a particle size distribution of an electrode ink for electronic parts composed of a plurality of metal powders of the same element having different particle diameters of 10 μm or less according to the present invention.

FIG. 2 is a diagram comparing the printing stability of the electrode ink for electronic components according to the first embodiment with the conventional electrode ink for electronic components.

FIG. 3 is a view showing a state in which various electronic components are manufactured by ink jet using the electrode ink for electronic components.

FIG. 4 is a diagram showing a state in which electrode ink is jetted onto a ceramic raw sheet by an ink jet.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base film 2 Ceramic raw sheet 3 Ink jet apparatus 4 Nozzle 5 Electrode ink 6 Ink droplet 7 Electrode pattern 8 Arrow 9 Aggregate 10 Base film 11 Ceramic raw sheet 12 Electrode ink for electronic components 13 Ink jet head 14 Element 15a, 15b Ink droplets 16a, 16b Ink pattern 17 Ceramic substrate 18 Break line

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 5E001 AB03 AC09 AC10 AF06 AH01 AH05 AH06 AH09 AJ01 5E082 AB03 BC38 BC40 EE04 EE22 EE23 EE35 FG06 FG26 GG10 LL03 MM22 PP03 PP09 PP10 5G301 DA03 DA10 DA11 DA12 DA42 DA

Claims (3)

[Claims] 1. An electrode for electronic parts comprising a plurality of metal powders of the same element having different particle diameters of 10 μm or less dispersed in water or an organic solvent at a weight of 1 to 80% by weight and a viscosity of 2 poise or less. ink. 2. Using a bead of 0.01 mmφ or more and 10 mmφ or less, a plurality of metal powders of the same element having different particle diameters of 10 μm or less in water or an organic solvent at 1% by weight to 80% by weight, and A method for producing an electrode ink for electronic parts, which is dispersed to a viscosity of 2 poise or less and then filtered through a filter. 3. An electrode for electronic parts, wherein a plurality of metal powders of the same element having different particle diameters of 10 μm or less are dispersed in water or an organic solvent to have a viscosity of 1 to 80% by weight and a viscosity of 2 poise or less. After forming the ink in a predetermined pattern on a ceramic raw sheet or ceramic substrate using an ink jet device, after laminating or firing,
A method for manufacturing an electronic component that is singulated and provided with external electrodes.