WO2023017747A1 - Electroconductive ink - Google Patents

Abstract

An electroconductive ink is provided in which metal nanoparticles are inhibited from aggregating.　The electroconductive ink comprises surface-modified metal nanoparticles (A) coated with a protectant comprising one or more amines, a wetting dispersant (B), and a dispersing solvent (C). The wetting dispersant (B) preferably has an amine value of 3-145 mgKOH/g and an acid value of 4-185 mgKOH/g. The amines in the surface-modified metal nanoparticles (A) preferably comprise: an aliphatic monoamine (1) having six or more carbon atoms in total; and an aliphatic monoamine (2) having five or more carbon atoms in total and/or an aliphatic diamine (3) having eight or less carbon atoms in total.

Description

conductive ink

The present disclosure relates to conductive ink. This application claims the priority of Japanese Patent Application No. 2021-130786 filed in Japan on August 10, 2021, the content of which is incorporated herein.

Because metal nanoparticles such as silver nanoparticles can be sintered at low temperatures, they are used to form electronic components such as electrodes and wiring on plastic substrates. In Patent Document 1, by coating the surface of silver nanoparticles with a protective agent containing an amine, good dispersion stability in a solvent can be obtained, and the silver nanoparticles are treated with alicyclic hydrocarbons, alcohols, etc. Disclosed is an ink obtained by dispersing in a solvent containing

WO2014/021270

However, in the ink of Cited Document 1, since the silver nanoparticles tend to aggregate, the aggregates cause clogging of the screen plate, etc., making continuous printing difficult. Since it is difficult to disperse, there is a problem of poor storage stability.

Therefore, an object of the present disclosure is to provide a conductive ink in which aggregation of metal nanoparticles is suppressed.

The inventors of the present disclosure have made intensive studies to solve the above problems, and as a result, an ink obtained by dispersing metal nanoparticles having a structure in which the surface is coated with a protective agent containing an amine in a dispersion solvent together with a dispersant. However, it was found that aggregation of metal nanoparticles hardly occurred. The present disclosure has been completed based on these findings.

That is, the present disclosure provides a conductive ink containing surface-modified metal nanoparticles (A) coated with a protective agent containing an amine, a wetting and dispersing agent (B), and a dispersing solvent (C).

The wetting and dispersing agent (B) preferably has an amine value of 3 to 145 mgKOH/g and an acid value of 4 to 185 mgKOH/g.

The amines in the surface-modified metal nanoparticles (A) include an aliphatic monoamine (1) having 6 or more carbon atoms, an aliphatic monoamine (2) having 5 or less carbon atoms and/or an aliphatic diamine having 8 or less carbon atoms ( 3) is preferably included.

The above aliphatic monoamine (1) is preferably an alkyl monoamine having a linear alkyl group with 6 to 18 carbon atoms and/or an alkyl monoamine having a branched alkyl group with 6 to 16 carbon atoms.

The above aliphatic monoamine (2) is preferably an alkyl monoamine having a linear or branched alkyl group with 2 to 5 carbon atoms.

The surface-modified metal nanoparticles (A) are preferably surface-modified silver nanoparticles.

The wetting and dispersing agent (B) preferably has an acidic group.

The content of the wetting and dispersing agent (B) is preferably 0.5 to 5.0% by mass with respect to 100% by mass of the conductive ink.

The conductive ink preferably further contains a binder resin (D).

The conductive ink may further contain an antifoaming agent (E).

The antifoaming agent (E) is preferably a polymer antifoaming agent.

The content of the antifoaming agent (E) is preferably 0.1 to 10% by mass with respect to 100% by mass of the conductive ink.

The conductive ink preferably further contains a sintering aid.

The sintering aid is preferably an aliphatic diamine having a primary amino group and/or a tertiary amino group.

The aliphatic diamine is preferably 3-diethylaminopropylamine.

The conductive ink preferably has a viscosity of 1 to 200 Pa·s at 25° C. and a shear rate of 10 s ⁻¹ .

The present disclosure also provides a method of manufacturing an electronic device, including a step of applying the conductive ink on a substrate by screen printing and a step of sintering.

The present disclosure also provides an electronic device comprising the sintered body of the conductive ink.

Since the conductive ink of the present disclosure has the above configuration, aggregation of metal nanoparticles is less likely to occur. Therefore, it can be suitably used for manufacturing an electronic device by forming electrodes, wiring, etc. on a plastic substrate by printing.

[Conductive ink]
The conductive ink of the present disclosure contains surface-modified metal nanoparticles (A) coated with an amine-containing protective agent, and further contains a wetting and dispersing agent (B) and a dispersing solvent (C). A conductive ink is an ink that can exhibit conductivity after being applied and sintered.

<Surface-modified metal nanoparticles (A)>
The surface-modified metal nanoparticles (A) according to the present disclosure have a structure in which the surface of the metal nanoparticles is coated with a protective agent containing an amine. It has a physically coordinated configuration.

The surface-modified metal nanoparticles according to the present disclosure preferably have a primary average particle size of 0.5 to 100 nm, more preferably 0.5 to 80 nm, even more preferably 1.0 to 65 nm, and particularly preferably 1.0 to 50 nm. is.

Examples of metals constituting the metal nanoparticles include metals having conductivity, such as gold, silver, copper, nickel, aluminum, rhodium, cobalt, ruthenium, platinum, palladium, chromium, and indium. Among the metal nanoparticles, silver is particularly preferred because it can fuse with each other at a temperature of about 100° C. and can form a bonding member such as an electronic component having conductivity even on a general-purpose plastic substrate with low heat resistance. Nanoparticles are preferred.

Examples of the amine include aliphatic monoamines having at least one amino group selected from primary amino groups, secondary amino groups and tertiary amino groups, or polyvalent amines having two or more (diamine etc.).

The amine is at least one selected from aliphatic monoamines (1) having a total carbon number of 6 or more, aliphatic monoamines having a total carbon number of 5 or less (2), and aliphatic diamines having a total carbon number of 8 or less (3). and more preferably containing an aliphatic monoamine (1) and an aliphatic monoamine (2) and/or an aliphatic diamine (3).

The aliphatic monoamine (1) has a total carbon number of 6 to 18 (more preferably 6 to 16, more preferably 6 to 12) amine compounds having a straight-chain alkyl group are preferred, for example, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexa decylamine, heptadecylamine, octadecylamine and the like.

In addition, as the aliphatic monoamine (1), a branched alkyl group having a total carbon number of 6 to 16 (more preferably 6 to 10) can be imparted with dispersibility even in a small amount due to steric factors. , such as isohexylamine, 2-ethylhexylamine, tert-octylamine, and the like.

The aliphatic monoamine (1) also includes, for example, primary amines having a cycloalkyl group (cyclohexylamine, etc.), primary amines having an alkenyl group, etc. (oleylamine, etc.), primary amines having a linear alkyl group, etc. Secondary amines (N,N-dipropylamine, N,N-dibutylamine, N,N-dipentylamine, N,N-dihexylamine, N,N-dipeptylamine, N,N-dioctylamine, N,N- dinonylamine, N,N-didecylamine, N,N-diundecylamine, N,N-didodecylamine, N-propyl-N-butylamine, etc.), secondary amines having branched alkyl groups (N,N- diisohexylamine, N,N-di(2-ethylhexyl)amine, etc.), tertiary amines having branched alkyl groups (tertiary amines having linear alkyl groups (tributylamine, trihexylamine, etc.) ), triisohexylamine, tri(2-ethylhexyl)amine, etc.).

The aliphatic monoamine (2) has a total carbon number of 2 to 5 (more preferably 3 to 5, more preferably 4 to 5) Amine compounds having a linear or branched alkyl group are preferred.

Specific examples of the aliphatic monoamine (2) include primary amines having a linear or branched alkyl group (ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec- butylamine, tert-butylamine, pentylamine, isopentylamine, tert-pentylamine, etc.), secondary amines having linear or branched alkyl groups (N,N-dimethylamine, N,N-diethylamine, N -methyl-N-propylamine, N-ethyl-N-propylamine, etc.).

As the above-mentioned aliphatic diamine (3), as a result of the difference in coordinating ability of the two amino groups, the complication of coordination can be suppressed. diamines (more preferably alkylenediamines), such as 2-dimethylaminoethylamine, 2-diethylaminoethylamine, 3-dimethylaminopropylamine, 3-diethylaminopropylamine, 4-dimethylaminobutylamine, 4-diethylaminobutylamine, 6- dimethylaminohexylamine and the like.

The aliphatic diamine (3) is a diamine having two primary amino groups (ethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine, 1 ,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,5-diamino-2-methylpentane, etc.), diamines having two secondary amino groups (N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3-propanediamine, N,N'- Dimethyl-1,4-butanediamine, N,N'-diethyl-1,4-butanediamine, N,N'-dimethyl-1,6-hexanediamine, etc.), diamines having two tertiary amino groups ( N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetramethyl-1,3-propanediamine, N,N , N′,N′-tetraethyl-1,3-propanediamine, N,N,N′,N′-tetramethyl-1,4-butanediamine, N,N,N′,N′-tetraethyl-1, 4-butanediamine, N,N,N',N'-tetramethyl-1,6-hexanediamine, etc.).

The aliphatic monoamine (1), the aliphatic monoamine (2), and the aliphatic diamine (3) may be used alone or in combination of two or more.

The amine according to the present disclosure may contain other amine compounds in addition to the aliphatic monoamine (1), the aliphatic monoamine (2), and the aliphatic diamine (3). The content of is preferably 40.0% by mass or less, more preferably 20.0% by mass or less, still more preferably 10.0% by mass or less, and particularly preferably 0% by mass with respect to 100% by mass of the amine according to the present disclosure. % by mass.

The content of the surface-modified metal nanoparticles (A) according to the present disclosure is preferably 30 to 90% by mass, more preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass with respect to 100% by mass of the conductive ink. % by mass.

<Wetting and dispersing agent (B)>
The wetting and dispersing agent (B) according to the present disclosure is a wetting and dispersing agent that can be easily applied to a low-polar dispersion solvent, such as a surfactant.

The wetting and dispersing agent (B) is preferably a compound having a basic polar functional group and/or an acidic polar functional group. Examples of the basic polar functional group include an amino group, an imino group, an amide group, an imide group and the like. The basic polar functional group adheres to the surface-modified metal nanoparticles (A) and exhibits the effect of imparting dispersibility to the surface-modified metal nanoparticles (A). The acidic polar functional group is a so-called acidic group, and examples thereof include a phosphate group. The acidic polar functional group exhibits affinity for a low-polar dispersing solvent. The wetting and dispersing agent (B) may form a salt. That is, the wetting and dispersing agent (B) may be a polymer salt.

Among them, the wetting and dispersing agent (B) preferably has at least an acidic polar functional group, and particularly preferably has an acidic polar functional group and a basic polar functional group, in terms of particularly excellent dispersibility. Accordingly, the wetting and dispersing agent (B) is preferably a compound having an acidic group, and particularly preferably a compound having both an acidic group and a basic group.

When the wetting and dispersing agent (B) has an acidic polar functional group and a basic polar functional group, the acid value preferably exceeds the amine value. The difference between the oxidation value and the amine value is, for example, preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 30 mgKOH/g or more, and particularly preferably 45 mgKOH/g or more. The difference between the oxidation value and the amine value is, for example, preferably 150 mgKOH/g or less, more preferably 100 mgKOH/g or less, still more preferably 70 mgKOH/g or less.

The acid value of the wetting and dispersing agent (B) is, for example, 4 to 185 mgKOH/g (preferably 40 to 145 mgKOH/g, more preferably 50 to 145 mgKOH/g, still more preferably 100 to 145 mgKOH/g, particularly preferably 110 to 135 mgKOH /g). The acid value is expressed in mg of KOH required to neutralize 1 g of sample.

The amine value of the wetting and dispersing agent (B) is, for example, 0 to 145 mgKOH/g (preferably 30 to 100 mgKOH/g, more preferably 40 to 100 mgKOH/g, still more preferably 50 to 100 mgKOH/g, particularly preferably 70 to 90 mgKOH /g). The amine value is expressed in mg of KOH equivalent to the amount of hydrochloric acid required to neutralize 1 g of sample.

The wetting and dispersing agent (B) has a molecular weight of, for example, 100-10,000, preferably 300-5,000.

The wetting and dispersing agent (B) specifically adsorbs to the surface of the surface-modified metal nanoparticles (A) and forms a network that maintains a certain distance by hydrogen bonding to suppress aggregation, so during storage Separation and sedimentation of aggregates are unlikely to occur, and stable re-dispersion is possible even if they do occur. As a result, it is excellent in printability capable of drawing fine lines with high precision by screen printing or the like, continuous printability capable of continuous printing while suppressing clogging of a screen plate, etc., and storage stability of the conductive ink.

Commercially available products can be used as the wetting and dispersing agent (B), and specific examples thereof include "DISPERBYK-106", "DISPERBYK-180", "DISPERBYK-102", "DISPERBYK-118" and "DISPERBYK-103". , "DISPERBYK-111", "DISPERBYK-145", "DISPERBYK-2155" (manufactured by BYK-Chemie Co., Ltd.), "Disparlon 2150", "Disparlon 1831", "Disparlon 1850", "Disparlon 1860", "Disparlon DA-703-50", "Disparlon DA-7301", "Disparlon DN-900", "Disparlon DA-325", "Disparlon DA-375", "Disparlon DA-234" (manufactured by Kusumoto Kasei Co., Ltd. ) and the like.

The content of the wetting and dispersing agent (B) according to the present disclosure is preferably 0.5 to 5.0% by mass, more preferably 0.7 to 4.0% by mass, with respect to 100% by mass of the conductive ink. More preferably, it is 1.0 to 3.0% by mass.

The content of the wetting and dispersing agent (B) according to the present disclosure is preferably 0.5 to 25.0 parts by mass, more preferably 0.8 to 20 parts by mass with respect to 100 parts by mass of the surface-modified metal nanoparticles (A). .0 parts by mass, more preferably 1.0 to 15.0 parts by mass.

<Dispersion solvent (C)>
The dispersion solvent (C) according to the present disclosure preferably contains at least a terpene solvent. Also, the content of the solvent having a boiling point of less than 130° C. is preferably 20% by mass or less of the total amount of the dispersing solvent. Since the conductive ink of the present disclosure uses the dispersing solvent (C), clogging of the screen plate due to volatilization of the solvent is unlikely to occur, and continuous printing is facilitated.

The terpene-based solvent preferably has a boiling point of 130°C or higher (more preferably 130 to 300°C, still more preferably 200 to 270°C).

Examples of the terpene solvent include 4-(1'-acetoxy-1'-methylethyl)-cyclohexanol acetate, 1,8-terpine-1-acetate, 1,8-terpine-8-acetate, 1, 8-terpine-1,8-diacetate, 1,2,5,6-tetrahydrobenzyl alcohol, 1,2,5,6-tetrahydrobenzyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, 4-t-butylcyclohexyl Acetate, terpineol, dihydroterpineol, dihydroterpineol acetate, α-terpineol, β-terpineol, γ-terpineol, L-α-terpineol, dihydroterpinyloxyethanol, terpinyl methyl ether, dihydroterpinyl methyl ether etc. can be mentioned. These may be used alone or in combination of two or more.

Commercially available products can be used as the terpene-based solvent, and specific examples include "Tersolve MTPH", "Tersolve IPG", "Tersolve IPG-Ac", "Tersolve IPG-2Ac", "Terpineol C" (α- mixture of terpineol, β-terpineol, and γ-terpineol), "Telsolve DTO-210", "Telsolve THA-70", "Telsolve THA-90", "Telsolve TOE-100" (Nippon Terpene Chemical Co., Ltd.) made) and the like.

The dispersion solvent (C) may contain solvents other than the terpene-based solvent. Examples of the other solvents include glycol ether solvents, glycol ester solvents, and the like.

Examples of the glycol ether compounds and glycol ester compounds include glycol diethers, glycol ether esters, glycol diesters, glycol monoethers and glycol monoesters.

The glycol diether, the glycol ether ester, and the glycol diester are preferably compounds represented by the following formula (1).

In formula (1), R ¹ and R ³ are the same or different and represent an alkyl group, and R ² represents an alkylene group. l and n are the same or different and represent 0 or 1, and m represents an integer of 1-8.

The alkyl group for R ¹ and R ³ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and specific examples thereof include methyl group, methylmethyl group, dimethylmethyl group, ethyl group, propyl group, trimethyl group, tetramethyl group, isobutyl group, tert-butyl group, pentamethyl group, hexamethyl group, heptyl group, octyl group, nonyl group, decyl group, etc. mentioned.

The alkylene group for R ² is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, still more preferably 2 to 3 carbon atoms, and specific examples are Examples include methylene group, methylmethylene group, ethylene group, dimethylmethylene group, trimethylene group, propylene group, tetramethylene group, 1-methylpropylene group, dimethylethylene group, pentamethylene group, hexamethylene group and the like. .

The above m is preferably an integer of 1 to 8, more preferably 1 to 3, and still more preferably 2 to 3.

Specific examples of the glycol diether include propylene glycol methyl-n-propyl ether, propylene glycol methyl-n-butyl ether, propylene glycol methyl isoamyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether. , diethylene glycol isopropyl methyl ether, diethylene glycol methyl-n-butyl ether, dipropylene glycol methyl-isopentyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, dipropylene glycol methyl Cyclopentyl ether, triethylene glycol dimethyl ether, triethylene glycol methyl-n-butyl ether, tripropylene glycol methyl-n-propyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether and the like can be mentioned. These may be used alone or in combination of two or more.

Specific examples of the glycol ether ester include ethylene glycol methyl ether acetate, ethylene glycol-n-butyl ether acetate, propylene glycol methyl ether acetate, 3-methoxybutyl acetate, diethylene glycol-n-butyl ether acetate, diethylene glycol ethyl ether acetate, Diethylene glycol butyl ether acetate, dipropylene glycol methyl ether acetate and the like can be mentioned. These may be used alone or in combination of two or more.

Specific examples of the glycol diester include propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, ethylene glycol dipropionate, and ethylene. Glycol dibutyrate, ethylene glycol diisobutyrate, ethylene glycol di-t-butyrate, ethylene glycol dihexylate and the like can be mentioned. These may be used alone or in combination of two or more.

The boiling point of the glycol diether, the glycol ether ester, and the glycol diester is preferably 130° C. or higher, more preferably 130 to 300° C., and still more preferably 170° C., because it is difficult to evaporate during printing and volatilizes easily during sintering. ~300°C, particularly preferably 200-300°C.

The glycol monoether and the glycol monoester are preferably compounds represented by the following formula (2).

In formula (2), ^R4 represents an alkyl group, an aryl group or an aralkyl group, and ^R5 represents an alkylene group. s represents 0 or 1, and t represents an integer of 1-8.

Examples of the alkyl group for R ⁴ include the same groups as those for R ¹ and R ³ above.

Examples of the aryl group for R ⁴ include phenyl group and naphthyl group, and examples of aralkyl group include benzyl group and phenethyl group.

Examples of the alkylene group for R ⁵ are the same as those for R ² .

The above t is preferably 1-8, more preferably 1-3, and still more preferably 2-3.

Specific examples of the glycol monoether include ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol mono-t-butyl ether, ethylene glycol monohexyl ether, ethylene glycol mono -2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, butyl carbitol, diethylene glycol monoisobutyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monopentyl ether, diethylene glycol monoisopentyl ether , diethylene glycol monohexyl ether, hexyl carbitol, diethylene glycol mono-2-ethylhexyl ether, diethylene glycol monophenyl ether, diethylene glycol monobenzyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, 3-methoxy-1-butanol and the like. These may be used alone or in combination of two or more.

Specific examples of the glycol monoester include ethylene glycol monoacetate, ethylene glycol monopropionate, ethylene glycol monobutyrate, ethylene glycol monoisobutyrate, ethylene glycol mono-t-butyrate, and ethylene glycol monohexylate. etc. These may be used alone or in combination of two or more.

The boiling point of the glycol monoether and glycol monoester is preferably 130° C. or higher, more preferably 130 to 300° C., still more preferably 150 to 270° C., especially since it is difficult to evaporate during printing and volatilizes easily during sintering. It is preferably 170 to 250°C.

The conductive ink of the present disclosure may contain other dispersion solvents in addition to the terpene-based solvent, the glycol ether-based solvent, and the glycol ester-based solvent.

The content of the dispersion solvent (C) according to the present disclosure is preferably 10 to 70% by mass, more preferably 15 to 60% by mass, and still more preferably 20 to 50% by mass with respect to 100% by mass of the conductive ink. be.

The content of the dispersion solvent (C) according to the present disclosure is preferably 15 to 200 parts by mass, more preferably 20 to 120 parts by mass, and even more preferably 25 parts by mass with respect to 100 parts by mass of the surface-modified metal nanoparticles (A). ~80 parts by mass.

<Binder resin (D)>
The conductive ink of the present disclosure preferably has an appropriate viscosity and contains a binder resin (D) from the viewpoint of facilitating drawing of fine lines with higher accuracy.

Examples of the binder resin (D) include vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, polyester resin, acrylic resin, cellulose resin (ethyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, cellulose acetate, nitrocellulose and the like, preferably ethyl cellulose), among others, cellulose-based resins are preferred. These may be used alone or in combination of two or more.

The weight-average molecular weight of the binder resin (D) is preferably 40,000 to 1,000,000, more preferably 45,000 to 600,000, and still more preferably 50,000 to 400,000 in terms of imparting an appropriate viscosity to the conductive ink. In addition, a weight average molecular weight can be measured by a gel permeation chromatography (GPC) method, for example.

Commercially available products can be used as the cellulose resin, and specific examples include "Metolose SM-100", "Metolose 90SH" (manufactured by Shin-Etsu Chemical Co., Ltd.), "Ethocel STD 200", and "Ethocel STD 300" (manufactured by Dow Chemical Co., Ltd.), "SANHEC", "NEOVISCO MC" (manufactured by Sansho Co., Ltd.) and the like.

The content ratio of the binder resin (D) according to the present disclosure is preferably 0.1 to 4.0% by mass with respect to 100% by mass of the conductive ink, from the viewpoint of making it easier to draw fine lines with higher accuracy. It is preferably 0.3 to 3.0% by mass, more preferably 0.5 to 2.0% by mass.

The content ratio of the binder resin (D) according to the present disclosure is also preferably 0.5 to 10.0 parts by mass, more preferably 0.8 to 100 parts by mass with respect to 100 parts by mass of the surface-modified metal nanoparticles (A). 7.0 parts by mass, more preferably 1.1 to 4.0 parts by mass.

<Antifoaming agent (E)>
The conductive ink of the present disclosure may contain an antifoaming agent (E) from the viewpoint of suppressing the generation of air bubbles during printing and drying.

Examples of the antifoaming agent (E) include polymer-based and silicone-based antifoaming agents, among which polymer-based antifoaming agents are preferred. These may be used alone or in combination of two or more.

Examples of the polymer antifoaming agent include "BYK-051N", "BYK-052N", "BYK-054", "BYK-055", "BYK-057", "BYK-354", "BYK- 392", "BYK-1752", "BYK-1759", "BYK-1788", "BYK-1790", "BYK-1791", "BYK-1794", "BYK-1795", "BYK-1797" , "BYK-1799", "BYK-011", "BYK-012", "BYK-014", "BYK-015", "BYK-1640", "BYK-1680" (above, BYK-Chemie Japan ( Co., Ltd.), “Dappo SN-348”, “Dappo SN-351”, “Dappo SN-354” (manufactured by San Nopco Co., Ltd.), “Disparon OX-881”, Disparon OX-883HF”, Disparon OX -77EF", Disparlon OX-60", and "Disparlon OX-750HF" (manufactured by Kusumoto Kasei Co., Ltd.).

Examples of the silicone antifoaming agent include "BYK-017", "BYK-018", "BYK-019", "BYK-065", "BYK-066N", "BYK-067A", "BYK- 077”, “BYK-081”, “BYK-1650”, “BYK-1719”, “BYK-1724”, “BYK-1730”, “BYK-1770”, “BYK-W9010” (above, BYK-Chemie Japan Co., Ltd.); "KF-96", "FA-630", "X-50-1039A", "KS-7708", "KS-66", "KSP-69", "X -50-1105G", "KS-602A", and "KSP-600" (manufactured by Shin-Etsu Silicone Co., Ltd.).

The content of the antifoaming agent (E) according to the present disclosure is preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass with respect to 100% by mass of the conductive ink, because the volume resistivity tends to be low. 5 to 7.0% by mass, more preferably 1.0 to 5.0% by mass.

The content of the antifoaming agent (E) according to the present disclosure is preferably 0.1 to 35.0 parts by mass, more preferably 0.5 parts by mass, with respect to 100 parts by mass of the surface-modified metal nanoparticles (A). 17.5 parts by mass, more preferably 1.0 to 10.0 parts by mass.

The viscosity (at 25° C. and shear rate of 10 s ⁻¹ ) of the conductive ink of the present disclosure is preferably 1 to 200 Pa·s, more preferably 3 to 175 Pa·s, still more preferably 5 to 150 Pa·s. The conductive ink of the present disclosure can be suitably used as a conductive ink for screen printing when it has a viscosity within the above range. The viscosity can be measured using, for example, a rheometer (product name “Physica MCR301”, manufactured by Anton Paar).

<Other ingredients>
In addition to the above components, the conductive ink of the present disclosure includes, for example, plasticizers (adipic plasticizers, maleates, organic phosphates, sulfonamides, polyethers, etc.), leveling agents (silicone leveling agents, fluorine leveling agents, etc.), adhesion agents (imidazole-based adhesion agents, thiazole-based adhesion agents, triazole-based adhesion agents, silane coupling agents, etc.), sintering aids, etc. can be included as appropriate.

As the sintering aid, for example, a diamine having at least one of a primary amino group, a secondary amino group and a tertiary amino group, preferably at least one amino group is a primary amino group or A diamine that is a tertiary amino group, more preferably a diamine in which one is a primary amino group or secondary amino group (more preferably a primary amino group) and the other is a tertiary amino group. , for example, the same aliphatic diamines as the above aliphatic diamine (3) (ethylenediamine, 1,3-propanediamine, 2,2-dimethyl-1,3-propanediamine, 1,4-butanediamine, 1,5- Pentanediamine, 1,6-hexanediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N'-dimethyl-1,3-propanediamine, N,N'-diethyl-1,3 -propanediamine, N,N'-dimethyl-1,4-butanediamine, 3-diethylaminopropylamine, 4-dimethylaminobutylamine, etc.) and aromatic diamines (p-phenylenediamine, m-phenylenediamine, o-phenylene diamine, N,N-diethyl-p-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2, 6-diaminonaphthalene, 2,3-diaminonaphthalene, etc.). Among them, an aliphatic diamine having a primary amino group and/or a tertiary amino group is preferred, an aliphatic diamine having a primary amino group and a tertiary amino group is more preferred, and 3-diethylaminopropylamine is further preferred. preferable.

<Method for producing conductive ink>
The conductive ink of the present disclosure includes, for example, a step of mixing a metal compound and a protective agent containing an amine to generate a complex, and thermally decomposing the generated complex to obtain surface-modified metal nanoparticles (A); It can be produced through a step of mixing the obtained surface-modified metal nanoparticles (A) with at least a wetting and dispersing agent (B) and a dispersing solvent.

Examples of the metal compounds include metal carboxylates (metal formates, metal acetates, metal oxalates, metal malonates, metal benzoates, metal phthalates, etc.), metal halides (metal fluorides , metal chlorides, metal bromides, metal iodides, etc.), metal inorganic acid salts (metal sulfates, metal nitrates, metal carbonates, etc.) can be used. Among them, metal oxalates are preferable because they easily generate metals by decomposition and are less likely to produce impurities other than metals.

The amount of the protective agent (preferably amine) used is preferably 1 to 50 mol with respect to 1 mol of the metal atom of the metal compound, in terms of imparting sufficient dispersibility to the surface-modified metal nanoparticles (A). , more preferably 10 to 40 mol, still more preferably 15 to 35 mol.

The reaction between the metal compound and the protective agent for forming the complex may be carried out in the presence of a reaction solvent or in the absence of a reaction solvent. As the reaction solvent, for example, an alcohol solvent (preferably an aliphatic alcohol) having 3 or more carbon atoms can be used.

The amount of the reaction solvent used is preferably 120 to 1000 parts by mass, more preferably 130 to 800 parts by mass, and even more preferably 150 to 500 parts by mass with respect to 100 parts by mass of the metal compound.

The reaction to generate the above complex can be carried out, for example, at a reaction temperature of 5 to 40°C and a reaction time of 30 minutes to 3 hours.

The above thermal decomposition may be carried out in the presence of a reaction solvent similar to the above reaction solvent. The thermal decomposition temperature is, for example, preferably 80 to 120° C., more preferably 100 to 110° C., and the thermal decomposition time is, for example, 10 minutes to 5 hours. Moreover, the thermal decomposition of the complex can be carried out in an air atmosphere or an inert gas (nitrogen, argon, etc.) atmosphere.

The surface-modified metal nanoparticles (A) obtained by the above pyrolysis may be washed by centrifugation or decantation.

Mixing with the surface-modified metal nanoparticles (A) obtained by the thermal decomposition, the wetting and dispersing agent (B), the dispersing solvent, the optional binder resin (C) and the antifoaming agent (D), for example, It can be carried out using a known mixing device such as a type stirring and defoaming device, homogenizer, planetary mixer, three-roll mill, bead mill, and the like. The above components may be mixed simultaneously or sequentially.

[Method for manufacturing electronic device]
The manufacturing method of the electronic device of the present disclosure includes a step of applying the conductive ink of the present disclosure to a substrate by a printing method (dispenser printing method, mask printing method, screen printing method, inkjet printing method, etc.), and a step of sintering. .

In the electronic device manufacturing method of the present disclosure, since the conductive ink is used, sintering is possible at a low temperature (for example, 60° C. or higher, 100° C. or higher, or 120° C. or higher). The upper limit of the sintering temperature is not particularly limited, and may be, for example, 500°C, 300°C, 200°C, or 150°C. The sintering time is, for example, 0.5 to 3 hours, preferably 0.5 to 2 hours, more preferably 0.5 to 1 hour.

When the conductive ink of the present disclosure is used, low-temperature sintering is possible as described above. Therefore, the substrate may be a glass substrate, a heat-resistant plastic substrate such as a polyimide film, or a polyethylene terephthalate (PET) film. General-purpose plastic substrates with low heat resistance, such as polyester films such as polyethylene naphthalate (PEN) films, and polyolefin films such as polypropylene, can also be suitably used.

[Electronic device]
Examples of electronic devices obtained by the electronic device manufacturing method of the present invention include liquid crystal displays, organic EL displays, field emission displays (FED), IC cards, IC tags, solar cells, LED elements, organic transistors, capacitors (capacitors ), electronic paper, flexible batteries, flexible sensors, membrane switches, touch panels, and EMI shields.

Each aspect disclosed in this specification can be combined with any other feature disclosed in this specification. Each configuration, combination thereof, etc. in each embodiment is an example, and addition, omission, replacement, and other changes of configuration are possible as appropriate without departing from the scope of the present disclosure. In addition, each invention according to the present disclosure is not limited by the embodiments or the following examples, but only by the claims.

The present disclosure will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

The surface-modified metal nanoparticles (A), wetting and dispersing agent (B), dispersing solvent (C), binder resin (D) and antifoaming agent (E) used in Examples and Comparative Examples are as follows.

<Surface-modified metal nanoparticles (A)>
Silver oxalate (molecular weight: 303.78) was obtained from silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) and oxalic acid dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). A 500 mL flask was charged with 40.0 g (0.1317 mol) of the above silver oxalate, and 60 g of n-butanol was added to prepare an n-butanol slurry of silver oxalate. To this slurry, at 30 ° C., n-butylamine (molecular weight: 73.14, reagent manufactured by Tokyo Chemical Industry Co., Ltd.) 115.58 g (1.5802 mol), 2-ethylhexylamine (molecular weight: 129.25, Fujifilm Sum Kojun Chemical Co., Ltd. reagent) 51.06 g (0.3950 mol) and n-octylamine (molecular weight: 129.25, Tokyo Chemical Industry Co., Ltd. reagent) 17.02 g (0.1317 mol) amine mixture The liquid was added dropwise. After dropping, the mixture was stirred at 30° C. for 1 hour to allow the complex formation reaction between silver oxalate and amine to proceed. After the formation of the silver oxalate-amine complex, the mixture was heated at 110° C. for 1 hour to thermally decompose the silver oxalate-amine complex to obtain a dark blue suspension containing surface-modified silver nanoparticles.

The resulting suspension is cooled, 120 g of methanol (reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special grade) is added and stirred, and then the surface-modified silver nanoparticles are precipitated by centrifugation. Liquid was removed. Next, 120 g of methanol is added to the surface-modified silver nanoparticles and stirred, then the surface-modified silver nanoparticles are precipitated by centrifugation, the supernatant is removed, and dipropylene glycol n-butyl ether ( Reagent manufactured by Dow Chemical Co., Ltd.) (120 g) was added and stirred, then the surface-modified silver nanoparticles were sedimented by centrifugation, and the supernatant was removed. Thus, surface-modified silver nanoparticles 1 in a wet state were obtained. From the results of thermal balance using a differential thermal thermogravimeter (product name "TG/DTA6300", manufactured by SII), the content of surface-modified silver nanoparticles 1 in the total amount of surface-modified silver nanoparticles in a wet state (100% by mass) The amount was 90% by weight.

In addition, the wet state surface-modified silver nanoparticles 1 were observed using a scanning electron microscope ("JSM-6700F", manufactured by JEOL Ltd.), and 10 arbitrarily selected silver nanoparticles were observed in the SEM photograph. The particle diameters of the particles were determined, and the average value thereof was taken as the average particle diameter. The average particle size (primary particle size) of the silver nanoparticle portion in the surface-modified silver nanoparticles 1 was about 50 nm.

<Wetting and dispersing agent (B)>
- BYK106: polymer salt having an acidic group, amine value 74 mgKOH / g, acid value 132 mgKOH / g, trade name "DISPERBYK-106", manufactured by BYK Chemie Japan Co., Ltd. - BYK180: copolymer alkylol containing an acid group Ammonium salt, amine value 94 mgKOH/g, acid value 94 mgKOH/g, trade name “DISPERBYK-180”, BYK-Chemie Japan Co., Ltd. BYK102: copolymer having an acidic group, no amine value, acid value 101 mgKOH/g, product Name “DISPERBYK-102”, BYK-Chemie Japan Co., Ltd. BYK118: Linear polymer having pigment affinity group, no amine value, acid value 36 mgKOH / g, trade name “DISPERBYK-118”, BYK-Chemie Japan Co., Ltd. ) BYK103: A copolymer with an affinity for pigments, no amine value, no acid value, trade name “DISPERBYK-103”, BYK Chemie Japan Co., Ltd. BYK111: A copolymer containing an acid group, amine No value, acid value 129 mgKOH/g, trade name “DISPERBYK-111” BYK-Chemie Japan Co., Ltd. BYK145: Phosphate ester salt of copolymer with affinity for pigment, amine value 71 mgKOH/g, acid value 76 mgKOH/g, trade name “DISPERBYK-145”, BYK-Chemie Japan Co., Ltd. BYK2155: Block copolymer with affinity for pigment, amine value 48 mgKOH/g, no acid value, trade name “DISPERBYK-2155” , BYK-Chemie Japan Co., Ltd.

<Dispersion solvent (C)>
・THA70: A mixture of 1,8-terpine-1-acetate, 1,8-terpine-8-acetate and 1,8-terpine-1,8-diacetate, boiling point 223°C, trade name “Tersolve THA-70” , manufactured by Nippon Terpene Chemical Co., Ltd. DPNB: dipropylene glycol mono-n-butyl ether, boiling point 230 ° C., manufactured by Dow Chemical Company

<Binder resin (D)>
・EC300: Ethyl cellulose, trade name “Ethocel STD 300”, Dow Chemical Co. ・EC200: Ethyl cellulose, weight average molecular weight 190000, trade name “Ethocel STD 200”, Dow Chemical Co.

<Antifoaming agent (E)>
・BYK054: Polymer antifoaming agent, trade name “BYK-054”, manufactured by BYK-Chemie Japan Co., Ltd. ・BYK066N: Silicone-based defoaming agent, trade name “BYK-066N”, manufactured by BYK-Chemie Japan Co., Ltd.

<Others>
・DEAPA: 3-diethylaminopropylamine

Example 1 (Preparation of silver ink)
The surface-modified silver nanoparticles 1, BYK106, THA70, DPNB, and EC300 were blended so that the content ratio (% by mass) shown in Table 1 below was obtained, and stirred and kneaded (2 minutes x 3 times) to give a black-brown color. A silver ink was prepared. The stirring and kneading was performed using a rotation-revolution type kneader (product name: "Mazerustar KKK2508", manufactured by Kurashiki Boseki Co., Ltd.).

Examples 2 to 16, Comparative Examples 1 and 2
A silver ink was prepared in the same manner as in Example 1, except that each component was blended so as to have the content ratio (% by mass) shown in Tables 1 and 2 below.

The silver inks prepared in Examples 1 to 16 and Comparative Examples 1 and 2 were evaluated for viscosity, electrical conductivity of the sintered body, number of aggregates, printability, continuous printability, storage stability, and defoaming effect by the following methods. evaluated.

(viscosity)
The viscosities (25° C., shear rate 10 s ⁻¹ ) of the silver inks prepared in Examples and Comparative Examples were measured using a rheometer (product name “Physica MCR301”, manufactured by Anton Paar).

(Electrical conductivity of sintered body)
The silver inks prepared in Examples 1 to 16 and Comparative Examples 1 and 2 were applied onto a glass plate to form a coating film. Immediately after forming the coating film, the coating film was sintered in a blower drying furnace at 120° C. for 30 minutes to obtain a sintered body having a thickness of about 4 μm. The conductivity of the obtained sintered body was evaluated by measuring the volume resistivity using a four-probe method (Loresta GP MCP-T610).

The conductivity evaluation criteria are as follows.
◎ (very good): 25 μΩ・cm or less ○ (good): over 25 μΩ・cm, 50 μΩ・cm or less × (defective): over 50 μΩ・cm

(Number of aggregates)
The silver inks prepared in Examples 1 to 16 and Comparative Examples 1 and 2 were applied onto a glass plate to form a coating film. Immediately after forming the coating film, the coating film was sintered in a blower drying furnace at 120° C. for 30 minutes to obtain a sintered body having a thickness of about 4 μm. Regarding the obtained sintered body, the number of aggregates of 15 μm or more (per 1 cm ² ) was evaluated by observation using an optical microscope.

Evaluation criteria for smoothness are as follows.
○ (good): 20 or less △ (slightly good): more than 20 and 100 or less × (poor): more than 100

(Printability)
The silver inks prepared in Examples and Comparative Examples were printed on a PET film at 25°C using a screen printer (product name: LS-150TV, manufactured by Newlong Seimitsu Kogyo Co., Ltd.). evaluated.

The printability evaluation criteria are as follows.
○ (good): can be printed with high accuracy by screen printing △ (somewhat good): can be printed by screen printing, but bleeding and disconnection are observed × (poor): cannot be printed by screen printing

(Continuous printability)
The silver inks prepared in Examples and Comparative Examples are continuously printed on a PET film at 25° C. using a screen printer (product name “LS-150TV” manufactured by Newlong Seimitsu Kogyo Co., Ltd.). Continuous printability was evaluated by

Evaluation criteria for continuous printability are as follows.
○ (Good): The number of times that printing was possible in succession was 40 or more × (Bad): The number of times that printing was possible in succession was less than 40

(Storage stability)
The viscosities of the silver inks prepared in Examples and Comparative Examples were measured after storage at 5° C. for 20 weeks. Storage stability was evaluated by the amount of increase in viscosity after storage relative to viscosity before storage.

The evaluation criteria for storage stability are as follows.
○ (good): the amount of increase in viscosity is less than 20% △ (slightly good): the amount of increase in viscosity is 20% or more and 50% or less × (poor): the amount of increase in viscosity is more than 50%

(Antifoaming effect)
The silver inks prepared in Examples 1 to 16 and Comparative Examples 1 and 2 were applied onto a glass plate to form a coating film. Immediately after forming the coating film, the coating film was sintered in a blower drying furnace at 120° C. for 30 minutes to obtain a sintered body having a thickness of about 4 μm. The defoaming effect of the obtained sintered body was evaluated by observing the number of pores (per 1 cm ² ) of 15 μm or more using an optical microscope.

The evaluation criteria for the defoaming effect are as follows.
◎ (very good): the number of holes is 0 ○ (good): the number of holes is 1 to 2 △ (slightly good): the number of holes is more than 25 and not more than 25 × (poor): holes is greater than 25

"-" for storage stability in Tables 1 and 2 indicates that it has not been evaluated.

Regarding the number of aggregates, Examples 1 to 16 were 0 to △, while Comparative Examples 1 and 2 were x. Regarding printability and continuous printability, both Example 2 and Comparative Example 1 were evaluated as ◯. The viscosity of Example 2 was 73.8 Pa·s, Example 6 was 113.4 Pa·s, and Comparative Example 1 was 78.0 a·s.

Variations of the invention according to the present disclosure are described below.
[Appendix 1] A conductive ink containing surface-modified metal nanoparticles (A) coated with a protective agent containing amine, a wetting and dispersing agent (B), and a dispersing solvent (C).
[Appendix 2] The average primary particle size of the surface-modified metal nanoparticles (A) is 0.5 to 100 nm (preferably 0.5 to 80 nm, more preferably 1.0 to 65 nm, and even more preferably 1.0 to 50 nm). The conductive ink according to Supplementary Note 1.
[Appendix 3] The amine value of the wetting and dispersing agent (B) is 0 to 145 mgKOH/g (preferably 30 to 100 mgKOH/g, more preferably 40 to 100 mgKOH/g, still more preferably 50 to 100 mgKOH/g, particularly preferably 70 to 90 mgKOH/g), the conductive ink according to appendix 1 or 2.
[Appendix 4] The wetting and dispersing agent (B) has an acid value of 4 to 185 mgKOH/g (preferably 40 to 145 mgKOH/g, more preferably 50 to 145 mgKOH/g, still more preferably 100 to 145 mgKOH/g, particularly preferably 110 to 135 mgKOH/g), the conductive ink according to appendix 1 or 2.
[Appendix 5] The amine value of the wetting and dispersing agent (B) is 0 to 145 mgKOH/g (preferably 30 to 100 mgKOH/g, more preferably 40 to 100 mgKOH/g, still more preferably 50 to 100 mgKOH/g, particularly preferably 70 to 90 mgKOH/g) and an acid value of 4 to 185 mgKOH/g (preferably 40 to 145 mgKOH/g, more preferably 50 to 145 mgKOH/g, more preferably 100 to 145 mgKOH/g, particularly preferably 110 to 135 mgKOH / g), the conductive ink according to Appendix 1 or 2.
[Appendix 6] The difference between the oxidation value and the amine value is 5 mgKOH/g or more (preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, still more preferably 45 mgKOH/g or more), and 150 mgKOH /g or less (preferably 100 mgKOH/g or less, more preferably 70 mgKOH/g or less).
[Appendix 7] The amines in the surface-modified metal nanoparticles (A) are an aliphatic monoamine (1) having a total carbon number of 6 or more and an aliphatic monoamine (2) having a total carbon number of 5 or less and/or the total carbon number 7. The conductive ink according to any one of Appendices 1 to 6, comprising an aliphatic diamine (3) of 8 or less.
[Appendix 8] The aliphatic monoamine (1) is an alkyl monoamine having a linear alkyl group with a total carbon number of 6 to 18 (preferably 6 to 16, more preferably 6 to 12), and / or total carbon The conductive ink according to appendix 7, which is an alkyl monoamine having a branched alkyl group of numbers 6 to 16 (preferably 6 to 10).
[Appendix 9] The aliphatic monoamine (2) is an alkyl monoamine having a linear or branched alkyl group with a total carbon number of 2 to 5 (preferably 3 to 5, more preferably 4 to 5). , Supplementary note 7 or 8 conductive ink.
[Appendix 10] Any one of Appendices 7 to 9, wherein the aliphatic diamine (3) is an aliphatic diamine (preferably alkylenediamine) having a primary amino group and a tertiary amino group. conductive ink.
[Appendix 11] The conductive ink according to any one of Appendices 1 to 10, wherein the surface-modified metal nanoparticles (A) are surface-modified silver nanoparticles.
[Appendix 12] Any of Appendices 1 to 11, wherein the content of the surface-modified metal nanoparticles (A) is 30 to 90% by mass (preferably 40 to 85% by mass, more preferably 50 to 80% by mass). The conductive ink according to any one of the above.
[Appendix 13] The conductive ink according to any one of Appendices 1 to 12, wherein the wetting and dispersing agent (B) is a compound having an acidic group.
[Appendix 14] The conductive ink according to any one of Appendices 1 to 13, wherein the wetting and dispersing agent (B) is a polymer salt.
[Appendix 15] The content of the wetting and dispersing agent (B) is 0.5 to 5.0% by mass (preferably 0.7 to 4.0% by mass, more preferably 1.0 to 3.0% by mass ), the conductive ink according to any one of appendices 1 to 14.
[Appendix 16] The content of the wetting and dispersing agent (B) is 0.5 to 25.0 parts by mass (preferably 0.8 to 20.0 parts by mass) with respect to 100 parts by mass of the surface-modified metal nanoparticles (A) 16 parts by weight, more preferably 1.0 to 15.0 parts by weight).
[Appendix 17] The conductive ink according to any one of Appendices 1 to 16, wherein the dispersion solvent (C) contains at least a terpene solvent.
[Appendix 18] The conductive ink according to any one of Appendices 1 to 17, wherein the content of the solvent having a boiling point of less than 130° C. is 20% by mass or less with respect to the total amount of the dispersion solvent (C).
[Appendix 19] The conductive ink according to Appendix 17, wherein the terpene-based solvent has a boiling point of 130° C. or higher (preferably 130 to 300° C., more preferably 200 to 270° C.).
[Appendix 20] The conductive ink according to any one of Appendices 1 to 19, wherein the dispersion solvent (C) contains a glycol ether solvent and/or a glycol ester solvent.
[Appendix 21] The dispersion solvent (C) has the following formula (1)

20. The conductive ink according to any one of Appendices 1 to 19, comprising a compound represented by:
[In Formula (1), R ¹ and R ³ are the same or different and represent an alkyl group, and R ² represents an alkylene group. l and n are the same or different and represent 0 or 1, and m represents an integer of 1-8. ]
[Appendix 22] The dispersion solvent (C) is represented by the following formula (2)

20. The conductive ink according to any one of Appendices 1 to 19, comprising a compound represented by:
[In formula (2), R ⁴ represents an alkyl group, an aryl group or an aralkyl group, and R ⁵ represents an alkylene group. s represents 0 or 1, and t represents an integer of 1-8. ]
[Appendix 23] Any one of Appendices 1 to 22, wherein the content of the wetting and dispersing agent (C) is 10 to 70% by mass (preferably 15 to 60% by mass, more preferably 20 to 50% by mass). The conductive ink according to 1.
[Appendix 24] The content ratio of the wetting and dispersing agent (C) is 15 to 200 parts by mass (preferably 20 to 120 parts by mass, more preferably 25 to 200 parts by mass with respect to 100 parts by mass of the surface-modified metal nanoparticles (A). 80 parts by mass), the conductive ink according to any one of appendices 1 to 23.
[Appendix 25] The conductive ink according to any one of Appendices 1 to 24, further comprising a binder resin (D).
[Appendix 26] The conductive ink according to Appendix 25, wherein the binder resin (D) is a cellulose resin.
[Appendix 27] The conductive ink according to Appendix 25 or 26, wherein the binder resin (D) has a weight average molecular weight of 40,000 to 1,000,000 (preferably 45,000 to 600,000, more preferably 50,000 to 400,000).
[Appendix 28] The content of the wetting and dispersing agent (D) is 0.1 to 4.0% by mass (preferably 0.3 to 3.0% by mass, more preferably 0.5 to 2.0% by mass ), the conductive ink according to any one of Appendices 25 to 27.
[Appendix 29] The content of the wetting and dispersing agent (D) is 0.5 to 10.0 parts by mass (preferably 0.8 to 7.0 parts by mass) with respect to 100 parts by mass of the surface-modified metal nanoparticles (A) parts by weight, more preferably 1.1 to 4.0 parts by weight).
[Appendix 30] The conductive ink according to any one of Appendices 1 to 29, further comprising an antifoaming agent (E).
[Appendix 31] The conductive ink according to Appendix 30, wherein the antifoaming agent (E) is a polymer antifoaming agent and/or a silicone antifoaming agent.
[Appendix 32] The conductive ink according to Appendix 30, wherein the antifoaming agent (E) is a polymer antifoaming agent.
[Appendix 33] The content of the antifoaming agent (E) is 0.1 to 10% by mass (preferably 0.5 to 7.0% by mass, more preferably 1.0 to 5.0% by mass). 33. The conductive ink according to any one of Appendices 30 to 32.
[Appendix 34] The content of the wetting and dispersing agent (E) is 0.1 to 35.0 parts by mass (preferably 0.5 to 17.5 parts by mass) with respect to 100 parts by mass of the surface-modified metal nanoparticles (A) parts by weight, more preferably 1.0 to 10.0 parts by weight).
[Appendix 35] The conductive ink according to any one of Appendices 1 to 34, further comprising a sintering aid.
[Appendix 36] The conductive ink according to Appendix 35, wherein the sintering aid is an aliphatic diamine having a primary amino group and/or a tertiary amino group.
[Appendix 37] The conductive ink according to Appendix 35, wherein the aliphatic diamine is 3-diethylaminopropylamine.
[Appendix 38] Any one of Appendices 1 to 37, wherein the viscosity at 25°C and a shear rate of 10 s ^-1 is 1 to 200 Pa s (preferably 3 to 175 Pa s, more preferably 5 to 150 Pa s). The conductive ink according to 1.
[Appendix 39] A method of manufacturing an electronic device, comprising the steps of applying the conductive ink according to any one of Appendices 1 to 38 on a substrate, and sintering.
[Appendix 40] An electronic device comprising a sintered body of the conductive ink according to any one of Appendices 1 to 38 on a substrate.

According to the inkjet head cleaning liquid of the present disclosure, after cleaning the inkjet head, it is possible to check the clogged state of the ejection port without actually trying to eject the inkjet ink, and the cleaning of the inkjet head becomes easy, and the cleaning time is reduced. can save money. Therefore, the present disclosure has industrial applicability.

Claims (18)

1. A conductive ink containing surface-modified metal nanoparticles (A) coated with a protective agent containing amine, a wetting and dispersing agent (B), and a dispersing solvent (C).
2. The conductive ink according to claim 1, wherein the wetting and dispersing agent (B) has an amine value of 0 to 145 mgKOH/g and an acid value of 4 to 185 mgKOH/g.
3. The amines in the surface-modified metal nanoparticles (A) are aliphatic monoamines (1) having a total carbon number of 6 or more, aliphatic monoamines having a total carbon number of 5 or less (2) and/or fats having a total carbon number of 8 or less. The conductive ink of claim 1, comprising a group diamine (3).
4. The aliphatic monoamine (1) is an alkyl monoamine having a straight-chain alkyl group with a total of 6 to 18 carbon atoms and/or an alkyl monoamine having a branched-chain alkyl group with a total of 6 to 16 carbon atoms. Item 4. The conductive ink according to item 3.
5. The conductive ink according to claim 3, wherein the aliphatic monoamine (2) is an alkyl monoamine having a linear or branched alkyl group with a total of 2 to 5 carbon atoms.
6. The conductive ink according to any one of claims 1 to 5, wherein the surface-modified metal nanoparticles (A) are surface-modified silver nanoparticles.
7. The conductive ink according to any one of claims 1 to 5, wherein the wetting and dispersing agent (B) is a compound having an acidic group.
8. The conductive ink according to any one of claims 1 to 5, wherein the content of the wetting and dispersing agent (B) is 0.5 to 5.0% by mass.
9. The conductive ink according to any one of claims 1 to 5, further comprising a binder resin (D).
10. The conductive ink according to any one of claims 1 to 5, further comprising an antifoaming agent (E).
11. The conductive ink according to claim 10, wherein the antifoaming agent (E) is a polymer antifoaming agent.
12. The conductive ink according to claim 10, wherein the content of the antifoaming agent (E) is 0.1 to 10% by mass.
13. The conductive ink according to any one of claims 1 to 5, further comprising a sintering aid.
14. The conductive ink according to claim 13, wherein the sintering aid is an aliphatic diamine having primary amino groups and/or tertiary amino groups.
15. The conductive ink according to claim 14, wherein the aliphatic diamine is 3-diethylaminopropylamine.
16. The conductive ink according to any one of claims 1 to 5, which has a viscosity of 1 to 200 Pa·s at 25°C and a shear rate of 10 s ^-1 .
17. A method of manufacturing an electronic device, comprising a step of applying the conductive ink according to any one of claims 1 to 5 on a substrate, and a step of sintering.
18. An electronic device comprising a sintered body of the conductive ink according to any one of claims 1 to 5 on a substrate.