TW202313866A - Conductive paste for gravure printing, electronic component, and laminate ceramic capacitor - Google Patents

Abstract

Provided is conductive paste which is for gravure printing, and which can suppress separation between a conductive powder and a ceramic powder. This conductive paste for gravure printing includes a conductive powder, a ceramic powder, a dispersant, a binder resin, and organic solvents. The organic solvents include a first organic solvent, and a solvent other than the first organic solvent. The binder resin contains a butyral-based resin. The first organic solvent is at least one selected from the group consisting of ester-based solvents and ether-based solvents. An HSP distance between an HSP value of the first organic solvent and an HSP value of the butyral-based resin is less than that between an HSP value of the solvent other than the first organic solvent and the HSP value of the butyral-based resin.

Description

Conductive paste for gravure printing, electronic parts, and multilayer ceramic capacitors

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

Along with miniaturization and higher performance of electronic equipment such as mobile phones and digital devices, miniaturization and higher capacity of electronic components including multilayer ceramic capacitors are also desired. A multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated. By reducing the thickness of the dielectric layers and internal electrode layers, miniaturization and high capacity can be achieved.

A multilayer ceramic capacitor is manufactured, for example, as follows. First, a conductive paste for internal electrodes is printed in a predetermined electrode pattern on the surface of a ceramic green sheet containing dielectric powder such as barium titanate (BaTiO ₃ ) and a binder resin, and dried to form a dry film. Next, the dry film and the ceramic green sheets are stacked alternately to obtain a laminate. Next, this laminated body is heated and pressure-bonded to be integrated to form a pressure-bonded body. The press-bonded body is cut, and the organic binder is removed in an oxidizing gas atmosphere or an inert gas atmosphere, and then fired to obtain a fired wafer. Next, the slurry for external electrodes is applied to both ends of the fired wafer, and after firing, nickel plating or the like is applied to the surface of the external electrodes to obtain a multilayer ceramic capacitor.

As a printing method used when printing conductive paste on dielectric green sheets, screen printing has been generally used in the past, but in view of the miniaturization, thinning and productivity improvement of electronic equipment, higher production efficiency is required. Print finer electrode patterns.

As one of the printing methods of conductive paste, the gravure printing method is proposed as a continuous printing method. The conductive paste is filled in the concave part provided in the plate and pressed to the surface to be printed, thereby transferring conductive ink from the plate. sexual slurry. The gravure printing method has a high printing speed and is excellent in productivity. When using the gravure printing method, it is necessary to appropriately select a binder resin, a dispersant, a solvent, and the like in the conductive paste, and adjust characteristics such as viscosity to a range suitable for gravure printing.

For example, Patent Document 1 describes a conductive paste used for forming an internal conductor film by gravure printing. The internal conductor film has a plurality of ceramic layers and An internal conductor film in a laminated ceramic electronic part with an internal conductor film extending at a specific interface between them, the conductive paste contains 30 to 70% by weight of solid content containing metal powder, and an ethoxylate content of 1 to 10% by weight 49.6% or more of ethyl cellulose resin component, 0.05~5% by weight of dispersant, and the balance of solvent component, the viscosity η _0.1 at a shear rate of 0.1 (s ^-1 ) is 1 Pa·s or more, Furthermore, it is a thixotropic fluid whose viscosity η _0.02 at a shear rate of 0.02 (s ⁻¹ ) satisfies the conditions expressed by a specific formula.

In addition, Patent Document 2 describes a conductive paste that is also used for forming an internal conductor film by gravure printing similarly to the above-mentioned Patent Document 1, and contains 30 to 70% by weight of The solid content of the metal powder, the resin content of 1 to 10% by weight, the dispersant of 0.05 to 5% by weight, and the solvent content as the balance, and the viscosity at a shear rate of 0.1 (s ^-1 ) is 1 Pa·s or more The thixotropic fluid, when the viscosity at the shear rate of 0.1 (s ^-1 ) is used as the reference, the viscosity change rate at the shear rate of 10 (s ^-1 ) is more than 50%.

According to the above-mentioned Patent Documents 1 and 2, the above-mentioned conductive paste is a thixotropic fluid having a viscosity of 1 Pa·s or more at a shear rate of 0.1 (s ^-1 ), and stable continuous printing at high speed can be obtained in gravure printing. characteristics, it is possible to manufacture multilayer ceramic electronic parts such as multilayer ceramic capacitors with good production efficiency.

Also, Patent Document 3 describes a conductive paste for gravure printing, which contains a conductive powder (A), an organic resin (B), an organic solvent (C), an additive (D), and a dielectric powder (E). The conductive paste for internal electrodes of laminated ceramic capacitors, the organic resin (B) is composed of polyvinyl butyral with a degree of polymerization of 10,000 to 50,000 and ethyl cellulose with a weight average molecular weight of 10,000 to 100,000, The organic solvent (C) is composed of any one of propylene glycol monobutyl ether, or a mixed solvent of propylene glycol monobutyl ether and propylene glycol methyl ether acetate, or a mixed solvent of propylene glycol monobutyl ether and mineral spirits, and the additive (D) consists of The separation inhibitor and the dispersant are composed of a composition containing a polycarboxylate polymer or a polycarboxylate as the separation inhibitor. According to Patent Document 3, the conductive paste has a viscosity suitable for gravure printing, improves the uniformity and stability of the paste, and has good drying properties. [Prior Technical Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-187638 [Patent Document 2] Japanese Patent Laid-Open No. 2003-242835 [Patent Document 3] Japanese Unexamined Patent Publication No. 2012-174797

[Technical problem to be solved by the invention]

In the conductive paste for gravure printing, low viscosity is required. However, when ceramic powders such as barium titanate and conductive powders such as Ni are added to low-viscosity conductive pastes compared to high-viscosity conductive pastes for screen printing, etc. The difference in sedimentation velocity caused by the difference in specific gravity has a more significant effect, and the conductive powder and ceramic powder are easily separated.

For example, in a conductive paste for gravure printing, a phenomenon called "floating" (two-layer separation) may occur in which a white separation layer containing ceramic powder is formed on the upper part when the conductive paste is produced.

In addition, as a result of studies conducted by the inventors of the present invention, it was found that in the case of segregation of the ceramic powder in the conductive paste, not only "floating" occurs, but also there is a sintering delay of the ceramic powder at the time of sintering when the internal electrode layer is formed. There is a problem that the effect becomes localized and the coverage ratio at the time of forming the internal electrode layer decreases. It is considered that in the conductive paste in which the conductive powder and the ceramic powder are separated, there is a partial difference in the shrinkage speed of the internal electrode layer at the time of sintering, thereby reducing the coverage of the internal electrode layer.

In view of such a situation, an object of the present invention is to provide an electroconductive paste which has a low paste viscosity suitable for gravure printing and can suppress separation of electroconductive powder and ceramic powder. [Technical means]

In the first aspect of the present invention, a conductive paste for gravure printing is provided, which contains conductive powder, ceramic powder, dispersant, binder resin and organic solvent, the binder resin contains butyral resin, organic The solvent contains at least two organic solvents other than hydrocarbon-based solvents, and contains a first organic solvent and a solvent other than the first organic solvent, and the first organic solvent is at least one selected from the group consisting of ester-based solvents and ether-based solvents The HSP distance between the HSP value of the first organic solvent and the HSP value of the butyral-based resin is shorter than the HSP distance between the HSP value of solvents other than the first organic solvent and the HSP value of the butyral-based resin.

Moreover, ideally, in the electroconductive paste for gravure printings, a 1st organic solvent is represented by following formula (1). R ¹ -(OR ² ) _n -OR ³ ･･･Formula (1) (wherein, R ¹ represents an acyl group with 1 to 4 carbon atoms, a linear or branched alkyl group, and R ² represents the number of carbon atoms is a straight chain or branched chain alkylene group of 2 to 6, R ³ represents hydrogen, an acyl group with 1 to 4 carbon atoms, a straight chain or branched chain alkyl group, and n is 1 to 3.)

Also, ideally, the organic solvent further contains a second organic solvent as a solvent other than the first organic solvent, and the second organic solvent is selected from terpineol, dihydroterpineol, dihydroterpineol acetate, isoacetic acid At least one of the group of bornyl esters. Also, desirably, the organic solvent further contains a third organic solvent as a solvent other than the first organic solvent, and the third organic solvent is at least one selected from the group consisting of ketone-based solvents. Moreover, it is desirable to contain the 1st organic solvent in 3 mass % or more and 25 mass % or less with respect to the whole electroconductive paste. Also, ideally, the binder resin is a mixed resin containing a butyral-based resin and a cellulose-based resin, and the HSP distance between the HSP value of the first organic solvent and the HSP value of the mixed resin is greater than that of solvents other than the first organic solvent. The HSP distance between the HSP value of the resin and the HSP value of the mixed resin is short. Also, the dispersant desirably contains a carboxylic acid-based dispersant. Also, the conductive powder desirably contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof. Moreover, it is desirable that the average particle diameter of an electroconductive powder is 0.05 micrometer or more and 1.0 micrometer or less. Also, ideally, the ceramic powder contains barium titanate. Also, ideally, the average particle diameter of the ceramic powder is 0.01 μm or more and 0.5 μm or less. Moreover, it is desirable that the above-mentioned conductive paste for gravure printing is used for internal electrodes of laminated ceramic parts. Also, preferably, the above-mentioned conductive paste for gravure printing has a viscosity of 3 Pa·S or less at a shear rate of 100 sec ⁻¹ and a viscosity of 1 Pa· ^S or less at a shear rate of 10000 sec −1 .

In the 2nd aspect of this invention, the electronic component formed using the said electroconductive paste for gravure printing is provided.

In a third aspect of the present invention, there is provided a laminated ceramic capacitor comprising at least a laminate formed by laminating dielectric layers and internal electrode layers, wherein the internal electrode layers are formed using the above-mentioned conductive paste for gravure printing. [Effect of the invention]

The conductive paste of the present invention has characteristics suitable for gravure printing, can suppress separation of conductive powder and ceramic powder even in a low-viscosity paste, and has excellent printability when forming a thinned electrode. In addition, the internal electrode layer formed using the conductive paste of the present invention can be uniformly coated on the dielectric layer even when thinned.

[Conductive Paste] The conductive paste of this embodiment contains conductive powder, ceramic powder, a dispersant, a binder resin, and an organic solvent. Each component will be described in detail below.

(conductive powder) The conductive powder is not particularly limited, and metal powder can be used. For example, one or more powders selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof can be used. Among these, powders of Ni or alloys thereof (hereinafter, may be referred to as “Ni powder”) are desirable from the viewpoint of electrical conductivity, corrosion resistance, and cost. As the Ni alloy, for example, an alloy of at least one element selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt, and Pd and Ni can be used. The content of Ni in the Ni alloy is, for example, 50% by mass or more, preferably 80% by mass or more. Also, in order to suppress rapid gas generation due to partial thermal decomposition of the binder resin during the binder removal process, the Ni powder may contain element S of the order of several hundred ppm.

The average particle size of the conductive powder is desirably not less than 0.05 μm and not more than 1.0 μm, more preferably not less than 0.1 μm and not more than 0.5 μm. When the average particle diameter of the conductive powder is within the above range, it can be suitably used as a slurry for internal electrodes of thinned multilayer ceramic capacitors (multilayer ceramic parts), for example, the smoothness and dry film density of the dry film are improved. The average particle diameter is a value obtained by observation with a scanning electron microscope (SEM), and is obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observing with a SEM at a magnification of 10,000 times. Mean (SEM mean particle size).

The content of the conductive powder is preferably 30 mass % or more and less than 70 mass % with respect to the whole conductive paste, and more preferably 40 mass % or more and 60 mass % or less. When content of electroconductive powder is the said range, electroconductivity and dispersibility are excellent.

(Ceramic Powder) The ceramic powder is not particularly limited. For example, in the case of a slurry for internal electrodes of a laminated ceramic capacitor, a known ceramic powder is appropriately selected according to the type of laminated ceramic capacitor to be applied. As the ceramic powder, for example, a perovskite-type oxide containing Ba and Ti, preferably barium titanate (BaTiO ₃ ), can be used.

As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent can also be used. Examples of oxides include oxides of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and one or more rare earth elements. Also, as the ceramic powder, for example, a perovskite-type oxide ferroelectric ceramic powder obtained by substituting Ba atoms and Ti atoms of barium titanate (BaTiO ₃ ) with other atoms such as Sn, Pb, or Zr can be used.

When used as a conductive paste for internal electrodes, the ceramic powder may have the same composition as the dielectric ceramic powder constituting a green sheet of a laminated ceramic capacitor (electronic component). According to this, generation of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering step can be suppressed. Examples of such ceramic powders include ZnO, ferrite, PZT, BaO, Al ₂ O ₃ , Bi ₂ O ₃ , R (rare earth elements) ₂ O ₃ , TiO ₂ , and Nd in addition to the above. ₂ O ₃ and other oxides. In addition, one type of ceramic powder may be used, or two or more types may be used.

The average particle size of the ceramic powder is, for example, in a range of 0.01 μm to 0.5 μm, preferably in a range of 0.01 μm to 0.3 μm. When the average particle size of the ceramic powder is within the above range, when used as a slurry for internal electrodes, a sufficiently thin and uniform internal electrode can be formed. The average particle diameter is a value obtained by observation with a scanning electron microscope (SEM), and is an average obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observing with a SEM at a magnification of 50,000 times. value (SEM mean particle size).

The content of the ceramic powder is preferably 1% by mass to 20% by mass based on the entire conductive paste, more preferably 3% by mass to 15% by mass. When the content of the ceramic powder is within the above range, dispersibility and sinterability are excellent.

Also, the content of the ceramic powder is preferably from 1 part by mass to 30 parts by mass, more preferably from 3 parts by mass to 30 parts by mass, relative to 100 parts by mass of the conductive powder.

(Binder resin) As the binder resin, it is desirable to contain a butyral-based resin. In addition, when used as a paste for internal electrodes, from the viewpoint of improving the adhesive strength with the green sheet, a butyral-based resin may be contained, or a butyral-based resin may be used alone. When the binder resin contains a butyral-based resin, the viscosity can be easily adjusted to a viscosity suitable for gravure printing, and the adhesive strength with the green sheet can be further improved. For example, the butyral-based resin may be contained in an amount of 20% by mass or more, 30% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more of the entire binder resin. .

As the binder resin, resins other than butyral-based resins may be contained. Resins other than butyral-based resins are not particularly limited, and known resins can be used, for example, celluloses such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose resins, acrylic resins, etc. Among them, from the viewpoint of solubility in a solvent, combustion decomposability, etc., it is desirable to contain a cellulose-based resin, and it is more desirable to contain ethyl cellulose.

When the binder resin contains cellulose-based resin and butyral-based resin, from the viewpoint of further suppressing the separation of conductive powder and ceramic powder, the total content of cellulose-based resin and butyral-based resin (100% by mass), butyral-based resin may contain 20% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more. Also, the upper limit of the content of the butyral-based resin is not particularly limited, and may be less than 100% by mass, may be 90% by mass or less, or may be 80% by mass or less.

In addition, the degree of polymerization and the weight average molecular weight of the binder resin can be appropriately adjusted within the above-mentioned ranges according to the required viscosity of the conductive paste.

For example, when a cellulose-based resin is contained as a binder resin, the weight average molecular weight (Mw) may be 10,000 to 300,000, 30,000 to 200,000, or 50,000 to 200,000. Below 150,000. When Mw of the cellulose-based resin is in the above-mentioned range, the viscosity of the conductive paste can be adjusted to an appropriate range, and the separation suppression effect can be enhanced.

Also, the hydroxyl value of the cellulose-based resin is not particularly limited, but is preferably 0.1 mgKOH/g to 15 mgKOH/g, more preferably 0.5 mgKOH/g to 7 mgKOH/g, and still more preferably 1.5 mgKOH/g to 3 mgKOH /g or less. When the hydroxyl value of the cellulose-based resin is in the above range, the dispersibility of the conductive powder and the ceramic powder is excellent, so it can be suitably used for a conductive paste for gravure printing. In addition, the hydroxyl value is a value measured in accordance with JIS K 0070, and is a value indicating the number of mg of potassium hydroxide corresponding to the hydroxyl group in 1 g of the sample.

For example, when a butyral-based resin is contained as the binder resin, the weight average molecular weight (Mw) may be 30,000 to 300,000, may be 50,000 to 200,000, and may be 100,000 or more. And less than 150,000. When Mw of the butyral resin is in the above-mentioned range, the viscosity of the conductive paste can be adjusted to an appropriate range, and the separation suppression effect can be enhanced.

The content of the binder resin is preferably not less than 0.5% by mass and not more than 10% by mass, more preferably not less than 1% by mass and not more than 7% by mass relative to the entire conductive paste. When content of binder resin is the said range, electroconductivity and dispersibility are excellent.

The content of the binder resin is preferably not less than 1 part by mass and not more than 20 parts by mass, more preferably not less than 1 part by mass and not more than 14 parts by mass, relative to 100 parts by mass of the conductive powder.

(Organic solvents) The conductive paste according to this embodiment contains a first organic solvent and a solvent other than the first organic solvent as an organic solvent, and the first organic solvent is one selected from the group consisting of acetate-based solvents and ether-based solvents.

As the first organic solvent, for example, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate (BCA), diethylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether acetate, Ester, 3-methoxy-3-methylbutyl acetate, 1-methoxypropyl-2-acetate, propylene glycol monomethyl ether acetate and other glycol ether acetates, propylene glycol di Acetate, 1,4-butanediol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate and other diol diacetates, diethylene glycol Alcohol mono-2-ethylhexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, ethylene glycol monohexyl ether, dipropylene glycol methyl n-propyl ether, dipropylene glycol methyl n- Glycol ethers such as butyl ether, propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether (PNB), dipropylene glycol dimethyl ether, and cyclohexanol acetic acid Esters etc.

Moreover, the first organic solvent is preferably at least one selected from the solvents represented by the following formula (1). R ¹ -(OR ² ) _n -OR ³ ･･･Formula (1)

In the above formula (1), R ¹ represents an acyl group with 1 to 4 carbon atoms, a linear or branched chain alkyl group with 1 to 4 carbon atoms, and R ² represents an acyl group with 2 to 6 carbon atoms. A linear or branched alkylene group, R ³ represents hydrogen, an acyl group with 1 to 4 carbon atoms, a straight or branched alkyl group with 1 to 4 carbon atoms, and n is 1 to 3.

From the point of view of further suppressing the generation of whitening, in the above formula (1), ^R3 is preferably hydrogen or an acyl group with 1 to 4 carbon atoms, preferably hydrogen or an acyl group with 1 to 2 carbon atoms. group, more preferably hydrogen or acetyl group, further desirably acetyl group.

In addition, ^R1 is preferably an acyl group having 1 to 4 carbon atoms or a straight-chain alkyl group having 1 to 4 carbon atoms, more preferably an acyl group having 1 or 2 carbon atoms or an acyl group having 2 carbon atoms. A straight-chain alkyl group of ~4, preferably an acetyl group or a straight-chain alkyl group with 2 to 4 carbon atoms.

When R ¹ and R ³ are both acetyl groups, R ² may be a linear or branched alkylene group with 4 to 6 carbon atoms, and may be n=1.

When only R ³ is an acetyl group, R ¹ may be a straight chain alkyl group having 1 to 4 carbon atoms, preferably a straight chain alkyl group having 2 to 4 carbon atoms. In addition, ^R2 is ideally a straight-chain or branched alkylene group having 2 or 3 carbon atoms, or may be a straight-chain alkylene group having 2 carbon atoms, and n is preferably 2 or more.

Also, in the above formula (1), when R ¹ is a linear or branched alkyl group, R ³ may be an acyl group with 1 to 4 carbon atoms, a straight chain with 1 to 4 carbon atoms. A chain or branched alkyl group may be an acyl group having 1 or 2 carbon atoms, and an acetyl group may further be used. Also, n is ideally 1 or 2.

The content of the first organic solvent is preferably 3% by mass to 40% by mass, more preferably 3% by mass to 30% by mass, and still more preferably 5% by mass to 25% by mass, based on the entire conductive paste. , may be 10% by mass or more and 20% by mass or less.

In addition, one kind of first organic solvent may be used, or two or more kinds may be used. As the first organic solvent, for example, the first organic solvent may contain a solvent selected from the group consisting of diethylene glycol monobutyl ether acetate (BCA), methyl carbitol acetate, and propylene glycol monobutyl ether (PNB). One or more than two.

When the first organic solvent contains propylene glycol monobutyl ether (PNB), the content of propylene glycol monobutyl ether is preferably 3% by mass to 20% by mass, may be 5% by mass to 20% by mass, or may be 12% by mass or more and 18% by mass or less. In addition, the first organic solvent may contain propylene glycol monobutyl ether (PNB) alone.

In addition, the first organic solvent may contain two or more of propylene glycol monobutyl ether (PNB) and other organic solvents represented by the above formula (1). In other organic solvents represented by the above formula (1), for example, at least one of R ¹ and R ³ may be an acyl group having 1 to 4 carbon atoms, or may be an acetyl group. Examples of other organic solvents represented by the above formula (1) include diethylene glycol monobutyl ether acetate (BCA), methyl carbitol acetate, di(propylene glycol) methyl ether acetate ( DPMA), propylene glycol monomethyl ether acetate, etc.

Also, when the first organic solvent is diethylene glycol monobutyl ether acetate (BCA), the content of the first organic solvent may be not less than 3% by mass and not more than 20% by mass.

In addition, as the organic solvent, a solvent other than the first organic solvent may be contained. Solvents other than the first organic solvent are not particularly limited, and known organic solvents capable of dissolving the above-mentioned binder resin can be used. In addition, one kind of solvent other than the first organic solvent may be used, or two or more kinds may be used.

Moreover, the electroconductive paste which concerns on this Embodiment may further contain a 2nd organic solvent as a solvent other than a 1st organic solvent. The second organic solvent is at least one selected from the group consisting of terpineol (TPO), dihydroterpineol (DHT), dihydroterpineol acetate and isobornyl acetate, ideally terpineol (TPO ) and at least one of dihydroterpineol (DHT), more preferably dihydroterpineol (DHT).

The second organic solvent is preferably 5% by mass to 40% by mass, may be 10% by mass to 30% by mass, or may be 12% by mass to 25% by mass with respect to the total amount of the conductive paste.

Moreover, the electroconductive paste which concerns on this Embodiment may further contain a 3rd organic solvent as a solvent other than a 1st organic solvent. The third organic solvent is at least one selected from the group consisting of ketone solvents.

Examples of the ketone-based solvent include methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), and the like. When the third organic solvent is contained together with the first organic solvent, the viscosity can be adjusted without impairing the separation suppression effect, and the dryness can be improved. For example, propylene glycol monobutyl ether (PNB) may be contained as the first organic solvent, and diisobutyl ketone (DIBK) may be contained as the third organic solvent.

In addition, the content of the third organic solvent is preferably not less than 1% by mass and not more than 20% by mass relative to the total amount of the conductive paste, may be not less than 3% by mass and not more than 15% by mass, or may be not less than 3% by mass and not more than 10% by mass. %the following. Also, when the third organic solvent is contained, the upper limit of the content of the first organic solvent may be 15% by mass or less, may be 10% by mass or less, and may be further 8% by mass or less.

In addition, the organic solvent may contain a hydrocarbon-based solvent as a solvent other than the first organic solvent. Examples of the hydrocarbon-based solvent (petroleum-based hydrocarbon solvent) containing an aliphatic hydrocarbon solvent include solvents containing tridecane, nonane, cyclohexane, etc., mineral spirits (MA), naphthene-based solvents, and the like. Among these, mineral spirits are ideally contained, and mineral spirits may be contained as a main component (the most abundant solvent among aliphatic hydrocarbon solvents). In addition, the mineral spirits may contain chain saturated hydrocarbons as a main component, or may contain 20% by mass or more of chain saturated hydrocarbons with respect to the whole mineral spirits.

In addition, the organic solvent contains at least two types of organic solvents other than hydrocarbon-based solvents. The compatibility of a butyral resin and an organic solvent can be improved by containing several types of organic solvents other than a hydrocarbon solvent. In addition, the organic solvent may or may not contain a hydrocarbon solvent as long as it satisfies the relationship of the HSP distance between the organic solvent and the binder resin described later.

In addition, in the conductive paste according to this embodiment, as a solvent other than the first organic solvent, known solvents other than the above-mentioned second organic solvent, third organic solvent, and hydrocarbon-based solvent may be contained, for example, It can contain 5 mass % or less with respect to the whole organic solvent.

The content of the organic solvent (whole) is preferably from 20% by mass to 60% by mass, more preferably from 25% by mass to 45% by mass, based on the total amount of the conductive paste. When content of an organic solvent is the said range, electroconductivity and dispersibility are excellent.

The content of the organic solvent is preferably not less than 50 parts by mass and not more than 130 parts by mass, more preferably not less than 60 parts by mass and not more than 90 parts by mass, relative to 100 parts by mass of the conductive powder. When content of an organic solvent is the said range, electroconductivity and dispersibility are excellent.

(HSP distance between organic solvent and binder resin) The HSP distance between the HSP value of the first organic solvent and the HSP value of the butyral resin is preferably shorter than the HSP distance between the HSP value of solvents other than the first organic solvent and the HSP value of the butyral resin. When the first organic solvent, other organic solvents, and butyral-based resin satisfy the above relationship, the effect of suppressing the separation of the conductive powder and the ceramic powder is further enhanced. The details of the reason are not yet clear, for example, as one of the reasons for the separation of the conductive powder and the ceramic powder, butyral-based resins have low compatibility with organic solvents. In the permanent paste, by improving the compatibility of the butyral resin and the organic solvent, the separation inhibition effect is improved.

The HSP distance between the HSP value of the first organic solvent and the HSP value of the butyral resin is not particularly limited as long as it satisfies the above relationship, and may be, for example, 4 or more and less than 8, or may be 5 or more and 7.5 or less.

Also, the HSP distance between the HSP value of the solvent other than the first organic solvent and the HSP value of the butyral resin is not particularly limited as long as it satisfies the above relationship, for example, it may be 6.5 or more and 20 or less, and may be 8 or more and 15 or less.

Also, when the binder resin is a mixed resin containing a butyral resin and a cellulose-based resin, ideally the HSP distance between the HSP value of the first organic solvent and the HSP value of the mixed resin is greater than that of the first organic solvent. The HSP distance between the HSP value of the solvent and the HSP value of the mixed resin is short. In addition, the HSP distance between the HSP value of the organic solvent and the HSP value of the mixed resin varies depending on the content ratio of the butyral-based resin and the cellulose-based resin in the mixed resin.

In addition, the HSP distance refers to the distance between the Hansen solubility parameters (HSP values) of the respective binder resins and organic solvents. The Hansen solubility parameter is one of the indexes expressing the solubility of a substance, and the solubility is represented by a three-dimensional vector. Typically, this three-dimensional vector can be represented by a dispersion term (δ _d ), a polar term (δ _p ), and a hydrogen bond term (δ _h ). The closer the distance of the Hansen solubility parameter (HSP distance), the higher the compatibility can be evaluated.

In this specification, the HSP distance between the binder resin and the organic solvent can be calculated using the HSP value of the organic solvent registered in the database of the Hansen solubility parameter software HSPiP (Hansen Solubility Parameter in Practice).

Also, in the present invention, for organic solvents registered in the database of HSPiP version 5, this value is used, for organic solvents not registered in the database, values estimated from HSPiP version 5 are used, for organic solvents not registered in the database For the resin, conduct a dissolution test in 10-20 organic solvents with clear HSP values, and use the software HSPiP to calculate based on the HSP values of the organic solvents that can dissolve the resin.

In addition, in the case of mixed resins using multiple types of binder resins (for example, cellulose-based resins, butyral-based resins, etc.), the HSP value is determined by the HSP value (three-dimensional vector Each component) is calculated by accumulating the mixing volume ratio and adding them up.

Also, when the first organic solvent or other organic solvents are mixed solvents in which a plurality of types of organic solvents are mixed, the HSP value is determined by the HSP value (each component of the three-dimensional vector) for the mixed organic solvent alone The calculation is done by accumulating the mixed volume fractions and adding them up equally.

(Dispersant) As the dispersant, known dispersants can be used. As a dispersant, an acid-based dispersant may be contained, for example. Moreover, as an acid-based dispersant, a dispersant having an acidic group such as a carboxyl group or a phosphoric acid group may be included. Among them, a dispersant having a carboxyl group (carboxylic acid-based dispersant) is ideal, and a polycarboxylate having a plurality of carboxyl groups is more desirable. Acid-based dispersant.

For example, when using a polycarboxylic acid type dispersant as a dispersant, the dispersibility of an electroconductive paste improves by containing a polycarboxylic acid type dispersant. In addition, one kind of dispersant may be used, and two or more kinds may be used. The conductive paste according to this embodiment improves dispersibility by containing a dispersant. In addition, the polycarboxylic acid-based dispersant may be a comb-shaped carboxylic acid having a comb-shaped structure.

Also, for example, an acid-based dispersant having a hydrocarbon group may be contained as a dispersant. Examples of such acid-based dispersants include carboxylic acid-based dispersants such as higher fatty acids and polymer surfactants, phosphoric acid-based dispersants, and the like. These dispersants can be used alone or in combination of two or more.

As the higher fatty acid, it may be an unsaturated carboxylic acid or a saturated carboxylic acid, and it is not particularly limited. Examples thereof include stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, and linolenic acid. A higher fatty acid with an atomic number of 11 or more. Among them, oleic acid or stearic acid is preferable.

It does not specifically limit as other acidic dispersants, For example, the alkylmonoamine salt type typified by monoalkylamine salt, etc. are mentioned.

As the alkyl monoamine salt type, for example, oleyl sarcosine which is a compound of glycine and oleic acid, and an amide compound in which a higher fatty acid such as stearic acid or lauric acid is used instead of oleic acid is ideal.

In addition, when the molecular weight of the acid-based dispersant is small or when the acid value is large, the occurrence rate of whitening may increase. Therefore, the molecular weight of the acid-based dispersant may be 400 or more, or may be 500 or more, from the viewpoint of further enhancing the separation suppression effect. The upper limit of the molecular weight of the acid-based dispersant is not particularly limited, and is, for example, 100,000 or less. In addition, the acid value of the acid-based dispersant may be, for example, 280 or less, may be 200 or less, and may be further 100 or less. Moreover, the lower limit of the acid value of an acidic dispersant is 20 or more, for example.

In addition, the dispersant may contain dispersants other than the acid-based dispersant. Examples of dispersants other than acid-based dispersants include alkali-based dispersants, nonionic dispersants, amphoteric dispersants, and the like. These dispersants can be used alone or in combination of two or more.

Examples of the alkali-based dispersant include aliphatic amines such as laurylamine, rosinamine, cetylamine, myristylamine, and stearylamine. When the conductive paste contains the above-mentioned acid-based dispersant and alkali-based dispersant, the dispersibility is more excellent, and the viscosity stability over time is also excellent.

It is desirable to contain the dispersant in an amount of 3% by mass or less with respect to the whole conductive paste. The range including the upper limit of the content of the dispersant is preferably 2% by mass or less, more preferably 1% by mass or less. The range including the lower limit of the content of the dispersant is not particularly limited, and is, for example, 0.01% by mass or more, preferably 0.05% by mass or more. When the content of the dispersant is within the above-mentioned range, the dispersibility of the conductive paste can be improved, and the viscosity of the paste can be adjusted to an appropriate range, and the deterioration of the drying property after printing can be prevented, and further, it can be suppressed. Sheet erosion and poor peeling of green sheets.

Moreover, a dispersant may contain only an acidic dispersant, or may contain an acidic dispersant and a basic dispersant. When containing an acidic dispersant and an alkaline dispersant, the content of the alkaline dispersant may be smaller than the content of the acidic dispersant, and may be 90% by mass relative to the content of the acidic dispersant (100% by mass). Below, it may be 50 mass % or less, and further may be 30 mass % or less.

Also, with respect to 100 parts by mass of the conductive powder, it is desirable to contain 0.01 to 5 parts by mass of the dispersant, more preferably to contain 0.05 to 3 parts by mass, and even more preferably to contain 0.2 to 2 parts by mass. the following. When the content of the dispersant is within the above range, the dispersibility of the conductive powder and the ceramic powder and the smoothness of the dry electrode surface after coating are more excellent, and the viscosity of the conductive paste can be adjusted to an appropriate range, In addition, deterioration of drying properties after printing can be prevented, and sheet erosion and peeling defects of green sheets can be further suppressed.

In addition, the conductive paste according to this embodiment may contain dicarboxylic acid as an additive. Dicarboxylic acid system A carboxylic acid-based additive having two carboxyl groups (COO-groups).

Moreover, the average molecular weight of a dicarboxylic acid is not specifically limited, For example, it may be 1000 or less, 500 or less, and further may be 400 or less. When the average molecular weight of a dicarboxylic acid is the said range, in the electroconductive paste using the conventional organic solvent, the separation suppression effect can be acquired. The average molecular weight of dicarboxylic acid may be 100 or more, for example, and may be 200 or more.

In addition, in the conductive paste according to this embodiment, dicarboxylic acid may be contained in an amount of less than 2.0% by mass, 1.0% by mass or less, or 0.5% by mass or less with respect to the entire conductive paste. , and further may be 0.1% by mass or less. When there is too much content of dicarboxylic acid, the separation suppression effect may not be acquired. Also, when the content of the dicarboxylic acid is too high, the drying may become insufficient in the printing and drying steps, and the internal electrode layer may be in a soft state, which may cause lamination deviation in the subsequent lamination step, or may occur during the firing process. The dicarboxylic acid remaining during production is vaporized, and internal stress is generated by the vaporized gas component, or the structure of the laminate is broken.

In addition, when the conductive paste contains a dispersant (other than dicarboxylic acid) and dicarboxylic acid, the total content of the dispersant and dicarboxylic acid may be 0.05% by mass or more and 3.0% by mass relative to the entire conductive paste. Mass % or less may be 0.1 mass % or more and 2.0 mass % or less, and further may be 0.1 mass % or more and 1.0 mass % or less.

In addition, the conductive paste according to this embodiment does not need to contain dicarboxylic acid. Even when the conductive paste according to this embodiment does not contain dicarboxylic acid, as mentioned above, it is possible to exhibit a high separation suppression effect by containing a specific binder resin and an organic solvent. In particular, when a commercially available dicarboxylic acid with a small molecular weight is used in combination with the above-mentioned organic solvent, although a certain separation suppression effect can be obtained, compared with the case of using other acid-based dispersants, separation may occur. The suppression effect will be reduced.

(other additives) The conductive paste of this embodiment may contain other additives other than the said components as needed. As other additives, for example, conventionally known additives such as antifoaming agents, plasticizers, surfactants, and thickeners can be used.

(conductive paste) The manufacturing method of the electroconductive paste which concerns on this embodiment is not specifically limited, A conventionally well-known method can be used. For example, the conductive paste can be produced by stirring and kneading each of the above-mentioned components with a three-roll mill, a ball mill, a mixer, or the like. In addition, dicarboxylic acid (separation inhibitor) is ideally weighed and added while stirring and kneading with a mixer etc. in the same way as other materials, but even after the stirring and kneading (dispersion) are completed, the material Adding it as a separation inhibitor can also obtain the same separation inhibition effect.

The viscosity of the conductive paste at a shear rate of 100 sec ⁻¹ is ideally 3 Pa·S or less, and may be 2 Pa·S or less. When the viscosity at the time of a shear rate of 100sec ^-1 is the said range, it can be suitably used as the electroconductive paste for gravure printing. When the above range is exceeded, the viscosity may be too high and may not be suitable for gravure printing. The lower limit of the viscosity at a shear rate of 100 sec ^-1 is not particularly limited, and is, for example, 0.2 Pa·S or more.

In addition, the viscosity of the conductive paste at a shear rate of 10000 sec ⁻¹ is preferably 1 Pa·S or less. When the viscosity at the time of a shear rate of 10000sec ^-1 is the said range, it can be suitably used as the electroconductive paste for gravure printing. When exceeding the said range, a viscosity may become too high and it may not be suitable for gravure printing. The lower limit of the viscosity at a shear rate of 10000 sec ^-1 is not particularly limited, and is, for example, 0.05 Pa·S or more.

In addition, the thickness of the floating white layer observed after seven days immediately after the preparation of the conductive paste is preferably less than 10%, may be 8% or less, or may be 5% or less with respect to the thickness of the entire conductive paste , may be 3% or less, and further may be 2% or less. The smaller the thickness of the floating layer, the more excellent the separation suppression effect. In addition, the thickness of the whitening layer can be measured by the method described in the Example mentioned later.

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

[Electronic Parts] Hereinafter, embodiments of electronic components and the like according to the present invention will be described with reference to the drawings. In the drawings, it may be shown schematically or with a scale changed as appropriate. Moreover, the position, direction, etc. of a member are demonstrated with reference to the XYZ rectangular coordinate system shown in FIG. 1 etc. suitably. In this XYZ rectangular coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is a vertical direction (vertical direction).

A in FIG. 1 and B in FIG. 1 are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component according to the embodiment. Multilayer ceramic capacitor 1 includes ceramic laminate 10 and external electrodes 20 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated.

Hereinafter, the manufacturing method of the laminated ceramic capacitor using the said electroconductive paste is demonstrated. First, a conductive paste is printed on a ceramic green sheet and dried to form a dry film, and a laminate is obtained by laminating a plurality of ceramic green sheets having the dry film on the upper surface by pressure bonding, and then the laminate is fired. The ceramic laminate 10 in which the internal electrode layers 11 and the dielectric layers 12 are alternately laminated is fabricated. Thereafter, the laminated ceramic capacitor 1 is produced by forming a pair of external electrodes 20 at both ends of the ceramic laminate 10 . Hereinafter, a more detailed description will be given.

First, ceramic green sheets are prepared as unfired ceramic sheets. As the ceramic green sheet, for example, a slurry for a dielectric layer obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate is exemplified. A ceramic green sheet formed by coating a support film such as a PET film in a sheet shape and drying to remove the solvent. In addition, the thickness of the dielectric layer made of the ceramic green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less in view of the need for miniaturization of multilayer ceramic capacitors.

Next, a plurality of sheets in which a dry film was formed on one surface of the ceramic green sheet was prepared by applying the above-mentioned conductive paste to one surface of the ceramic green sheet by gravure printing and drying. In addition, from the viewpoint of the requirement for thinning the internal electrode layer 11 , the thickness of the dried film formed from the conductive paste is desirably 1 μm or less after drying.

Next, the ceramic green sheet is peeled off from the support film, and laminated so that the ceramic green sheet and the dry film formed on one surface of the ceramic green sheet are alternately arranged, and the laminate is obtained by heating and pressurizing. body. In addition, a configuration in which protective ceramic green sheets not coated with the conductive paste are further arranged on both surfaces of the laminate may be employed.

Next, after cutting the laminated body into a predetermined size to form a green wafer, the green wafer is subjected to a binder removal process and fired in a reducing gas atmosphere to manufacture a laminated ceramic fired body (ceramic laminated body 10 ). In addition, the gas environment in the binder removal process is ideally the air or N ₂ gas gas environment. The temperature at the time of performing binder removal process is 200 degreeC or more and 400 degreeC or less, for example. In addition, the retention time at the above-mentioned temperature when performing the binder removal treatment is preferably not less than 0.5 hours and not more than 24 hours. In addition, in order to suppress the oxidation of the metal used in the internal electrode layer, the firing is performed in a reducing gas atmosphere, and the temperature when firing the laminate is, for example, 1000°C or more and 1350°C or less. The holding time of the temperature is, for example, not less than 0.5 hours and not more than 8 hours.

By firing the green wafer, the organic binder in the ceramic 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 dry film is removed, and nickel powder or nickel alloy powder as the main component is sintered or melted to integrate, thereby forming the internal electrode layer 11, and further forming the dielectric layer 12 and the internal electrode layer 11 alternately. A laminated ceramic fired body formed by building up layers. In addition, from the viewpoint of improving reliability by introducing oxygen into the interior of the dielectric layer and suppressing reoxidation of internal electrodes, an annealing treatment may be performed on the fired laminated ceramic fired body.

Then, the laminated ceramic capacitor 1 is produced by providing a pair of external electrodes 20 on the produced laminated ceramic fired body. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22 . The external electrode layer 21 is electrically connected to the internal electrode layer 11 . In addition, as a material of the external electrode 20, for example, an alloy of copper, nickel, or the like can be preferably used. In addition, as electronic components, electronic components other than multilayer ceramic capacitors can further be used. [Example]

Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to an Example at all.

[Evaluation Method] (Viscosity of Electroconductive Paste) The viscosity after production of the electroconductive paste was measured using a rheometer (manufactured by Anton Paar Japan Co., Ltd.: Rheometer MCR302). The viscosity uses the value when it measured using the cone-plate with a cone angle of 1 degree and a diameter of 25 mm under conditions of a shear rate (shear rate) of 100 sec ⁻¹ and 10000 sec ⁻¹ .

(floating white) Put 10 g of the conductive paste just after production into a glass bottle (diameter φ30×height 65 mm), and after seven days, observe the appearance of the conductive paste visually, and measure the proportion of whitening observed. The whitening ratio (%) was calculated by (thickness of the whitening layer/thickness of the whole slurry amount)×100.

[Materials used] (conductive powder) As the conductive powder, Ni powder (SEM average particle size: 0.2 μm) was used.

(ceramic powder) As the ceramic powder, barium titanate (BaTiO3; SEM average particle size: 0.10 μm) was used.

(Binder resin) As the binder resin, polyvinyl butyral resin and ethyl cellulose resin are used.

(Dispersant) As the acid-based dispersant, comb-type carboxylic acid (molecular weight: 10000 or more, acid value: 60), monocarboxylic acid-based dispersant and phosphoric acid-based dispersant, and dicarboxylic acid (molecular weight: 370, acid value: 299/Hypermer KD-16, manufactured by Croda Japan Co., Ltd.), and as an alkali-based dispersant, oleylamine was used. In addition, in Table 1, comb-type carboxylic acid is represented by "acid type a", "monocarboxylic acid type dispersant and phosphoric acid type dispersant" (mass ratio 1:1) is represented by "acid type b", and "dicarboxylic acid type dispersant" is represented by "acid type b". Acid" is represented by "acid system c".

(Organic solvents) As the organic solvent, the following solvents were used. (1) The first organic solvent Propylene glycol monobutyl ether (PNB), diethylene glycol monobutyl ether acetate (BCA), 1,6-hexanediol diacetate (1,6-HDDA), 1,3-butanediol diethyl Diethylene glycol monoethyl ether acetate (1,3-BGDA), diethylene glycol monoethyl ether acetate (EDGAC), ethylene glycol monobutyl ether acetate (EGBA), di(propylene glycol) methyl ether acetate (DPMA) (2) The second organic solvent Dihydroterpineol (DHT), Terpineol (TPO) (3) Other organic solvents Diisobutyl ketone (DIBK), mineral spirits (MA), ethanol (EtOH), isobornyl acetate (IBA) (in addition, ethanol and isobornyl acetate are not the first organic solvent, but are compatible with the first organic solvent For comparison, in Table 1, "EtOH*" and "IBA*" are described in the item of the first organic solvent).

[example 1] Add 49% by mass of conductive powder, 12% by mass of ceramic powder, 0.1% by mass of acid-based dispersant, and 2.5% by mass of binder resin (polyvinyl butyral resin: ethyl cellulose = 7:3 (mass ratio)) , 10.9% by mass of PNB as an organic solvent, 7.3% by mass of MA, and DHT as the balance, were blended so that the whole was 100% by mass, and these materials were mixed to prepare a conductive paste. Table 1 shows the content of each material of the conductive paste and the evaluation results of floating (%).

[Examples 1 to 19] Except having changed the kind and content ratio of an organic solvent, and the kind and content ratio of a dispersing agent as shown in Table 1, it carried out similarly to Example 1, and produced and evaluated the electroconductive paste. Table 1 shows the content of each material of the conductive paste and the evaluation results of floating (%).

[Table 1]

(Evaluation results) The conductive pastes of Examples 1 to 11 suppressed generation of whitening compared with the conductive pastes of Examples 9 to 18 which did not contain the first organic solvent. In addition, in Example 19 in which only one type of first organic solvent was used as an organic solvent other than a hydrocarbon-based organic solvent, the occurrence rate of whitening was high.

In addition, in all the conductive pastes of Examples and Comparative Examples shown in Table 1, the viscosity when the shear rate is 100 sec ^-1 is 3 Pa·s or less, and the viscosity when the shear rate is 10000 sec ^-1 is 1 Pa·s. Below S. The above viscosity range can be suitably used for gravure printing. [Industrial Utilization]

When the electroconductive paste of this invention is used for formation of the internal electrode of a laminated ceramic capacitor, the laminated ceramic capacitor with high reliability can be obtained with high productivity. Therefore, the conductive paste of the present invention can be particularly suitably used as a raw material for internal electrodes of laminated ceramic capacitors, which are chip parts of electronic equipment such as mobile phones and digital equipment, which are increasingly miniaturized, and can be suitably used for gravure printing. conductive paste.

In addition, the technical scope of this invention is not limited to the aspect demonstrated in the said embodiment etc. In some cases, one or more requirements described in the above-mentioned embodiments and the like are omitted. In addition, the requirements described in the above-mentioned embodiments and the like may be appropriately combined. In addition, the disclosures of Japanese Patent Application No. 2021-093299, which is a Japanese patent application, and all documents cited in this specification are incorporated as part of the description of this specification within the scope permitted by law.

1: Multilayer ceramic capacitor 10: Ceramic laminate 11: Internal electrode layer 12: Dielectric layer 20: External electrodes 21: External electrode layer 22: Plating layer

[ FIG. 1 ] is a perspective view and a cross-sectional view showing a multilayer ceramic capacitor according to an embodiment.

1: Multilayer ceramic capacitor

10: Ceramic laminate

11: Internal electrode layer

12: Dielectric layer

20: External electrode

21: External electrode layer

22: Plating layer

Claims (15)

A conductive paste for gravure printing, which contains conductive powder, ceramic powder, dispersant, binder resin and organic solvent, and its characteristics are: The binder resin contains a butyral-based resin; The organic solvent contains at least two organic solvents other than hydrocarbon-based solvents, and contains a first organic solvent and a solvent other than the first organic solvent. The first organic solvent is selected from ester-based solvents and ether-based solvents. at least one of the group; The HSP distance between the HSP value of the first organic solvent and the HSP value of the butyral-based resin is greater than the HSP distance between the HSP value of solvents other than the first organic solvent and the HSP value of the butyral-based resin short. The conductive paste for gravure printing according to Claim 1, wherein the first organic solvent is represented by the following formula (1), R ¹ -(OR ² ) _n -OR ³ ･･･Formula (1) Wherein, R ¹ represents an acyl group with 1 to 4 carbon atoms, a straight chain or branched chain alkyl group, R ² represents a straight chain or branched chain alkylene group with 2 to 6 carbon atoms, and R ³ represents hydrogen , an acyl group with 1 to 4 carbon atoms, a linear or branched chain alkyl group, n is 1 to 3. The conductive paste for gravure printing as described in Claim 2, wherein the organic solvent further contains a second organic solvent as a solvent other than the first organic solvent, and the second organic solvent is selected from terpineol, dihydroterpene At least one of the group consisting of pinol, dihydroterpineol acetate, and isobornyl acetate. The conductive paste for gravure printing according to any one of claims 1 to 3, wherein the organic solvent further contains a third organic solvent as a solvent other than the first organic solvent, and the third organic solvent is selected from ketones At least one of the group of solvents. The electroconductive paste for gravure printing in any one of Claims 1-4 which contains the said 1st organic solvent in 3 mass % or more and 25 mass % or less with respect to the whole electroconductive paste. The conductive paste for gravure printing according to any one of claims 1 to 5, wherein the binder resin is a mixed resin containing the butyral resin and the cellulose resin, and the first organic solvent The HSP distance between the HSP value and the HSP value of the mixed resin is shorter than the HSP distance between the HSP values of solvents other than the first organic solvent and the HSP value of the mixed resin. The conductive paste for gravure printing according to any one of claims 1 to 6, wherein the dispersant contains a carboxylic acid-based dispersant. The conductive paste for gravure printing according to any one of Claims 1 to 7, wherein the conductive powder contains an alloy selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and the like. at least one metal powder. The conductive paste for gravure printing according to any one of claims 1 to 8, wherein the conductive powder has an average particle diameter of 0.05 μm or more and 1.0 μm or less. The conductive paste for gravure printing according to any one of claims 1 to 9, wherein the ceramic powder contains barium titanate. The conductive paste for gravure printing according to any one of claims 1 to 10, wherein the average particle diameter of the ceramic powder is 0.01 μm or more and 0.5 μm or less. The conductive paste for gravure printing according to any one of claims 1 to 11, which is used for internal electrodes of laminated ceramic parts. The conductive paste for gravure printing as described in any one of Claims 1 to 12, wherein the conductive paste for gravure printing has a viscosity of 3 Pa·S or less at a shear rate of 100 sec ^-1 . The viscosity when the shear rate is 10000sec ^-1 is 1Pa·S or less. An electronic component characterized in that the electronic component is formed by using the conductive paste for gravure printing according to any one of Claims 1 to 13. A multilayer ceramic capacitor, characterized in that the multilayer ceramic capacitor has a laminate formed by stacking at least a dielectric layer and an internal electrode layer; The internal electrode layer is formed using the conductive paste for gravure printing described in any one of Claims 1 to 13.

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