WO2020022291A1

WO2020022291A1 - Conductive paste, electronic component, and laminated ceramic capacitor

Info

Publication number: WO2020022291A1
Application number: PCT/JP2019/028713
Authority: WO
Inventors: 鈴木　伸寿; 勝彦高木; 亮関塚
Original assignee: 住友金属鉱山株式会社
Priority date: 2018-07-25
Filing date: 2019-07-22
Publication date: 2020-01-30
Also published as: CN112470236B; CN112470236A; JP2020017405A; KR20210040290A; TWI810336B; JP7206671B2; TW202008394A

Abstract

The purpose of the present invention is to provide a conductive paste which has high dry film surface smoothness and a high dry film density, has excellent dispersibility of conductive powder and high adhesion when forming a laminate, and has very small chronological viscosity changes and excellent viscosity stability. Provided is a conductive paste that comprises a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein the dispersant includes an amino acid dispersant represented by general formula (1) indicated in the description and an amine dispersant represented by general formula (2) indicated in the description, the compounding ratio of the amino acid dispersant to the amine dispersant (amino acid dispersant/ amine dispersant) is in a range of 1/4 to 1/2 in mass ratio, and the total content of the amino acid dispersant and the amine dispersant relative to the total of the conductive paste is 0.7 to 1.2 mass%.

Description

Conductive paste, electronic components and multilayer ceramic capacitors

The present invention relates to a conductive paste, an electronic component, and a multilayer ceramic capacitor.

電子 With the miniaturization and high performance of electronic devices such as mobile phones and digital devices, miniaturization and high capacity of electronic components including multilayer ceramic capacitors are also desired. Multilayer ceramic capacitors have a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately stacked, and by reducing the thickness of these dielectric layers and internal electrode layers, miniaturization and high capacitance are achieved. Can be achieved.

The multilayer ceramic capacitor is manufactured, for example, as follows. First, a conductive paste for an internal electrode is printed (applied) on a surface of a green sheet containing a dielectric powder such as barium titanate (BaTiO ₃ ) and a binder resin in a predetermined electrode pattern, dried, and dried. Form a dry film. Next, a laminated body is formed in which the dried film and the green sheet are laminated so as to be alternately overlapped, and then heat-pressed and integrated. The laminate is cut, subjected to a deorganizing binder treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip. Next, an external electrode paste is applied to both ends of the fired chip, and after firing, nickel plating is applied to the surface of the external electrode to obtain a multilayer ceramic capacitor.

Generally, the conductive paste used to form the internal electrode layer contains a conductive powder, a ceramic powder, a binder resin, and an organic solvent. In addition, the conductive paste may include a dispersant in order to improve the dispersibility of the conductive powder and the like. With the recent thinning of the internal electrode layer, the conductive powder also tends to be reduced in particle size. When the particle size of the conductive powder is small, the specific surface area of the particle surface becomes large, so that the surface activity of the conductive powder (metal powder) becomes high, which may cause a decrease in dispersibility and a decrease in viscosity characteristics. .

Therefore, attempts have been made to improve the viscosity characteristics of the conductive paste over time. For example, Patent Document 1 discloses a conductive paste containing at least a metal component, an oxide, a dispersant, and a binder resin, wherein the metal component has a surface composition of Ni having a specific composition ratio. A conductive paste is described, which is a powder, the acid point amount of the dispersant is 500 to 2000 μmol / g, and the acid point amount of the binder resin is 15 to 100 μmol / g. According to Patent Literature 1, this conductive paste has good dispersibility and viscosity stability.

Further, Patent Document 2 discloses a conductive paste for an internal electrode, comprising a conductive powder, a resin, an organic solvent, a common material of ceramic powder mainly composed of TiBaO ₃ , and a coagulation inhibitor, which contains the coagulation inhibitor. The conductive paste for an internal electrode is described in which the amount is 0.1% by weight or more and 5% by weight or less and the aggregation inhibitor is a tertiary amine or a secondary amine represented by a specific structural formula. According to Patent Literature 2, the conductive paste for an internal electrode suppresses aggregation of the common material component, is excellent in long-term storage properties, and can make a multilayer ceramic capacitor thinner.

On the other hand, when thinning the internal electrode layer, it is required that the density of a dry film obtained by printing a conductive paste for the internal electrode on the surface of the green sheet and drying it is high. For example, Patent Document 3 discloses a metal ultrafine powder slurry containing an organic solvent, a surfactant, and metal ultrafine particles, wherein the surfactant is oleoyl sarcosine, and the metal ultrafine powder slurry contains A metal ultrafine powder slurry containing 70% by mass or more and 95% by mass or less of the metal ultrafine powder, and containing the surfactant in an amount of more than 0.05 part by mass and less than 2.0 parts by mass based on 100 parts by mass of the metal ultrafine powder. Has been proposed. According to Patent Document 3, by preventing aggregation of ultrafine particles, it is possible to obtain a metal ultrafine powder slurry having excellent dispersibility and dry film density in which no aggregated particles are present.

JP-A-2015-216244 JP 2013-149457 A JP 2006-063441 A

However, with the recent trend toward thinner electrode patterns, further improvement in viscosity characteristics over time and improvement in surface smoothness of the dried film after application are required.

In view of such circumstances, the present invention has high dry film surface smoothness and high dry film density, is excellent in dispersibility of conductive powder, has high adhesion at the time of forming a laminate, and has a long life It is an object of the present invention to provide a conductive paste that has a very small change in viscosity and is excellent in viscosity stability.

According to a first aspect of the present invention, there is provided a conductive paste containing a conductive powder, a ceramic powder, a dispersant, a binder resin and an organic solvent, wherein the dispersant is an amino acid-based dispersant represented by the following general formula (1): And an amine-based dispersant represented by the following general formula (2), and the compounding ratio of the amino acid-based dispersant and the amine-based dispersant (amino acid-based dispersant / amine-based dispersant) is 1/100 by mass ratio. It is in the range of 4 or more and 1/2 or less, and the total content of the amino acid-based dispersant and the amine-based dispersant is 0.7% by mass or more and 1.2% by mass or less with respect to the entire conductive paste. , A conductive paste is provided.

(However, in the formula (1), R ₁ represents a chain hydrocarbon having 10 to 20 carbon atoms.)

(Wherein, in the formula (2), R ₂ represents an alkyl group, an alkenyl group, or an alkynyl group having 8 to 16 carbon atoms, R ₃ represents an oxyethylene group, an oxypropylene group, or a methylene group; ₄ oxyethylene groups, or represents a oxypropylene group, _{R 3} and _{R 4} may be the same, or a different may. N atom in formula (2), in _{R 3} and _{R 4} It is not directly bonded to an O atom, Y is a number of 0 to 2, and Z is a number of 1 to 2.)

Further, in the general formula (1), R ₁ preferably represents a linear hydrocarbon group having 10 to 20 carbon atoms. Further, the conductive powder preferably contains at least one kind of metal powder selected from Ni, Pd, Pt, Au, Ag, Cu and alloys thereof. Further, it is preferable that the conductive powder is contained in an amount of 40% by mass or more and 60% by mass or less based on the whole conductive paste. The conductive powder preferably has an average particle size of 0.05 μm or more and 1.0 μm or less. Further, the ceramic powder preferably contains a perovskite oxide. Further, the ceramic powder preferably has an average particle size of 0.01 μm or more and 0.5 μm or less. The binder resin preferably contains at least one of a cellulose resin, an acrylic resin, and a butyral resin. Preferably, the conductive paste is for an internal electrode of a multilayer ceramic capacitor.

According to a second aspect of the present invention, there is provided an electronic component formed using the conductive paste.

According to a third aspect of the present invention, there is provided a multilayer ceramic capacitor having a laminate in which a dielectric layer and an internal electrode formed using the conductive paste are laminated.

The conductive paste of the present invention has a very small change in viscosity over time, is excellent in viscosity stability, is excellent in dispersibility of conductive powder, and has a high surface smoothness and a high dry film density in a dried film after application. Having. Further, the electrode pattern of an electronic component such as a multilayer ceramic capacitor formed using the conductive paste of the present invention has excellent adhesion of the conductive paste even when a thinned electrode is formed, and has a uniform width and precision. It has a thickness.

FIG. 1A is a perspective view illustrating a multilayer ceramic capacitor according to the present embodiment, and FIG. 1B is a cross-sectional view of the multilayer ceramic capacitor according to the present embodiment.

導電 The conductive paste of the present embodiment contains a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent. Hereinafter, each component will be described in detail.

(Conductive powder)
The conductive powder is not particularly limited, and a metal powder can be used. For example, one or more powders selected from Ni, Pd, Pt, Au, Ag, Cu, and an alloy thereof can be used. Among them, Ni or an alloy powder thereof is preferable from the viewpoints of conductivity, corrosion resistance and cost. As the Ni alloy, for example, an alloy of at least one or more elements selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt and Pd with Ni (Ni alloy) Can be used. The content of Ni in the Ni alloy is, for example, 50% by mass or more, and preferably 80% by mass or more. Further, the Ni powder may contain about several hundred ppm of S in order to suppress rapid gas generation due to partial thermal decomposition of the binder resin during the binder removal treatment.

平均 The average particle size of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less, and more preferably 0.1 μm or more and 0.5 μm or less. When the average particle size of the conductive powder is within the above range, the conductive powder can be suitably used as a paste for an internal electrode of a laminated ceramic capacitor having a reduced thickness, and for example, the smoothness of a dry film and the dry film density are improved. The average particle diameter is a value obtained by observation with a scanning electron microscope (SEM). The average particle diameter is obtained by measuring the particle diameter of each of a plurality of particles from an image observed with a SEM at a magnification of 10,000 times. Average value.

含有 The content of the conductive powder is preferably 30% by mass or more and less than 70% by mass, more preferably 40% by mass or more and 60% by mass or less based on the total amount of the conductive paste. When the content of the conductive powder is in the above range, the conductivity and the dispersibility are excellent.

(Ceramic powder)
The ceramic powder is not particularly limited. For example, when it is a paste for an internal electrode of a multilayer ceramic capacitor, a known ceramic powder is appropriately selected depending on the type of the multilayer ceramic capacitor to be applied. Examples of the ceramic powder include a perovskite oxide containing Ba and Ti, and preferably barium titanate (BaTiO ₃ ).

As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent may be used. Examples of the oxide include oxides of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and one or more rare earth elements. As such a ceramic powder, for example, a perovskite-type oxide ferroelectric ceramic powder in which Ba atom or Ti atom of barium titanate (BaTiO ₃ ) is replaced with another atom, for example, Sn, Pb, Zr, or the like. No.

In the internal electrode paste, a powder having the same composition as the dielectric ceramic powder constituting the green sheet of the multilayer ceramic capacitor may be used. This suppresses the occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering step. Examples of such a ceramic powder other than the above include, for example, ZnO, ferrite, PZT, BaO, Al ₂ O ₃ , Bi ₂ O ₃ , R (rare earth element) ₂ O ₃ , TiO ₂ , Nd ₂ O _{3 and the} like. Oxides. One type of ceramic powder may be used, or two or more types may be used.

(4) The average particle size of the ceramic powder is, for example, 0.01 μm or more and 0.5 μm or less, and preferably 0.01 μm or more and 0.3 μm or less. When the average particle diameter of the ceramic powder is in the above range, when used as an internal electrode paste, a sufficiently thin and thin uniform internal electrode can be formed. The average particle size is a value obtained by observation with a scanning electron microscope (SEM). The average particle size is obtained by measuring the particle size of each of a plurality of particles from an image observed at a magnification of 50,000 times with a SEM. Average value.

The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the conductive powder.

The content of the ceramic powder is preferably 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 20% by mass or less based on the total amount of the conductive paste. When the content of the ceramic powder is in the above range, the conductivity and the dispersibility are excellent.

(Binder resin)
The binder resin is not particularly limited, and a known resin can be used. Examples of the binder resin include cellulosic resins such as methylcellulose, ethylcellulose, ethylhydroxyethylcellulose, and nitrocellulose; acrylic resins; and butyral-based resins such as polyvinyl butyral. Among them, it is preferable to contain ethyl cellulose from the viewpoint of solubility in a solvent, combustion decomposability, and the like. When used as an internal electrode paste, a butyral-based resin may be used alone, or a butyral-based resin may be used alone from the viewpoint of improving the adhesive strength to the green sheet. One type of binder resin may be used, or two or more types may be used. As the binder resin, for example, a cellulose resin and a butyral resin can be used. The molecular weight of the binder resin is, for example, about 20,000 to 200,000.

含有 The content of the binder resin is preferably from 1 part by mass to 10 parts by mass, more preferably from 1 part by mass to 8 parts by mass, based on 100 parts by mass of the conductive powder.

(4) The content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less based on the total amount of the conductive paste. When the content of the binder resin is in the above range, the conductivity and the dispersibility are excellent.

(Organic solvent)
The organic solvent is not particularly limited, and a known organic solvent that can dissolve the binder resin can be used. Examples of the organic solvent include dihydroterpinyl acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like. And terpene solvents such as terpineol and dihydroterpineol, and hydrocarbon solvents such as tridecane, nonane and cyclohexane. One type of organic solvent may be used, or two or more types may be used.

含有 The content of the organic solvent is preferably 40 parts by mass or more and 100 parts by mass or less, more preferably 65 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the conductive powder.

(4) The content of the organic solvent is preferably from 20% by mass to 60% by mass, more preferably from 35% by mass to 55% by mass, based on the total amount of the conductive paste. When the content of the organic solvent is in the above range, the conductivity and the dispersibility are excellent.

(Dispersant)
The conductive paste of the present embodiment contains a dispersant. The dispersant includes an amino acid dispersant represented by the general formula (1) (amino acid surfactant) and an amine dispersant represented by the general formula (2). The dispersant may include a dispersant other than the amino acid dispersant represented by the general formula (1) and the amine dispersant represented by the general formula (2).

The present inventors have studied various dispersants for the conductive paste, and as a result, by combining the two types of dispersants at a specific compounding ratio, the viscosity change of the conductive paste over time. , The viscosity stability is very excellent, the dispersibility of the conductive powder is excellent, and the dried film after application has high surface smoothness and high dried film density.

In addition, the present inventors combine the two types of dispersants in a specific compounding ratio, and set the total content of the two types of dispersants to a specific amount, thereby improving the viscosity stability of the conductive paste. It has been found that the dispersibility can be further improved, and the adhesiveness when the laminate is formed is excellent.

詳細 The details of this reason are unknown, but it is considered that the amino group and carboxyl group present in the molecule of the dispersant act to coordinate with the metal atom of the conductive powder. Hereinafter, the dispersant used in the present embodiment will be described.

The amino acid-based dispersant used in the present embodiment has an N-acylamino acid skeleton and has a chain hydrocarbon group having 10 to 20 carbon atoms as shown in the following general formula (1).

(However, in the formula (1), R1 represents a chain hydrocarbon having 10 to 20 carbon atoms.)

In the above formula (1), R ₁ represents a chain hydrocarbon group having 10 to 20 carbon atoms. R ₁ preferably has 15 to 20 carbon atoms. Further, the chain hydrocarbon group may be a linear hydrocarbon group or a branched hydrocarbon group. Further, the chain hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group. R ₁ is preferably a straight-chain hydrocarbon group, more preferably a straight-chain alkenyl group, having a double bond.

アミノ酸 As the amino acid-based dispersant represented by the above formula (1), for example, one that satisfies the above characteristics can be selected from commercially available products and used. In addition, the amino acid-based dispersant may be manufactured using a conventionally known manufacturing method so as to satisfy the above-described properties.

The amine-based dispersant is a tertiary amine or a secondary amine as shown by the following general formula (2), and has a structure in which an amine group and one or two oxyalkylene groups are bonded. .

(Wherein, in the formula (2), R ₂ represents an alkyl group, an alkenyl group, or an alkynyl group having 8 to 16 carbon atoms, R ₃ represents an oxyethylene group, an oxypropylene group, or a methylene group; ₄ oxyethylene groups, or represents a oxypropylene group, _{R 3} and _{R 4} may be the same or may be different. also, the N atom in formula (2), _{R 3} and _{R 4} (It is not directly bonded to the O atom therein, Y is a number of 0 to 2, and Z is a number of 1 to 2.)

In the above formula (2), R ₂ represents an alkyl group having 8 to 16 carbon atoms, an alkenyl group, or an alkynyl group. When the carbon number of R ₂ is in the above range, the powder in the conductive paste has sufficient dispersibility and is excellent in solubility in a solvent. Note that R ₂ is preferably a straight-chain hydrocarbon group.

In the above formula (2), R ₃ represents an oxyethylene group, an oxypropylene group or a methylene group, R ₄ represents an oxyethylene group or an oxypropylene group, and R ₃ and R ₄ may be the same. Or may be different. Further, the N atom in the formula (2) and the O atom in R ₃ and R ₄ are not directly bonded, Y is a number from 0 to 2, and Z is a number from 1 to 2.

For example, in the above formula (2), when R ₃ is an oxyalkylene group represented by —AO— and Y is 1 to 2, the O atom in the endmost oxyalkylene group is (R ₃ ) Bonds to an H atom adjacent to _Y. When R ₃ is a methylene group, (R ₃ ) _Y is represented by — (CH ₂ ) _Y —, and when Y is 1 to 2, it is bonded to an adjacent H element to form a methyl group (—CH 2 ₃ ) or an ethyl group (—CH ₂ —CH ₃ ). When R ₄ is an oxyalkylene group represented by —AO—, the O atom in the oxyalkylene group at the extreme end bonds to an H atom adjacent to (R ₄ ) _Z.

In the above formula (2), when Y is 0, the amine-based dispersant is a secondary amine having —R ₂ , one hydrogen group, and — (R ₄ ) _z H. For example, when Y is 0 and Z is 2, the amine-based dispersant includes an alkyl group, an alkenyl group, or an alkynyl group having 8 to 16 carbon atoms, one hydrogen group, and — (R ₄ ) ₂ A secondary amine composed of-(AO) ₂ H in which H is bonded to any of a dioxyethylene group or a dioxypropylene group and an H element.

Further, in the above formula (2), when Y is 1, the amine-based dispersants, and -R _2, and -R ₃ H, - a tertiary amine having a _(R _{4) z} H. And, when Y is 2, the amine-based dispersant is composed of -R ₂ and any one of-(R ₃ ) ₂ H, a dioxyethylene group, a dioxypropylene group, or an ethylene group, and an H element. Is a tertiary amine having — (AO) ₂ H or —C ₂ H ₅ bonded thereto and — (R ₄ ) _z H.

アミン As the amine-based dispersant represented by the above formula (2), for example, a commercially available product that satisfies the above characteristics can be selected and used. Further, the amine-based dispersant may be manufactured so as to satisfy the above characteristics by using a conventionally known manufacturing method.

配合 The compounding ratio of the amino acid-based dispersant and the amine-based dispersant contained in the conductive paste (amino acid-based dispersant / amine-based dispersant) is in the range of 1/4 or more and 1/2 or less by mass ratio. In particular, when the mixing ratio of the amino acid-based dispersant and the amine-based dispersant is 1/4 or more and 2/5 or less, the conductive paste has very high viscosity stability.

When the lower limit of the mixing ratio of the amino acid-based dispersant and the amine-based dispersant is 1/4 or more, the effect of improving the viscosity of the conductive paste over time is further improved, and the dispersibility of the conductive powder is improved. As a result, a high dry film surface smoothness and a high dry film density can be obtained. In addition, when the upper limit of the mixing ratio of the amino acid-based dispersant and the amine-based dispersant is 1/2 or less, the amount of the amine-based dispersant is relatively increased, thereby greatly reducing the change over time in the viscosity of the conductive paste. be able to.

The total content of the amino acid-based dispersant represented by the above formula (1) and the amine-based dispersant represented by the above formula (2) is 0.7% by mass or more and 1.2% by mass based on the whole conductive paste. % Or less. When the total content of the amino acid-based dispersant and the amine-based dispersant is within the above range, the dispersibility of the conductive paste is improved, the dried film has a high dried film density, and has excellent surface smoothness. And the sheet attack and the peeling failure of the green sheet caused by the residual dispersant can be suppressed.

When the lower limit of the total content of the amino acid-based dispersant and the amine-based dispersant is 0.7% by mass or more, a conductive material containing the amino acid-based dispersant and the amine-based dispersant in the above-described mixing ratio. In the conductive paste, the dispersibility can be further improved, the smoothness of the dried film and the dried film density can be increased, and the change with time in the viscosity of the conductive paste can be further reduced. When the upper limit of the total content of the amino acid-based dispersant and the amine-based dispersant is 1.2% by mass or less, the residual amount of the dispersant on the surface of the dried film is further reduced, and drying during lamination and pressing is performed. Inhibition of adhesion between the film surface and the green sheet surface to prevent peeling is suppressed.

Note that the conductive paste may contain a dispersant other than the above-described amino acid-based dispersant and amine-based dispersant within a range not to impair the effects of the present invention. Examples of dispersants other than those described above include, for example, acid dispersants including higher fatty acids, polymer surfactants, cationic dispersants other than acid dispersants, nonionic dispersants, amphoteric surfactants, and polymer dispersants. It may contain a dispersant and the like. These dispersants may be used alone or in combination of two or more.

(Conductive paste)
The conductive paste of the present embodiment can be manufactured by preparing the above-described components and stirring and kneading them with a mixer. At this time, if the dispersant is applied to the surface of the conductive powder in advance, the conductive powder is sufficiently loosened without agglomeration, and the dispersant spreads over the surface, so that a uniform conductive paste can be easily obtained. Also, the binder resin is dissolved in an organic solvent for the vehicle, an organic vehicle is prepared, and the conductive powder, the ceramic powder, the organic vehicle and the dispersant are added to the organic solvent for the paste, and the mixture is stirred and kneaded with a mixer. A conductive paste may be prepared.

中 In the organic solvent, it is preferable to use the same organic solvent for the paste as that for adjusting the viscosity of the conductive paste in order to improve the familiarity of the organic vehicle. The content of the organic solvent for the vehicle is, for example, 5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the conductive powder. The content of the organic solvent for the vehicle is preferably 10% by mass or more and 40% by mass or less based on the total amount of the conductive paste.

Assuming that the viscosity of the conductive paste 24 hours after the production of the conductive paste is a reference (0%), the viscosity after standing for 28 days from the reference date is preferably within ± 10%. The viscosity of the conductive paste is measured, for example, by the method described in the examples (method of measuring with a Brookfield B-type viscometer at 10 rpm (shear speed = 4 sec ^-1 )). be able to.

表面 The surface smoothness of a dried film formed by printing a conductive paste can be evaluated by surface roughness. The surface roughness of the conductive paste is measured, for example, by the method described in the examples (method of measuring arithmetic average height Sa based on the standard of ISO 25178 using VK-X120 manufactured by Keyence Corporation). can do. The surface smoothness of the dried film, when evaluated by the arithmetic mean height Sa, is preferably 0.17 μm or less.

The conductive paste can be suitably used for electronic components such as multilayer ceramic capacitors. The multilayer ceramic capacitor has a dielectric layer formed using a green sheet and an internal electrode layer formed using a conductive paste.

In the multilayer ceramic capacitor, it is preferable that the dielectric ceramic powder contained in the green sheet and the ceramic powder contained in the conductive paste have the same composition. In the multilayer ceramic capacitor manufactured by using the conductive paste of the present embodiment, even if the thickness of the green sheet is, for example, 3 μm or less, sheet attack and poor peeling of the green sheet are suppressed.

[Electronic components]
Hereinafter, embodiments of an electronic component and the like of the present invention will be described with reference to the drawings. In the drawings, they may be represented in a schematic manner or in a modified scale as appropriate. The position and direction of the members will be described with reference to an XYZ orthogonal coordinate system shown in FIG. In this XYZ orthogonal coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is a vertical direction (up-down direction).

FIGS. 1A and 1B are views showing a multilayer ceramic capacitor 1 which is an example of an electronic component according to an embodiment. The multilayer ceramic capacitor 1 includes a multilayer body 10 in which dielectric layers 12 and internal electrode layers 11 are alternately stacked, and external electrodes 20.

Hereinafter, a method for manufacturing a multilayer ceramic capacitor using the conductive paste will be described. First, a conductive paste is printed on a green sheet and dried to form a dried film. A plurality of green sheets having the dried film on the upper surface are laminated and pressed together to obtain a laminate, and then the laminate is fired and integrated to form the internal electrode layer 11 and the dielectric layer 12. Are alternately laminated to produce a ceramic laminate 10. Thereafter, a pair of external electrodes 20 is formed on both ends of the ceramic laminate 10 to manufacture the multilayer ceramic capacitor 1. The details will be described below.

First, a green sheet, which is an unfired ceramic sheet using a dielectric material, is prepared. As the green sheet, for example, a dielectric layer paste obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to raw material powder of a predetermined ceramic such as barium titanate is supported on a PET film or the like. Examples thereof include those coated on a film in a sheet form and dried to remove the solvent. The thickness of the green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less from the viewpoint of demand for miniaturization of the multilayer ceramic capacitor.

Next, the above-mentioned conductive paste is printed (applied) on one surface of the green sheet by a known method such as a screen printing method and dried, and a plurality of dried sheets are prepared. Note that the thickness of the conductive paste after printing is preferably set to a thickness such that the thickness of the dried film after drying is 1 μm or less from the viewpoint of a demand for thinning the internal electrode layer 11.

Next, the green sheet is peeled off from the support film, and the green sheet and the dried film formed on one side thereof are laminated alternately, and then a laminate is obtained by heating and pressing. Note that a configuration may be adopted in which protective green sheets to which the conductive paste is not applied are further disposed on both surfaces of the laminate.

Next, after cutting the laminate to a predetermined size to form a green chip, the green chip is subjected to a binder removal treatment and fired in a reducing atmosphere to produce the ceramic laminate 10. Note that the atmosphere in the binder removal treatment is preferably air or an N ₂ gas atmosphere. The temperature at the time of performing the binder removal treatment is, for example, 200 ° C. or more and 400 ° C. or less. In addition, it is preferable that the holding time of the above-mentioned temperature when performing the binder removal treatment is 0.5 hours or more and 24 hours or less. The firing is performed in a reducing atmosphere in order to suppress the oxidation of the metal used for the internal electrode layer. The firing temperature of the stacked body is, for example, 1000 ° C. or more and 1350 ° C. or less. The temperature holding time at the time of performing is, for example, 0.5 hours or more and 8 hours or less.

(4) By firing the green chip, the organic binder in the green sheet is completely removed, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12. In addition, the organic vehicle in the dried film is removed, and the nickel powder or the alloy powder containing nickel as a main component is sintered or melted and integrated to form the internal electrode layer 11, thereby forming the dielectric layer 12. And a plurality of internal electrode layers 11 are alternately laminated to form a laminated ceramic fired body. The fired multilayer ceramic fired body may be annealed from the viewpoint of improving reliability by taking oxygen into the dielectric layer and suppressing re-oxidation of the internal electrode.

{Circle around (1)} The multilayer ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 to the manufactured multilayer ceramic fired body. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. External electrode layer 21 is electrically connected to internal electrode layer 11. In addition, as a material of the external electrode 20, for example, copper, nickel, or an alloy thereof can be preferably used. Note that the electronic component is not limited to the multilayer ceramic capacitor, but may be an electronic component other than the multilayer ceramic capacitor.

Hereinafter, the present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to the examples.

[Materials used]
(Conductive powder)
Ni powder (SEM average particle size 0.3 μm) was used as the conductive powder.

(Ceramic powder)
As the ceramic powder, barium titanate (BaTiO ₃ ; SEM average particle size 0.06 μm) was used.

(Binder resin)
As the binder resin, an ethyl cellulose resin and a polyvinyl butyral resin (PVB resin) were used. The binder resin used was prepared as a vehicle dissolved in terpineol.

(Dispersant)
(1) As the amino acid-based dispersant, a dispersant represented by R ₁ ＣC ₁₇ H ₃₃ (linear hydrocarbon group) in the general formula (1) was used.
(2) As the amine-based dispersant, in the above general formula (2), R ₂ ＣC ₁₂ H ₂₅ , R ₃ ＣC ₂ H ₄ O, R ₄中 C ₂ H ₄ O, Y = 1, Z = 1 Was used.

(Organic solvent)
Terpineol was used as the organic solvent.

[Example 1]
Ni powder 46 mass%, ceramic powder 11.5 mass%, binder resin (composed of ethyl cellulose resin and polyvinyl butyral resin) in the vehicle in a total of 3.2 mass%, amino acid dispersant 0.2 mass%, amine 0.6 mass% of the system dispersant and 100 mass% of terpineol (organic solvent) as the balance were blended, and these materials were mixed to prepare a conductive paste. The viscosity stability, dispersibility (dry film density, dry film surface roughness), and adhesion of the prepared conductive paste were evaluated by the following methods. Table 1 shows the evaluation results.

[Evaluation method]
(Viscosity stability: change in viscosity of conductive paste)
The viscosity of each sample after 24 hours of production of the conductive paste is set as a reference time, and the viscosity of each sample after standing at room temperature (25 ° C.) for 7, 14, and 28 days from the reference time is determined by the following method. Was measured. Then, when the viscosity after 24 hours of production (reference time point) is defined as a reference (0%), the amount of change in the viscosity of the sample after each standing is expressed as a percentage (%) ([( (Viscosity after 24 hours of production) / viscosity after 24 hours of production] × 100) was determined as the amount of change in viscosity. The viscosity of the conductive paste was measured using a Brookfield B-type viscometer at 10 rpm (shear rate = 4 sec ⁻¹ ). Note that it is preferable that the amount of change in the viscosity of the conductive paste be as small as possible. The viscosity stability of the conductive paste was evaluated as “A” when the amount of change in the viscosity of the conductive paste after standing for 28 days was 10% or less and “B” when the amount exceeded 10%.

(Dispersibility: dry film surface roughness, dry film density)
<Surface roughness>
The prepared conductive paste was screen-printed on a 2.54 cm (1 inch) square heat-resistant glass and dried in air at 120 ° C. for 1 hour to form a dried film of 20 mm square and a film thickness of 1 to 3 μm. . When the dispersibility of the conductive paste is good, the surface of the dried film becomes a smooth film. If the dispersibility is poor, agglomeration occurs in the conductive paste, the surface of the dried film becomes rough, and the surface smoothness decreases. Then, the surface roughness Sa (arithmetic mean height) and Sz (maximum height) of the manufactured dried film were measured based on the standard of ISO 25178 using a laser microscope (VK-X120 manufactured by Keyence Corporation). The smaller the values of the surface roughness Sa (arithmetic mean height) and Sz (maximum height), the smoother the surface of the dried film is.

<Dry Film Density (DFD)>
The prepared conductive paste was placed on a PET film and stretched to about 100 mm in length with an applicator having a width of 50 mm and a gap of 125 μm. After drying the obtained PET film at 120 ° C. for 40 minutes to form a dried body, the dried body was cut into four pieces of 2.54 cm (1 inch) square, and the PET film was peeled off. The thickness and mass of each of the dried films were measured, and the dry film density (average value) was calculated. When the dispersibility of the conductive paste is low and the conductive powder causes agglomeration, the dry film density is reduced, and the electrical characteristics may be poor. The higher the dry film density, the better the dispersibility.

<Evaluation of dispersibility>
When the surface roughness Sa (arithmetic mean height) of the dried film is 0.17 μm or less and the dry film density DFD is 5.50 g / cm ³ or more, “A” is defined as the surface roughness Sa of the dried film. (A) when either (arithmetic mean height) is greater than 0.17 μm and / or when dry film density DFD is less than 5.50 g / cm ³ , or when both are satisfied, the dispersibility is defined as “B”. Was evaluated.

(Adhesion)
The prepared conductive paste was printed (applied) on a green sheet by a screen printing method, and dried to prepare a plurality of sheets each having a dried film formed on the green sheet. Five of these sheets were laminated and subjected to thermocompression treatment at 80 ° C. and a pressure of 100 kg / cm ² for 3 minutes to form a laminate. In the obtained laminate, the adhesiveness between the dried film surface (electrode layer surface) and the bottom surface of the green sheet laminated thereon was weak, and if any peeling occurred at any one place, "x" and other peeling were observed. The case where no occurrence occurred was evaluated as “○”, and the adhesion was evaluated.

[Examples 2, 3 and Comparative Examples 1, 2]
A conductive paste was prepared under the same conditions as in Example 1 except that the contents of the amino acid-based dispersant and the amine-based dispersion were set to the amounts shown in Table 1 and the mixing ratio of the dispersant was changed. The amount of change in viscosity, the dry film density, the surface roughness of the dry film, and the adhesion of the prepared conductive paste were evaluated by the above-described methods. Table 1 shows the evaluation results.

[Examples 4 to 6, Comparative Examples 3 and 4]
Except that the content of the amino acid-based dispersant and the content of the amine-based dispersion were set to the amounts shown in Table 2 while the mixing ratio of the dispersant was kept constant, and the total content of the dispersant in the conductive paste was changed. A conductive paste was produced under the same conditions as in Example 1. The amount of change in viscosity, the dry film density, the surface roughness of the dry film, and the adhesion of the prepared conductive paste were evaluated by the above-described methods. Table 2 shows the evaluation results.

[Evaluation results]
As shown in Tables 1 and 2, the conductive paste of the example had a dry film density of 5.5 g / cm ³ or more, a surface roughness Sa (arithmetic mean height) of 0.17 μm or less, and a laminate. No delamination was observed, indicating good dispersibility and adhesion. In addition, the conductive paste of the example has a very low change of the viscosity of the conductive paste over time of 5.4% or less after 28 days, indicating that the conductive paste has very good viscosity stability. .

On the other hand, the conductive paste of Comparative Example 1, which has a low compounding ratio of the amino acid-based dispersant and the amine-based dispersant and contains a large amount of the amine-based dispersant, has good viscosity stability, but has a low dry film density. It was 5.5 g / cm ³ or less, the surface roughness Sa exceeded 0.17 μm, and the dispersibility was low as compared with the conductive paste of Example. Further, the surface roughness Sz (maximum height) also showed a slightly larger value as compared with the example. Further, the conductive paste of Comparative Example 2 containing a large amount of the amino acid-based dispersant and the amino acid-based dispersant and containing a large amount of the amino acid-based dispersant had a change in the viscosity of the conductive paste after 28 days of 16.7%. And changed by 10% or more.

In addition, the conductive paste of Comparative Example 3 in which the total content of the amino acid-based dispersant and the amine-based dispersant was less than 0.7% by mass had lower dispersibility than the conductive paste of Example, The viscosity stability was also lower as compared with the examples. In addition, the conductive paste of Comparative Example 4 in which the total content of the amino acid-based dispersant and the amine-based dispersant exceeds 1.2% by mass may cause peeling of a laminate manufactured using the conductive paste, The adhesiveness was lower than that of the conductive paste of the example.

技術 Note that the technical scope of the present invention is not limited to the modes described in the above embodiments and the like. One or more of the requirements described in the above embodiments may be omitted. Further, the requirements described in the above embodiments and the like can be appropriately combined. In addition, to the extent permitted by laws and regulations, the contents of Japanese Patent Application No. 2018-139501 and all documents cited in this specification are incorporated herein by reference.

The conductive paste according to the present embodiment is excellent in dispersibility, smoothness of the dried film after application, and, excellent in dry film density, and, because it is very excellent in viscosity stability over time, In particular, it can be suitably used as a raw material for an internal electrode of a multilayer ceramic capacitor which is a chip component (electronic component) of an electronic device such as a mobile phone or a digital device.

DESCRIPTION OF SYMBOLS 1 Multilayer ceramic capacitor 10 Ceramic laminated body 11 Internal electrode layer 12 Dielectric layer 20 External electrode 21 External electrode layer 22 Plating layer

Claims

Conductive paste containing conductive powder, ceramic powder, dispersant, binder resin and organic solvent,
The dispersant contains an amino acid-based dispersant represented by the following general formula (1) and an amine-based dispersant represented by the following general formula (2),
The mixing ratio of the amino acid-based dispersant and the amine-based dispersant (amino acid-based dispersant / amine-based dispersant) is in a mass ratio of 以上 or more and 以下 or less,
A conductive paste, wherein the total content of the amino acid-based dispersant and the amine-based dispersant is 0.7% by mass or more and 1.2% by mass or less based on the entire conductive paste.

(However, in the formula (1), R 1 represents a chain hydrocarbon group having 10 to 20 carbon atoms.)

(Wherein, in the formula (2), R 2 represents an alkyl group, an alkenyl group, or an alkynyl group having 8 to 16 carbon atoms, R 3 represents an oxyethylene group, an oxypropylene group, or a methylene group; 4 oxyethylene groups, or represents a oxypropylene group, R 3 and R 4 may be the same or may be different. also, the N atom in formula (2), R 3 and R 4 (It is not directly bonded to the O atom therein, and Y is a number from 0 to 2 and Z is a number from 1 to 2.)
The conductive paste according to claim 1, wherein in the general formula (1), R 1 represents a linear hydrocarbon group having 10 to 20 carbon atoms.
The conductive paste according to claim 1 or 2, wherein the conductive powder includes at least one metal powder selected from Ni, Pd, Pt, Au, Ag, Cu, and an alloy thereof.
(4) The conductive paste according to any one of (1) to (3), wherein the conductive powder is contained in an amount of 40% by mass or more and 60% by mass or less based on the whole conductive paste.
The conductive paste according to any one of claims 1 to 4, wherein the conductive powder has an average particle size of 0.05 μm or more and 1.0 μm or less.
(6) The conductive paste according to any one of (1) to (5), wherein the ceramic powder contains a perovskite oxide.
The conductive paste according to any one of claims 1 to 6, wherein the ceramic powder has an average particle size of 0.01 μm or more and 0.5 μm or less.
The conductive paste according to any one of claims 1 to 7, wherein the binder resin includes at least one of a cellulose resin, an acrylic resin, and a butyral resin.
The conductive paste according to any one of claims 1 to 8, which is used for an internal electrode of a multilayer ceramic capacitor.
An electronic component formed by using the conductive paste according to any one of claims 1 to 8.
A multilayer ceramic capacitor having a laminate in which an internal electrode layer formed by using the conductive paste according to claim 9 and a dielectric layer are laminated.