WO2017057188A1

WO2017057188A1 - Silver ink composition, process for producing same, and layered product

Info

Publication number: WO2017057188A1
Application number: PCT/JP2016/078013
Authority: WO
Inventors: 久美廣瀬
Original assignee: トッパン・フォームズ株式会社
Priority date: 2015-09-29
Filing date: 2016-09-23
Publication date: 2017-04-06
Also published as: JPWO2017057188A1; JP6802798B2

Abstract

This silver ink composition is obtained by mixing from: a silver carbonate; one or more nitrogenous compounds selected from the group consisting of C₂₅ and lower amine compounds and quaternary ammonium salts, ammonia, and ammonium salts obtained by the reaction of any of the amine compounds or ammonia with an acid; one or more reducing agents selected from the group consisting of oxalic acid, hydrazine, and compounds represented by the following general formula (5); and a C₉ or higher acetylene alcohol compound represented by the following general formula (20). H-C(=O)-R²¹ (5)

Description

Silver ink composition, method for producing the same, and laminate

The present invention relates to a novel silver ink composition, a method for producing the same, and a laminate.
This application claims priority based on Japanese Patent Application No. 2015-191853 filed in Japan on September 29, 2015, the contents of which are incorporated herein by reference.

Metallic silver is widely used as a recording material, a printing plate material, and a highly conductive material because of its excellent conductivity.
As a method for producing metallic silver, for example, a method using a silver ink composition containing a metallic silver forming material that is decomposed by heating or the like to form metallic silver is known. In this production method, the silver ink composition is attached to a target location, and metal silver can be easily formed by decomposing the forming material of the metallic silver under various conditions. When the silver ink composition is attached, Since various printing methods can be applied, it is extremely versatile.

Examples of such a silver ink composition include silver carboxylate having a group represented by the formula “—COOAg”, an amine compound having a carbon number of 25 or less, a quaternary ammonium salt, ammonia, and the amine compound or 1 selected from the group consisting of one or more nitrogen-containing compounds selected from the group consisting of ammonium salts obtained by reacting ammonia with an acid, and oxalic acid, hydrazine, and a compound represented by the following general formula (5) A silver ink composition in which at least one kind of reducing agent is blended is known (see Patent Document 1).
HC (= O) -R ²¹ (5)
(Wherein R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, or an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

The silver ink composition described in Patent Document 1 is extremely useful because it can form metallic silver having sufficient conductivity without performing heat treatment at a high temperature. On the other hand, in recent years, the application range of silver ink compositions has become extremely wide, their usage methods have diversified, and the storage forms when not in use have also diversified, further improving the storage stability of silver ink compositions than before. Improvement has come to be desired. When the storage stability of the silver ink composition is not sufficient, the conductivity of metallic silver formed using the silver ink composition after storage may be lowered. On the other hand, the silver ink composition described in Patent Document 1 has sufficient storage stability that has been desired in the past, but it is unclear whether further improvement in storage stability is possible. .

Japanese Patent Application Laid-Open No. 2014-199391

Therefore, an object of the present invention is to provide a novel silver ink composition excellent in storage stability and a method for producing the same.

In order to solve the above problems, the present invention provides a silver carboxylate having a group represented by the formula “—COOAg”, an amine compound having a carbon number of 25 or less, a quaternary ammonium salt, ammonia, and the amine compound or ammonia. Selected from the group consisting of one or more nitrogen-containing compounds selected from the group consisting of ammonium salts obtained by reacting an acid with oxalic acid, hydrazine and the compound represented by the following general formula (5) Provided is a silver ink composition comprising the above reducing agent and an acetylene alcohol having 9 or more carbon atoms represented by the following general formula (20).
HC (= O) -R ²¹ (5)
(Wherein R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, or an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

Wherein R ′ and R ″ are each independently a hydrogen atom, an alkyl group, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, provided that R ′ and R ′ At least one of 'is the alkyl group or the phenyl group.)

In the silver ink composition of the present invention, the total number of carbon atoms of R ′ and R ″ may be 6-9.
The silver ink composition of the present invention may be formulated with acetylene alcohol represented by the following general formula (21).

(Wherein R ⁹ ′ and R ⁹ ″ are each independently a hydrogen atom or an alkyl group, provided that the total number of carbon atoms of R ⁹ ′ and R ⁹ ″ is 0 to 5)

The present invention also relates to a silver carboxylate having a group represented by the formula “—COOAg”, an amine compound having a carbon number of 25 or less, a quaternary ammonium salt, ammonia, and the amine compound or ammonia reacting with an acid. One or more nitrogen-containing compounds selected from the group consisting of ammonium salts, and one or more reducing agents selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5) The manufacturing method of the silver ink composition which has the process of mix | blending with C9 or more acetylene alcohol represented by following General formula (20) is provided.
HC (= O) -R ²¹ (5)
(Wherein R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, or an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

The present invention also provides a laminate in which a silver layer is laminated on the surface of a substrate, and the silver layer is formed using the silver ink composition.

The silver ink composition of the present invention is excellent in storage stability. In addition, the silver ink composition having excellent storage stability can be obtained by the production method of the present invention.
The laminate of the present invention comprises metallic silver formed using the silver ink composition of the present invention, and this metallic silver is excellent in conductivity.

It is sectional drawing which shows typically one Embodiment of the laminated body obtained using the silver ink composition of this invention.

Preferred examples of the silver ink composition of the present invention, the method for producing the silver ink composition, and the laminate will be described below. However, the present invention is not limited to these examples. For example, additions, omissions, substitutions, and other changes (amount, number, position, size, etc.) are possible without departing from the spirit of the present invention. It is.

<Silver ink composition>
The silver ink composition of the present invention comprises a silver carboxylate having a group represented by the formula “—COOAg”, an amine compound having a carbon number of 25 or less, a quaternary ammonium salt, ammonia, and the amine compound or ammonia is an acid. One or more nitrogen-containing compounds selected from the group consisting of ammonium salts formed by reaction with oxalic acid, hydrazine, and one or more selected from the group consisting of compounds represented by the following general formula (5) A reducing agent and an acetylene alcohol having 9 or more carbon atoms represented by the following general formula (20) are blended.
HC (= O) -R ²¹ (5)
(Wherein R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, or an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

The silver ink composition of the present invention has storage stability superior to that of conventional silver ink compositions by combining specific compounding components as described above.

The silver ink composition of the present invention is preferably in a liquid state, and preferably one in which the silver carboxylate is uniformly dispersed.

[Silver carboxylate]
The silver carboxylate in the present invention has a group represented by the formula “—COOAg”, and the number of groups represented by the formula “—COOAg” may be only one or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.
In this invention, silver carboxylate may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

The silver carboxylate is represented by the following general formula (1) β-ketocarboxylate silver (hereinafter sometimes abbreviated as “β-ketocarboxylate (1)”) and the following general formula (4). One or more selected from the group consisting of silver carboxylates (hereinafter sometimes abbreviated as “silver carboxylate (4)”).
In this specification, the simple description of “silver carboxylate” is not limited to “silver β-ketocarboxylate (1)” and “silver carboxylate (4)”, unless otherwise specified. It is intended to mean “silver carboxylate having a group represented by the formula“ —COOAg ””.

(Wherein R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R ¹ -CY ¹ _2- "," CY ¹ _3- "," R ¹ -CHY ^1- "," R ² O- "," R ⁵ R ⁴ N- "," (R ³ O) ₂ CY ^1- "or" R ⁶ —C (═O) —CY ¹ ₂ — ”;
Y ¹ is each independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R ¹ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group; R ² is an aliphatic having 1 to 20 carbon atoms R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R ⁶ is An aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO—”;
X ¹ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or benzyl group in which one or more hydrogen atoms may be substituted with a substituent, a cyano group, N -Phthaloyl-3-aminopropyl group, 2-ethoxyvinyl group, or “R ⁷ O—”, “R ⁷ S—”, “R ⁷ —C (═O) —” or “R ⁷ —C ( ═O) —O— ”;
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )

(Wherein R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group, or a group represented by the formula “—C (═O) —OAg”, wherein the aliphatic hydrocarbon group is a methylene group. And one or more of the methylene groups may be substituted with a carbonyl group.)

(Silver β-ketocarboxylate (1))
The silver β-ketocarboxylate (1) is represented by the general formula (1).
In the formula, R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a group represented by the general formula “R ¹ -CY ¹ ” in which one or more hydrogen atoms may be substituted with a substituent. _2- "," CY ¹ _3- "," R ¹ -CHY ^1- "," R ² O- "," R ⁵ R ⁴ N- "," (R ³ O) ₂ CY ^1- "or" R ⁶ —C (═O) —CY ¹ ₂ — ”.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be any of linear, branched and cyclic (aliphatic cyclic group), and may be monocyclic or polycyclic when cyclic. . Further, the aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Preferred examples of the aliphatic hydrocarbon group for R include an alkyl group, an alkenyl group, and an alkynyl group.

Examples of the linear or branched alkyl group in R include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl group. N-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3- Ethylbutyl group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group Group, 4-methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3 -Dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propyl Butyl group, n-octyl group, isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl Group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
Examples of the cyclic alkyl group in R include, for example, a cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, Examples thereof include a 2-adamantyl group and a tricyclodecyl group.

Examples of the alkenyl group in R include a group in which one single bond (C—C) between carbon atoms of the alkyl group in R is substituted with a double bond (C═C).
Examples of the alkenyl group include a vinyl group (ethenyl group, —CH═CH ₂ ), an allyl group (2-propenyl group, —CH ₂ —CH═CH ₂ ), and a 1-propenyl group (—CH═ CH—CH ₃ ), isopropenyl group (—C (CH ₃ ) ═CH ₂ ), 1-butenyl group (—CH═CH—CH ₂ —CH ₃ ), 2-butenyl group (—CH ₂ —CH═CH) —CH ₃ ), 3-butenyl group (—CH ₂ —CH ₂ —CH═CH ₂ ), cyclohexenyl group, cyclopentenyl group and the like.

Examples of the alkynyl group in R include a group in which one single bond (C—C) between carbon atoms of the alkyl group in R is substituted with a triple bond (C≡C).
Examples of such alkynyl group include ethynyl group (—C≡CH), propargyl group (—CH ₂ —C≡CH), and the like.

In the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R, one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a fluorine atom, a chlorine atom, and a bromine atom. In the aliphatic hydrocarbon group, the number and position of the substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, all the substituents may be the same, all the substituents may be different, or only some of the substituents may be different.

In the phenyl group in R, one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, a monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, fluorine An atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C≡N), a phenoxy group (—O—C ₆ H ₅ ), and the like. In the phenyl group having a substituent, the number and position of the substituent are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
Examples of the aliphatic hydrocarbon group which is a substituent include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 16.

Y ^{1 in} R is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. In the general formulas “R ¹ —CY ¹ ₂ —”, “CY ¹ ₃ —” and “R ⁶ —C (═O) —CY ¹ ₂ —”, a plurality of Y ¹ may be the same as each other. May be different.

R ¹ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group (C ₆ H ₅ —). Examples of the aliphatic hydrocarbon group for R ¹ include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 19 carbon atoms.
R ² in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the same as the aliphatic hydrocarbon group in R.
R ³ in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms. Examples of the aliphatic hydrocarbon group for R ³ include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 16.
R ⁴ and R ⁵ in R are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms. That is, R ⁴ and R ⁵ may be the same or different from each other, and the aliphatic hydrocarbon group in R ⁴ and R ⁵ is, for example, the above in R except that it has 1 to 18 carbon atoms. The thing similar to an aliphatic hydrocarbon group is mentioned.
R ⁶ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group, or a group represented by the formula “AgO—”. Examples of the aliphatic hydrocarbon group for R ⁶ include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 19.

Among them, R is a linear or branched alkyl group, a group represented by the general formula “R ⁶ —C (═O) —CY ¹ ₂ —”, a hydroxyl group, or a phenyl group. preferable. R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group, or a group represented by the formula “AgO—”.

In the general formula (1), each X ¹ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, or A benzyl group (C ₆ H ₅ —CH ₂ —), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C ₂ H ₅ —O—CH═CH—), or the general formula “R ⁷ O— ”,“ R ⁷ S— ”,“ R ⁷ —C (═O) — ”or“ R ⁷ —C (═O) —O— ”.
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X ¹ include those similar to the aliphatic hydrocarbon group in R.

The halogen atom in X ^1, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the phenyl group and benzyl group in X ¹ , one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group (—NO ₂ ) and the like. In the phenyl group and benzyl group having a substituent, the number and position of the substituent are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.

R ⁷ in X ¹ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group (C ₄ H ₃ S—), a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, or A diphenyl group (biphenyl group, C ₆ H ₅ —C ₆ H ₄ —); Examples of the aliphatic hydrocarbon group for R ⁷ include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 10. Further, examples of the substituent having a phenyl group and a diphenyl group in R ^7, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. In the phenyl group and diphenyl group having a substituent, the number and position of the substituent are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other.
When R ⁷ is a thienyl group or a diphenyl group, there are no particular limitations on the bonding position of these groups with an adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X ¹ . For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.

In the general formula (1), two X ^{1 s} may be bonded as one group through a double bond with a carbon atom sandwiched between two carbonyl groups. Examples of such X ¹ include a group represented by the formula “═CH—C ₆ H ₄ —NO ₂ ”.

X ¹ is preferably a hydrogen atom, a linear or branched alkyl group, a benzyl group, or a group represented by the general formula “R ⁷ —C (═O) —” among the above. It is preferable that at least one X ¹ is a hydrogen atom.

Silver β-ketocarboxylate (1) is silver 2-methylacetoacetate (CH ₃ —C (═O) —CH (CH ₃ ) —C (═O) —OAg), silver acetoacetate (CH ₃ —C (= O) —CH ₂ —C (═O) —OAg), silver 2-ethylacetoacetate (CH ₃ —C (═O) —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver propionyl acetate (CH ₃ CH ₂ —C (═O) —CH ₂ —C (═O) —OAg), silver isobutyryl acetate ((CH ₃ ) ₂ CH—C (═O) —CH ₂ —C (═O) — OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C—C (═O) —CH ₂ —C (═O) —OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH ₂ —C (═O ) —CH ₂ —C (═O) —OAg), silver 2-n-butylacetoacetate (CH ₃ —C (═O) —CH (C H ₂ CH ₂ CH ₂ CH ₃ ) —C (═O) —OAg), silver 2-benzylacetoacetate (CH ₃ —C (═O) —CH (CH ₂ C ₆ H ₅ ) —C (═O) —OAg), silver benzoyl acetate (C ₆ H ₅ —C (═O) —CH ₂ —C (═O) —OAg), silver pivaloyl acetoacetate ((CH ₃ ) ₃ C—C (═O) —CH ₂ —C (═O) —CH ₂ —C (═O) —OAg), silver isobutyrylacetoacetate ((CH ₃ ) ₂ CH—C (═O) —CH ₂ —C (═O) —CH ₂ -C (= O) -OAg), silver 2-acetylpivaloyl acetate ((CH ₃ ) ₃ CC (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg), 2- acetyl isobutyryl silver acetate _{_{((CH 3) 2 CH-}} C (= O) -CH (-C (= O) -CH 3) -C (= O) - Ag), or is preferably acetone dicarboxylic silver _{(AgO-C (= O)} -CH 2 -C (= O) -CH 2 -C (= O) -OAg).

In the conductor (metal silver) formed by solidification treatment such as drying treatment or heating (firing) treatment using silver β-ketocarboxylate (1), the concentration of the remaining raw materials and impurities can be further reduced. In such a conductor, the smaller the raw materials and impurities, for example, the better the contact between the formed metal silvers, the easier the conduction, and the lower the resistivity.

The β-ketocarboxylate (1) is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent known in the art, as will be described later. Metal silver can be formed. The silver β-ketocarboxylate (1) is decomposed at a lower temperature to form metallic silver when used in combination with a reducing agent. The reducing agent will be described later.

In the present invention, the silver β-ketocarboxylate (1) may be used singly or in combination of two or more, and when two or more are used in combination, the combination and ratio are as follows: Can be adjusted arbitrarily.

(Silver carboxylate (4))
The silver carboxylate (4) is represented by the general formula (4).
In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (—COOH), or a group represented by the formula “—C (═O) —OAg”.
Examples of the aliphatic hydrocarbon group for R ⁸ include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 19 carbon atoms. However, the aliphatic hydrocarbon group for R ⁸ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

When the aliphatic hydrocarbon group for R ⁸ has a methylene group (—CH ₂ —), one or more of the methylene groups may be substituted with a carbonyl group. The number and position of the methylene groups that may be substituted with a carbonyl group are not particularly limited, and all methylene groups may be substituted with a carbonyl group. Here, the “methylene group” is not only a single group represented by the formula “—CH ₂ —” but also one of alkylene groups in which a plurality of groups represented by the formula “—CH ₂ —” are linked. And a group represented by the formula “—CH ₂ —”.

Silver carboxylate (4) includes silver pyruvate (CH ₃ —C (═O) —C (═O) —OAg), silver acetate (CH ₃ —C (═O) —OAg), silver butyrate (CH ₃ — (CH ₂ ) ₂ —C (═O) —OAg), silver isobutyrate ((CH ₃ ) ₂ CH—C (═O) —OAg), silver 2-ethylhexanoate (CH ₃ — (CH ₂ ) ₃ —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver neodecanoate (CH ₃ — (CH ₂ ) ₅ —C (CH ₃ ) ₂ —C (═O) —OAg), Shu It is preferably silver oxide (AgO—C (═O) —C (═O) —OAg) or silver malonate (AgO—C (═O) —CH ₂ —C (═O) —OAg). Further, silver oxalate (AgO—C (═O) —C (═O) —OAg) and silver malonate (AgO—C (═O) —CH ₂ —C (═O) —OAg) Of the groups represented by the formula “—COOAg”, one of the groups represented by the formula “—COOH” (HO—C (═O) —C (═O) —OAg, HO) Also preferred is —C (═O) —CH ₂ —C (═O) —OAg).

Similarly to the β-ketocarboxylate silver (1), silver carboxylate (4) is also used in the conductor (metal silver) formed by solidification treatment such as drying treatment or heating (firing) treatment. The concentration can be further reduced. And silver carboxylate (4) is also decomposed | disassembled at lower temperature by using together with a reducing agent, and forms metallic silver.

In this invention, silver carboxylate (4) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, the combination and ratio are arbitrary. Can be adjusted.

The silver carboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver caproylacetate, silver 2-n-butylacetoacetate, 2-benzylacetoacetate Silver acetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, silver acetone dicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, silver One or more selected from the group consisting of silver oxide and silver malonate are preferred.
Among these silver carboxylates, silver 2-methylacetoacetate and silver acetoacetate are excellent in compatibility with a nitrogen-containing compound (particularly an amine compound) described later, and are particularly suitable for increasing the concentration of silver ink compositions. It is mentioned as a thing.

In the silver ink composition, the content of silver derived from the silver carboxylate is preferably 5% by mass or more, and more preferably 10% by mass or more. When the silver content is within such a range, the formed conductor (metal silver) becomes more excellent in quality. The upper limit of the silver content is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably 25% by mass in consideration of the handleability of the silver ink composition.
In the present specification, “silver derived from carboxylate” is synonymous with silver in silver carboxylate blended at the time of producing the silver ink composition unless otherwise specified, and continues after blending. Includes all of the silver that constitutes silver carboxylate, the silver in the decomposition product produced by decomposition of silver carboxylate after compounding, and the silver itself (metal silver) produced by decomposition of silver carboxylate after compounding Let it be a concept.

[Nitrogen-containing compounds]
The nitrogen-containing compound in the present invention includes an amine compound having 25 or less carbon atoms (hereinafter sometimes abbreviated as “amine compound”), a quaternary ammonium salt having 25 or less carbon atoms (hereinafter, “quaternary ammonium salt”). Ammonia, an ammonium salt formed by a reaction of an amine compound having 25 or less carbon atoms with an acid (hereinafter sometimes abbreviated as “ammonium salt derived from an amine compound”), and ammonia as an acid. It is one or more selected from the group consisting of ammonium salts obtained by reaction (hereinafter sometimes abbreviated as “ammonium salts derived from ammonia”). That is, the nitrogen-containing compound to be blended may be only one type, or two or more types, and when two or more types are used in combination, the combination and ratio can be arbitrarily adjusted.

(Amine compound, quaternary ammonium salt)
The amine compound has 1 to 25 carbon atoms, and may be any of primary amine, secondary amine, and tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either chain or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or ammonium salt moiety (for example, the nitrogen atom constituting the amino group (—NH ₂ ) of the primary amine) may be one, or two or more.

Examples of the primary amine include monoalkylamines, monoarylamines, mono (heteroaryl) amines, and diamines in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the monoalkylamine may be linear, branched or cyclic, and examples of such an alkyl group include the same alkyl groups as those described above for R. The alkyl group is preferably a linear or branched alkyl group having 1 to 19 carbon atoms or a cyclic alkyl group having 3 to 7 carbon atoms.
Specific examples of preferable monoalkylamine include n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3 -Aminopentane, 3-methylbutylamine, 2-heptylamine (2-aminoheptane), 2-aminooctane, 2-ethylhexylamine, 1,2-dimethyl-n-propylamine and the like.

Examples of the aryl group constituting the monoarylamine include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. The aryl group preferably has 6 to 10 carbon atoms.

The heteroaryl group constituting the mono (heteroaryl) amine has a heteroatom as an atom constituting the aromatic ring skeleton. Examples of the heteroatom include a nitrogen atom, a sulfur atom, an oxygen atom, A boron atom etc. are mentioned. Moreover, the number of the said hetero atom which comprises an aromatic ring frame is not specifically limited, One may be sufficient and two or more may be sufficient. When there are two or more, these heteroatoms may be the same or different from each other. That is, these heteroatoms may all be the same, may all be different, or may be partially different.
The heteroaryl group may be either monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is not particularly limited, but is preferably a 3- to 12-membered ring.

Examples of the monoaryl group having 1 to 4 nitrogen atoms as the heteroaryl group include, for example, pyrrolyl group, pyrrolinyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, triazolyl group, Examples include a tetrazolyl group, a pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazolidinyl group, a piperazinyl group, and the like. Such a heteroaryl group is preferably a 3- to 8-membered ring, and preferably a 5- to 6-membered ring. More preferred.
Examples of the monoaryl group having one oxygen atom as the heteroaryl group include a furanyl group, and such a heteroaryl group is preferably a 3- to 8-membered ring. More preferably, it is a member ring.
Examples of the monoaryl group having one sulfur atom as the heteroaryl group include a thienyl group. The heteroaryl group is preferably a 3- to 8-membered ring, and preferably from 5 to 6 More preferably, it is a member ring.
Examples of the monoaryl group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms as the heteroaryl group include an oxazolyl group, an isoxazolyl group, an oxadiazolyl group, and a morpholinyl group. The heteroaryl group is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring.
Examples of the monoaryl group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms as the heteroaryl group include a thiazolyl group, a thiadiazolyl group, a thiazolidinyl group, and the like. Is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring.
Examples of the polyaryl group having 1 to 5 nitrogen atoms as the heteroaryl group include, for example, indolyl group, isoindolyl group, indolizinyl group, benzimidazolyl group, quinolyl group, isoquinolyl group, indazolyl group, benzotriazolyl group A tetrazolopyridyl group, a tetrazolopyridazinyl group, a dihydrotriazolopyridazinyl group, and the like. Such a heteroaryl group is preferably a 7-12 membered ring, More preferably, it is a ring.
Examples of the polyaryl group having 1 to 3 sulfur atoms as the heteroaryl group include a dithianaphthalenyl group and a benzothiophenyl group. Such a heteroaryl group has 7 to 12 members. A ring is preferable, and a 9- to 10-membered ring is more preferable.
Examples of the polyaryl group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms as the heteroaryl group include a benzoxazolyl group and a benzoxdiazolyl group. The heteroaryl group is preferably a 7-12 membered ring, more preferably a 9-10 membered ring.
Examples of the polyaryl group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms as the heteroaryl group include a benzothiazolyl group, a benzothiadiazolyl group, and the like. Is preferably a 7 to 12-membered ring, more preferably a 9 to 10-membered ring.

The diamine only needs to have two amino groups, and the positional relationship between the two amino groups is not particularly limited. As the preferred diamine, for example, in the monoalkylamine, monoarylamine or mono (heteroaryl) amine, one hydrogen atom other than the hydrogen atom constituting the amino group (—NH ₂ ) is substituted with an amino group. And the like.
The diamine preferably has 1 to 10 carbon atoms, and more preferable examples include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, and the like.

Examples of the secondary amine include dialkylamine, diarylamine, di (heteroaryl) amine and the like in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the dialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms, or having 3 to 7 carbon atoms. A cyclic alkyl group is preferred. Two alkyl groups in one molecule of dialkylamine may be the same as or different from each other.
Specific examples of preferable dialkylamines include N-methyl-n-hexylamine, diisobutylamine, and di (2-ethylhexyl) amine.

The aryl group constituting the diarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms. Two aryl groups in one molecule of diarylamine may be the same as or different from each other.

The heteroaryl group constituting the di (heteroaryl) amine is the same as the heteroaryl group constituting the mono (heteroaryl) amine, and is preferably a 6-12 membered ring. Two heteroaryl groups in one molecule of di (heteroaryl) amine may be the same or different from each other.

Examples of the tertiary amine include trialkylamine and dialkylmonoarylamine in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the trialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 19 carbon atoms, or 3 to 7 carbon atoms. The cyclic alkyl group is preferably. Further, the three alkyl groups in one molecule of trialkylamine may be the same as or different from each other. That is, all three alkyl groups may be the same, all may be different, or only a part may be different.
Specific examples of the preferable trialkylamine include N, N-dimethyl-n-octadecylamine, N, N-dimethylcyclohexylamine and the like.

The alkyl group constituting the dialkyl monoarylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 6 carbon atoms, or 3 to 3 carbon atoms. 7 is a cyclic alkyl group. Two alkyl groups in one molecule of dialkyl monoarylamine may be the same or different from each other.
The aryl group constituting the dialkyl monoarylamine is the same as the aryl group constituting the monoarylamine, and preferably has 6 to 10 carbon atoms.

In the present invention, examples of the quaternary ammonium salt include halogenated tetraalkylammonium, in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group constituting the halogenated tetraalkylammonium is the same as the alkyl group constituting the monoalkylamine, and preferably has 1 to 19 carbon atoms. Further, the four alkyl groups in one molecule of the tetraalkylammonium halide may be the same as or different from each other. That is, all four alkyl groups may be the same, all may be different, or only a part may be different.
Examples of the halogen constituting the halogenated tetraalkylammonium include fluorine, chlorine, bromine, iodine and the like.
Specific examples of the preferred tetraalkylammonium halide include dodecyltrimethylammonium bromide.

So far, the chain amine compound and the quaternary organic ammonium salt have been mainly described. However, in the amine compound and the quaternary ammonium salt, the nitrogen atom constituting the amine moiety or the ammonium salt moiety is a ring skeleton structure ( A heterocyclic compound which is a part of a heterocyclic skeleton structure) may be used. That is, the amine compound may be a cyclic amine, and the quaternary ammonium salt may be a cyclic ammonium salt. At this time, the ring (ring containing the nitrogen atom constituting the amine moiety or ammonium salt moiety) structure may be either monocyclic or polycyclic, and the number of ring members (number of atoms constituting the ring skeleton) is also particularly limited. Any of an aliphatic ring and an aromatic ring may be sufficient.
If it is a cyclic amine, as a preferable thing, a pyridine etc. will be mentioned, for example.

In the primary amine, secondary amine, tertiary amine and quaternary ammonium salt, the “hydrogen atom optionally substituted with a substituent” means a nitrogen atom constituting an amine moiety or an ammonium salt moiety. A hydrogen atom other than a hydrogen atom bonded to. The number of substituents at this time is not particularly limited, and may be one or two or more, and all of the hydrogen atoms may be substituted with a substituent. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, the plurality of substituents may all be the same, may all be different, or only some may be different. Further, the position of the substituent is not particularly limited.

Examples of the substituent in the amine compound and the quaternary ammonium salt include an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, and a trifluoromethyl group (—CF ₃ ). Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example.

When the alkyl group constituting the monoalkylamine has a substituent, the alkyl group has an aryl group as a substituent, a linear or branched alkyl group having 1 to 9 carbon atoms, or a substituent A cyclic alkyl group having 3 to 7 carbon atoms and an alkyl group having 1 to 5 carbon atoms is preferable. Specific examples of the monoalkylamine having such a substituent include 2-phenylethylamine, benzylamine, 2,3-dimethylcyclohexylamine and the like.
In the aryl group and alkyl group which are substituents, one or more hydrogen atoms may be further substituted with a halogen atom. Examples of the monoalkylamine having a substituent substituted with a halogen atom include 2-bromobenzylamine. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When the aryl group constituting the monoarylamine has a substituent, the aryl group is preferably an aryl group having 6 to 10 carbon atoms having a halogen atom as a substituent. Specific examples of the monoarylamine having such a substituent include bromophenylamine. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When the alkyl group constituting the dialkylamine has a substituent, the alkyl group is a linear or branched alkyl group having 1 to 9 carbon atoms and having a hydroxyl group or an aryl group as a substituent. Is preferred. Specific examples of the dialkylamine having such a substituent include diethanolamine and N-methylbenzylamine.

The amine compound includes n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-methylbutylamine, 2-heptylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, Diisobutylamine, N-methylbenzylamine, di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine It is preferable.
Among these amine compounds, 2-ethylhexylamine is excellent in compatibility with the silver carboxylate, particularly suitable for increasing the concentration of the silver ink composition, and particularly for reducing the surface roughness of the conductive layer. Listed as suitable.

(Ammonium salts derived from amine compounds)
In the present invention, the ammonium salt derived from the amine compound is an ammonium salt formed by reacting the amine compound with an acid. The acid may be an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid, or may be an organic acid such as acetic acid, and the type of acid is not particularly limited.
Examples of the ammonium salt derived from the amine compound include n-propylamine hydrochloride, N-methyl-n-hexylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride, and the like. It is not limited.

(Ammonium salt derived from ammonia)
In the present invention, the ammonium salt derived from ammonia is an ammonium salt formed by reacting ammonia with an acid. Here, examples of the acid include the same ones as in the case of the ammonium salt derived from the amine compound.
Examples of the ammonium salt derived from ammonia include ammonium chloride, but are not limited thereto.

In the present invention, the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from ammonia may be used alone or in combination of two or more. Well, when using 2 or more types together, the combination and ratio can be adjusted arbitrarily.
And as said nitrogen-containing compound, you may use individually 1 type selected from the group which consists of said amine compound, quaternary ammonium salt, ammonium salt derived from amine compound, and ammonium salt derived from ammonia, Two or more kinds may be used in combination, and when two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

In the silver ink composition, the compounding amount of the nitrogen-containing compound is preferably 0.3 to 15 mol, and more preferably 0.3 to 5 mol, per mol of the carboxylate silver. When the blending amount of the nitrogen-containing compound is within such a range, the silver ink composition is further improved in stability and the quality of the conductor (metal silver) is further improved. Furthermore, the conductor can be formed more stably without performing heat treatment at a high temperature.

[Reducing agent]
The reducing agent in the present invention may be abbreviated as oxalic acid (HOOC-COOH), hydrazine (H ₂ N—NH ₂ ) and a compound represented by the following general formula (5) (hereinafter referred to as “compound (5)”). One or more selected from the group consisting of:
HC (= O) -R ²¹ (5)
(Wherein R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, or an N, N-dialkylamino group, a hydroxyl group, or an amino group.)
That is, the reducing agent to be blended may be only one type, or two or more types, and when two or more types are used in combination, the combination and ratio can be arbitrarily adjusted.

The alkyl group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms and may be linear, branched or cyclic. Examples of the alkyl group for R ²¹ include those similar to the alkyl group for R in the general formula (1).

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms. Examples of such alkoxy groups include a monovalent group formed by bonding the alkyl group in R ^{21 to} an oxygen atom, and the like. Is mentioned.

The N, N-dialkylamino group having 20 or less carbon atoms in R ²¹ has 2 to 20 carbon atoms, and the two alkyl groups bonded to the nitrogen atom may be the same as or different from each other. The alkyl group in the N, N-dialkylamino group has 1 to 19 carbon atoms. However, the total value of the carbon number of these two alkyl groups is 2 to 20.
Each of the alkyl groups bonded to the nitrogen atom may be linear, branched or cyclic. Examples of such an alkyl group include those similar to the alkyl group in R of the general formula (1) except that the number of carbon atoms is 1 to 19.

Hydrazine as the reducing agent may be a monohydrate (H ₂ N—NH ₂ .H ₂ O).

Preferred examples of the reducing agent include formic acid (HC (═O) —OH); methyl formate (HC (═O) —OCH ₃ ), ethyl formate (HC—═O) — Formic acid esters such as OCH ₂ CH ₃ ) and butyl formate (HC (═O) —O (CH ₂ ) ₃ CH ₃ ); propanal (HC (═O) —CH ₂ CH ₃ ), butanal ( Aldehydes such as HC (═O) — (CH ₂ ) ₂ CH ₃ ) and hexanal (HC (═O) — (CH ₂ ) ₄ CH ₃ ); formamide (HC (═O) —NH ₂ ), formamides such as N, N-dimethylformamide (HC (═O) —N (CH ₃ ) ₂ ) (represented by the formula “HC (═O) —N (−) —”) A compound having a group); oxalic acid and the like.

In the silver ink composition, the compounding amount of the reducing agent is preferably 0.04 to 3.5 mol, and more preferably 0.06 to 2.5 mol per mol of the silver carboxylate. preferable. When the blending amount of the reducing agent is within such a range, the silver ink composition can form a conductor (metal silver) more easily and more stably.

[Acetylene alcohols]
The acetylene alcohols in the present invention are those represented by the following general formula (20) and having 9 or more carbon atoms (hereinafter sometimes abbreviated as “acetylene alcohol (20)”).

In the formula, R ′ and R ″ each independently represent a hydrogen atom, an alkyl group, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group in R ′ and R ″ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. However, the total value of the carbon number of R ′ and R ″ (the total value of the carbon number of R ′ and the carbon number of R ″) is 6 or more.
That is, acetylene alcohol (20) has 9 or more carbon atoms.

Examples of the alkyl group in R ′ and R ″ include those similar to the alkyl group in R, and those having 1 to 20 carbon atoms are preferable.
The linear or branched alkyl group in R ′ and R ″ preferably has 1 to 20 carbon atoms. Examples of such an alkyl group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, Neopentyl group, tert-pentyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1 -Dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, 1-ethyl-1- Methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl Group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 4, 4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group, n-octyl group , Isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4 -Ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl Group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1-propylpentyl group, 2-propylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.
The number of carbon atoms of the cyclic alkyl group in R ′ and R ″ is preferably 3-20. Examples of such alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, isobornyl, 1-adamantyl, 2- Examples thereof include an adamantyl group and a tricyclodecyl group.

The number of carbon atoms of the alkyl group in R ′ and R ″ is preferably 1 to 15, more preferably 1 to 12, still more preferably 1 to 10, and 1 to 8. Is particularly preferred.

At least one of the alkyl groups in R ′ and R ″ is preferably linear or branched, and more preferably both are linear or branched.

Examples of the substituent in which the hydrogen atom of the phenyl group in R ′ and R ″ may be substituted include, for example, a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the aliphatic group A monovalent group formed by bonding an aromatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, and the like. These substituents are the same as the substituents in which the hydrogen atom of the phenyl group in R may be substituted. In the phenyl group having a substituent, the number and position of the substituents are not particularly limited, and when the number of substituents is plural, the plural substituents may be the same as or different from each other.

The total number of carbon atoms of R ′ and R ″ is preferably 6 to 16, more preferably 6 to 13, still more preferably 6 to 11, and particularly preferably 6 to 9. preferable.
That is, the carbon number of the acetylene alcohol (20) is preferably 9 to 19, more preferably 9 to 16, further preferably 9 to 14, and particularly preferably 9 to 12. .

However, at least one of R ′ and R ″ is the alkyl group or the phenyl group, and R ′ and R ″ are not both hydrogen atoms.

The acetylene alcohol (20) may be either liquid or solid, for example, but is preferably liquid because it is easy to handle.
Moreover, what can be removed by vaporizing acetylene alcohol (20) under normal pressure or pressure reduction is preferable.

Preferred acetylene alcohol (20) includes, for example, 3-ethyl-1-heptin-3-ol, 4-ethyl-1-octyn-3-ol, and the like.

Acetylene alcohol (20) may be used alone or in combination of two or more, and the combination and ratio thereof can be arbitrarily adjusted.

The amount of acetylene alcohol (20) is preferably 0.003 to 0.7 mol per mol of the silver carboxylate, for example, 0.01 to 0.7 mol, 0.02 to 0 It may be any of 0.7 mol and 0.02 to 0.3 mol. The storage stability of a silver ink composition improves more because the said compounding quantity of acetylene alcohol (20) is such a range.

In the silver ink composition of the present invention, a thin line pattern can be more easily formed among metallic silvers by blending both the reducing agent and acetylene alcohol (20).

[Other ingredients]
The silver ink composition may contain other components other than the silver carboxylate, nitrogen-containing compound, reducing agent and acetylene alcohol (20).
The other components in the silver ink composition can be arbitrarily selected according to the purpose and are not particularly limited. Examples of the other components include acetylene alcohols other than acetylene alcohol (20), solvents other than the other acetylene alcohols, and the like, and can be arbitrarily selected according to the type and amount of the compounding components.
As the other components in the silver ink composition, one kind may be used alone, two or more kinds may be used in combination, and two or more kinds may be used in combination. Can be adjusted.

The other acetylene alcohol is an alcohol other than acetylene alcohol (20) having a triple bond (“C≡C”) between carbon atoms. Other acetylene alcohols may or may not have a double bond (“C═C”) between carbon atoms, but preferably do not have.
By using a silver ink composition in which other acetylene alcohols are blended, blurring can be further suppressed in a printing pattern formed by applying various printing methods described later. As a result, metallic silver in which fading is further suppressed can be formed.

Preferred examples of the other acetylene alcohol include those represented by the following general formula (21) (hereinafter sometimes abbreviated as “acetylene alcohol (21)”).

Wherein, R 9 ^'and R ^9' 'are each independently a hydrogen atom or an alkyl group, provided that, R ^9' and R ^{9 'sum} of the carbon atoms of' (R 9 carbon number of ^'and R ⁹ The total value of '' and the number of carbon atoms) is 0-5.
That is, acetylene alcohol (21) has 3 to 8 carbon atoms.

The alkyl group in R ⁹ ′ and R ⁹ ″ is the same as the alkyl group in R ′ and R ″ in the general formula (20) except that the number of carbon atoms is limited as described above. It is. The alkyl group in R ⁹ ′ and R ⁹ ″ has 1 to 5 carbon atoms.

Preferred acetylene alcohols (21) include, for example, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, and the like. Can be mentioned.

Acetylene alcohol (21) may be used alone or in combination of two or more, and the combination and ratio thereof can be arbitrarily adjusted.

When the other acetylene alcohol is used, the blending amount of the other acetylene alcohol in the silver ink composition is preferably 0.2 to 11 moles per mole of the acetylene alcohol (20). It is more preferably from ˜10 mol, particularly preferably from 0.2 to 9 mol. The effect by using other acetylene alcohol is acquired more notably because the said compounding quantity of another acetylene alcohol is more than the said lower limit. Moreover, the effect by using acetylene alcohol (20) and the effect by using other acetylene alcohol are obtained in a more balanced manner because the blending amount of other acetylene alcohol is not more than the upper limit. It is done.

The solvent is not particularly limited as long as it is other than acetylene alcohol (20) and the other acetylene alcohol.
Examples of the solvent include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; pentane, hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, and pentadecane. Aliphatic hydrocarbons such as ethanol; saturated aliphatic alcohols such as ethanol and 2-propanol; unsaturated alcohols other than acetylene alcohol (20) and other acetylene alcohols; halogenated hydrocarbons such as dichloromethane and chloroform; ethyl acetate and glutaric acid Esters such as monomethyl and dimethyl glutarate; ethers such as diethyl ether, tetrahydrofuran (THF) and 1,2-dimethoxyethane (dimethyl cellosolve); acetone, methyl ethyl ketone (MEK), cyclohexanone and the like Ketone; nitriles such as acetonitrile; N, N-dimethylformamide (DMF), N, N-but amides of dimethylacetamide, and the like, without limitation.

The unsaturated alcohol has acetylene alcohol (20) and other acetylenes having a double bond between carbon atoms (“C═C”) and no triple bond between carbon atoms (“C≡C”). It is something other than alcohol.
The aliphatic hydrocarbon preferably has 15 or less carbon atoms.

In the silver ink composition, the ratio of the amount of the solvent to the amount of acetylene alcohol (20) is preferably as small as possible, preferably 10% by mass or less, more preferably 5% by mass or less. The content is more preferably not more than mass%, particularly preferably not more than 1 mass%, and most preferably 0 mass, that is, the solvent is not blended.

In the silver ink composition, the ratio of the blending amount of other components not corresponding to any of the other acetylenic alcohols and solvents to the total blending component amount is preferably 10% by mass or less, and preferably 5% by mass or less. It is more preferable that the silver ink composition exhibits its effect sufficiently even when 0 mass, that is, without adding such other components.

In the silver ink composition, all the components may be dissolved, or a part or all of the components may be dispersed without dissolving, but it is preferable that all the components are dissolved. The undissolved component is preferably dispersed uniformly.

<Method for producing silver ink composition>
The method for producing a silver ink composition of the present invention includes a step of blending the silver carboxylate, a nitrogen-containing compound, a reducing agent, and acetylene alcohol (20) (hereinafter sometimes abbreviated as “blending step”).

After the blending step, the obtained blend may be used as it is as a silver ink composition, or the resulting blend is further stirred at a predetermined temperature and time for a stirring step. It is good also as a silver ink composition, and it is good also as what was passed through the refinement | purification process which refine | purifies what was obtained by the well-known method in any step after a compounding process as a silver ink composition. In the present invention, particularly when β-ketocarboxylate (1) is used as the carboxylate, no impurities that inhibit conductivity are generated in the blending step, or the amount of such impurities generated is extremely small. Can be suppressed. Therefore, even when a silver ink composition that has not been subjected to a purification step is used, a conductor (metal silver) having sufficient conductivity can be obtained.

In the blending step, all the components may be added and then mixed, or some components may be mixed while being sequentially added, or all components may be mixed while being sequentially added. Good.

In the blending step, the order of adding the blending components is not particularly limited, and can be appropriately selected according to the purpose. However, it is assumed that the reducing agent promotes the formation of metallic silver from the silver carboxylate, and that acetylene alcohol (20) is strongly involved in improving the storage stability of the silver ink composition. On the other hand, depending on the types of the reducing agent and acetylene alcohol (20), these components may directly react with each other. For these reasons, in the blending step, the reducing agent is added to the silver carboxylate prior to acetylene alcohol (20) to promote the formation of metallic silver, and the resulting mixture is further added to acetylene. It is preferred to add alcohol (20). Examples of such an addition method include a method of adding the silver carboxylate, the reducing agent, and the acetylene alcohol (20) in this order to the nitrogen-containing compound.
When using the said other acetylene alcohol, it is preferable to handle other acetylene alcohol similarly to acetylene alcohol (20). Depending on the type of reducing agent and other acetylenic alcohols, these components may also react directly. Therefore, in the blending step, it is preferable to add other acetylene alcohols as in the case of acetylene alcohol (20). And it is preferable to mix | blend other acetylene alcohol simultaneously with acetylene alcohol (20).

In the blending step, the reducing agent is preferably blended dropwise, and the surface roughness of the metallic silver tends to be further reduced by suppressing fluctuations in the dropping speed.
Moreover, in the said mixing | blending process, it is preferable to mix | blend acetylene alcohol (20) by dripping.
When using the said other acetylene alcohol, it is preferable to mix | blend another acetylene alcohol by dripping in the said mixing | blending process.

Both the blending step and the stirring step may be performed in an air atmosphere, but at least one of the blending step and the stirring step is performed in an inert gas atmosphere such as nitrogen gas, helium gas, or argon gas. Preferably, both the blending step and the stirring step are more preferably performed in the inert gas atmosphere.
In addition, whether the blending step and the stirring step are performed in an air atmosphere or the inert gas atmosphere, the moisture content of the air and the inert gas is adjusted by a desiccant or the like. Those are preferred.

The mixing method of compounding ingredients is not particularly limited, and is a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill, or the like; What is necessary is just to select suitably from well-known methods, such as a method.
In the silver ink composition, when the undissolved component is uniformly dispersed, it is preferable to apply a method of dispersing using, for example, the above-described three-roll, kneader or bead mill.

The temperature in each step until the silver ink composition is obtained, such as the blending step and the stirring step, is not particularly limited as long as each blending component does not deteriorate, but is preferably −5 to 60 ° C. And the said temperature is good to adjust suitably according to the kind and quantity of a compounding component so that the mixture obtained by mix | blending may become the viscosity which is easy to stir.

The total time of the blending step and the stirring step is not particularly limited as long as each blending component does not deteriorate, but is preferably 10 minutes to 36 hours.

[carbon dioxide]
The silver ink composition may be further supplied with carbon dioxide. Such a silver ink composition has a high viscosity. For example, a flexographic printing method, a screen printing method, a gravure printing method, a gravure offset printing method, a pad printing method, etc. Suitable for application.

Carbon dioxide may be supplied at any time during the production of the silver ink composition.
In the present invention, for example, carbon dioxide is supplied to the first mixture in which the silver carboxylate and the nitrogen-containing compound are blended to form a second mixture, and the reducing agent is further added to the second mixture. It is preferable to produce a silver ink composition by blending acetylene alcohol (20). Moreover, when mix | blending the said other component, these can be mix | blended at the time of manufacture of any one or both of a 1st mixture and a 2nd mixture, and can be arbitrarily selected according to the objective.

The first mixture can be produced by the same method as the above silver ink composition except that the blending components are different.

In the first mixture, all the components may be dissolved, or a part or all of the components may be dispersed without dissolving, but it is preferable that all the components are dissolved, It is preferable that the components which are not dissolved are uniformly dispersed.

The compounding temperature at the time of producing the first mixture is not particularly limited as long as each compounding component does not deteriorate, but it is preferably −5 to 30 ° C. In addition, the blending time may be appropriately adjusted according to the type of blending component and the temperature at the time of blending, but is preferably 0.5 to 12 hours, for example.

Carbon dioxide (CO ₂ ) supplied to the first mixture may be either gaseous or solid (dry ice), or both gaseous and solid. By supplying carbon dioxide, it is estimated that this carbon dioxide dissolves in the first mixture and acts on the components in the first mixture, thereby increasing the viscosity of the obtained second mixture.

The carbon dioxide gas may be supplied by various known methods for blowing gas into the liquid, and a suitable supply method may be selected as appropriate. For example, a method of immersing one end of the pipe in the first mixture, connecting the other end to a carbon dioxide gas supply source, and supplying the carbon dioxide gas to the first mixture through the pipe can be mentioned. At this time, the carbon dioxide gas may be supplied directly from the end of the pipe. For example, a plurality of voids that can serve as gas flow paths, such as a porous one, are provided to diffuse the introduced gas. A gas diffusion member that can be discharged as minute bubbles may be connected to the end of the pipe, and the carbon dioxide gas may be supplied through the gas diffusion member. Moreover, you may supply a carbon dioxide gas, stirring the 1st mixture by the method similar to the time of manufacture of a 1st mixture. By doing in this way, carbon dioxide can be supplied efficiently.

The supply amount of carbon dioxide gas is not particularly limited, and may be appropriately adjusted according to the amount of the first mixture at the supply destination and the viscosity of the target silver ink composition or the second mixture. For example, in order to obtain about 100 to 1000 g of a silver ink composition having a viscosity at 20 to 25 ° C. of 5 Pa · s or more, it is preferable to supply 100 L or more of carbon dioxide gas, and more preferably 200 L or more. Although the viscosity at 20 to 25 ° C. of the silver ink composition has been described here, the temperature at the time of using the silver ink composition is not limited to 20 to 25 ° C. and can be arbitrarily selected. In the present specification, “viscosity” means a value measured using an ultrasonic vibration viscometer unless otherwise specified.

The flow rate of carbon dioxide gas may be appropriately adjusted in consideration of the required supply amount of carbon dioxide gas, but is preferably 0.5 mL / min or more per 1 g of the first mixture, and is 1 mL / min or more. More preferably. The upper limit value of the flow rate is not particularly limited, but is preferably 40 mL / min per 1 g of the mixture in consideration of handling properties and the like.
The carbon dioxide gas supply time may be appropriately adjusted in consideration of the required supply amount and flow rate of carbon dioxide gas.

The temperature of the first mixture at the time of supplying carbon dioxide gas is preferably 5 to 70 ° C., more preferably 7 to 60 ° C., and particularly preferably 10 to 50 ° C. When the temperature is equal to or higher than the lower limit value, carbon dioxide can be supplied more efficiently, and when the temperature is equal to or lower than the upper limit value, a silver ink composition having better quality with fewer impurities can be obtained.

The flow rate and supply time of carbon dioxide gas, and the temperature at the time of supplying carbon dioxide gas may be adjusted to a suitable range while considering each value. For example, even if the temperature is set lower, the carbon dioxide gas flow rate is set higher, the carbon dioxide gas supply time is set longer, or both are performed efficiently. Can supply carbon. Moreover, even if the flow rate of carbon dioxide gas is set to a small value, the carbon dioxide gas can be efficiently produced by increasing the temperature, setting the carbon dioxide gas supply time longer, or both. Can supply. That is, a silver ink of good quality can be obtained by flexibly combining the numerical values in the above numerical range exemplified as the flow rate of carbon dioxide gas and the temperature at the time of carbon dioxide gas supply while considering the supply time of carbon dioxide gas. A composition is obtained efficiently.

The supply of carbon dioxide gas is preferably performed while stirring the first mixture. By doing in this way, the supplied carbon dioxide gas diffuses more uniformly in the first mixture, and carbon dioxide can be supplied more efficiently.
The stirring method at this time may be the same as in the case of the mixing method at the time of producing the above silver ink composition not using carbon dioxide.

The supply of dry ice (solid carbon dioxide) may be performed by adding dry ice to the first mixture. The total amount of dry ice may be added all at once, or may be added stepwise (continuously across a time zone during which no addition is performed).
What is necessary is just to adjust the usage-amount of dry ice in consideration of the supply amount of said carbon dioxide gas.
During and after the addition of dry ice, the first mixture is preferably stirred. For example, the first mixture is preferably stirred in the same manner as in the production of the silver ink composition described above without using carbon dioxide. By doing in this way, carbon dioxide can be supplied efficiently.
The temperature at the time of stirring may be the same as that at the time of supplying carbon dioxide gas. Moreover, what is necessary is just to adjust stirring time suitably according to stirring temperature.

The viscosity of the second mixture may be appropriately adjusted according to the purpose, such as a method for handling the silver ink composition or the second mixture, and is not particularly limited. For example, when the silver ink composition is applied to a printing method using a high viscosity ink such as a screen printing method or a flexographic printing method, the viscosity of the second mixture at 20 to 25 ° C. is 3 Pa · s or more. Is preferred. Here, the viscosity of the second mixture at 20 to 25 ° C. has been described, but the temperature at the time of use of the second mixture is not limited to 20 to 25 ° C. and can be arbitrarily selected.

In the second mixture, the reducing agent and acetylene alcohol (20) may be further blended, and the other components may be blended as necessary to obtain a silver ink composition. The reducing agent and acetylene alcohol (20) may be blended in this order, may be blended simultaneously, or may be blended in the order of acetylene alcohol (20) and reducing agent. However, for the reason explained above, the reducing agent is added to the second mixture before acetylene alcohol (20) to promote the formation of metallic silver, and then the acetylene alcohol (20) is further added to the obtained mixture. Is preferably added.
The silver ink composition at this time can be manufactured by the same method as the above silver ink composition not using carbon dioxide except that the blending components are different. In the obtained silver ink composition, all the components may be dissolved, or some or all of the components may be dispersed without being dissolved, but all the components are dissolved. It is preferable that the undissolved components are uniformly dispersed.

The temperature in each step from the blending of each blending component into the second mixture until obtaining the silver ink composition is not particularly limited as long as each blending component does not deteriorate, but is preferably −5 to 60 ° C. And the temperature at the time of this mixing | blending is good to adjust suitably so that the mixture obtained by mix | blending may become the viscosity which is easy to stir according to the kind and quantity of a mixing | blending component.
In addition, the total time of blending each blending component into the second mixture and the subsequent stirring may be appropriately adjusted according to the type of blending component and the temperature at the blending. Time is preferred.

As described above, the other components may be blended during the production of either the first mixture or the second mixture, or may be blended during the production of both.
That is, when the other component is a solvent, in the process of producing a silver ink composition through the first mixture and the second mixture, the ratio of the amount of the solvent to the amount of acetylene alcohol (20) ([solvent (Mass)] / [acetylene alcohol (20) (mass)] × 100) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. The content is preferably 1% by mass or less, particularly 0%, that is, the silver ink composition exhibits its effect sufficiently even when no solvent is added.

On the other hand, when the other component does not correspond to any of the other acetylene alcohol and solvent, the ratio of the blended amount of the other component to the total amount of blended components other than carbon dioxide ([other acetylene alcohol and solvent Other components (mass) not corresponding to any of the above] / [silver carboxylate, nitrogen-containing compound, reducing agent, acetylene alcohol (20), and other components (mass)] × 100) is 10% by mass or less. Preferably, the amount is 5% by mass or less, more preferably 0% by mass, that is, the silver ink composition exhibits its effect sufficiently even when no other components are blended.

The silver ink composition to which carbon dioxide is supplied is, for example, a viscosity at 20 to 25 ° C. when the silver ink composition is applied to a printing method using a high viscosity ink such as a screen printing method or a flexographic printing method. Is preferably 1 Pa · s or more.

For example, when a reducing agent is blended, the resulting blend (silver ink composition) tends to generate heat relatively easily. And when the temperature at the time of the compounding of the reducing agent is high, this compound is in the same state as at the time of the heat treatment of the silver ink composition described later. It is presumed that the formation of metallic silver may start in at least part of the silver. Such a silver ink composition containing metallic silver may be able to form metallic silver by performing post-treatment under milder conditions than a silver ink composition not containing metallic silver during the formation of metallic silver. Further, when the amount of the reducing agent is sufficiently large, metallic silver may be formed by performing post-treatment under the same mild conditions. In this way, by adopting conditions that promote the decomposition of silver carboxylate, as a post-treatment, metallic silver is formed by a heat treatment at a lower temperature or only by a drying treatment at room temperature without performing the heat treatment. There are things you can do. Moreover, the silver ink composition containing such metal silver can be handled in the same manner as the silver ink composition not containing metal silver, and the handleability is not particularly inferior.

In addition, the 2nd mixture in this invention has a viscosity higher than usual by supply of a carbon dioxide as mentioned above. On the other hand, when the reducing agent is blended into the second mixture, depending on the type of the second mixture or the reducing agent, formation of metallic silver is started in at least part of the silver carboxylate as described above, and metallic silver is deposited. Sometimes. Here, when the viscosity of the second mixture is high, aggregation of the precipitated metallic silver is suppressed, and the dispersibility of the metallic silver in the obtained silver ink composition is improved. A conductor obtained by forming metallic silver by a method described later using such a silver ink composition is obtained by blending a reducing agent in a mixture having a low viscosity, that is, carbon dioxide is not supplied. In addition, it has higher electrical conductivity (lower volume resistivity), lower surface roughness, and more favorable characteristics than a conductor using a silver ink composition.

The silver ink composition of the present invention has better storage stability than conventional silver ink compositions. The storage stability of the silver ink composition can be determined, for example, by dividing the silver ink composition into two or more and storing the obtained silver ink compositions having the same composition for different periods of time. Metallic silver is formed using the ink composition, and physical property values serving as conductivity indicators such as volume resistivity of the metallic silver are measured, and the difference can be confirmed by the difference in these physical property values.
Here, it is preferable that two or more silver ink compositions to be compared have the same storage conditions other than the storage period.

<Laminate>
The silver ink composition of the present invention can form metallic silver having high conductivity by solidification treatment such as heating (firing) treatment. For example, the silver ink composition of the present invention is deposited on a substrate, heat-treated, and the silver carboxylate is decomposed to form a layer made of metallic silver on the substrate (hereinafter abbreviated as “silver layer”). To obtain a laminate.

A silver ink composition can be made to adhere on a base material by well-known methods, such as a printing method, the apply | coating method, and the immersion method, for example.
Examples of the printing method include screen printing method, flexographic printing method, offset printing method, dip printing method, ink jet printing method, dispenser printing method, jet dispenser printing method, gravure printing method, gravure offset printing method, The pad printing method etc. are mentioned.
Examples of the coating method include various coaters such as a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, a gravure coater, and a wire bar. Methods and the like.

At the time of forming the silver layer, the thickness of the silver layer can be adjusted by adjusting the amount of the silver ink composition to be deposited on the substrate or the blending amount of the silver carboxylate in the silver ink composition.

When the silver ink composition deposited on the substrate is subjected to a drying process, it may be performed by a known method. That is, the drying treatment may be performed, for example, under normal pressure, reduced pressure, or air blowing conditions, and may be performed under air or an inert gas atmosphere. Also, the drying temperature is not particularly limited, and may be either heat drying or room temperature drying. As a preferable drying method when the heat treatment is unnecessary, for example, a method of drying in the atmosphere at 18 to 30 ° C. can be mentioned.

When the silver ink composition deposited on the substrate is heated (baked), the conditions may be adjusted as appropriate according to the type of compounding component of the silver ink composition. Usually, the heating temperature is preferably 60 to 370 ° C., more preferably 70 to 280 ° C. The heating time may be adjusted according to the heating temperature, but it is usually preferably 1 minute to 24 hours, and more preferably 1 minute to 12 hours. Among the silver carboxylates, in particular, the β-ketocarboxylate (1) is different from a metal silver forming material such as silver oxide, for example, at a low temperature without using a reducing agent known in the art. Decompose. Reflecting such decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional one as described above.

When the silver ink composition is attached to a substrate having low heat resistance and is heated (baked), the heating temperature is preferably less than 130 ° C, more preferably 125 ° C or less, and 120 ° C or less. It is particularly preferred that

The method for heat treatment of the silver ink composition is not particularly limited. The heat treatment can be performed by, for example, heating with an electric furnace, heating with a thermal head, heating with far-infrared irradiation, or heating by blowing a hot gas. Further, the heat treatment may be performed in the atmosphere, in an inert gas atmosphere, or may be performed under humidified conditions. The heat treatment may be performed under normal pressure, reduced pressure, or increased pressure.

In this specification, “humidification” means that the humidity is artificially increased unless otherwise specified, and the relative humidity is preferably 5% or more. At the time of heat treatment, since the humidity in the treatment environment becomes extremely low due to the high treatment temperature, it can be said that the relative humidity of 5% is clearly artificially increased.

The relative humidity when the heat treatment of the silver ink composition is performed under humidified conditions is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, and 70%. It is particularly preferable that it be 90% or more, or 100%. And you may perform the heat processing under humidification conditions by spraying the high pressure steam heated to 100 degreeC or more. Thus, by heat-processing under humidification conditions, highly pure metallic silver can be formed in a short time.

The heat treatment of the silver ink composition may be performed in two stages. For example, in the first stage heat treatment, there is a method in which the silver ink composition is mainly dried rather than the formation of metallic silver, and in the second stage heat treatment, the formation of metallic silver is performed to the end.
In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition, but is preferably 60 to 120 ° C, more preferably 70 to 120 ° C. The temperature is preferably 80 to 110 ° C. The heating time may be adjusted according to the heating temperature, but it is usually preferably 5 seconds to 12 hours, and more preferably 30 seconds to 2 hours.
In the second stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition so that metallic silver is formed satisfactorily, but it should be 60 to 280 ° C. Preferably, the temperature is 70 to 260 ° C. The heating time may be adjusted according to the heating temperature, but it is usually preferably 1 minute to 12 hours, and more preferably 1 minute to 10 hours.
When the silver ink composition is attached to a substrate having low heat resistance and is heated (baked), the heating temperature in the first stage and second stage heat treatment is preferably less than 130 ° C. More preferably, it is not higher than 120 ° C, particularly preferably not higher than 120 ° C.

The heat treatment of the silver ink composition described so far is performed in the gas phase. However, when the heat treatment of the silver ink composition is performed in two steps, the heat treatment in the second step is performed in the gas phase. You may carry out in a liquid phase instead of inside. The silver ink composition that has been completely or partially dried through the first stage heat treatment can be subjected to the second stage heat treatment without impairing its shape by contacting with the heated liquid. And it is preferable to perform the heat processing in the liquid phase of the 2nd step after performing the heat processing of the 1st step of a silver ink composition by immersing a silver ink composition in the heated liquid. The heating temperature and heating time in the heat treatment in the liquid phase are the same as the heating temperature and heating time in the second-stage heat treatment described above.
The heated liquid is preferably hot water (heated water), and the second stage heat treatment is performed by immersing the silver ink composition subjected to the first stage heat treatment in hot water, that is, by hot water bathing. Preferably it is done.
When the second stage heat treatment is performed in the liquid phase, the metallic silver formed by this heat treatment may be further dried.

When the second stage heat treatment of the silver ink composition is performed in a liquid phase, the first stage heat treatment of the silver ink composition is preferably performed under non-humidified conditions.
In the present specification, “non-humidification” means that the above “humidification” is not performed, that is, the humidity is not artificially increased, and preferably the relative humidity is less than 5%. .

When heat treatment under humidified conditions is employed, it is particularly preferable to perform the heat treatment of the silver ink composition by the following two-step method. That is, in the first stage heat treatment, the silver ink composition is mainly dried under the non-humidified condition as described above, rather than the formation of metallic silver, and in the second stage heat treatment, under the humidified condition, As described above, it is particularly preferable to heat-treat the silver ink composition by forming metal silver to the end.

When the second stage heat treatment is performed under humidified conditions, the heating temperature during the heat treatment under the first stage non-humidified conditions is preferably 60 to 120 ° C, and preferably 70 to 120 ° C. More preferred is 80 to 110 ° C. The heating time is preferably 5 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and particularly preferably 30 seconds to 10 minutes.
The heating temperature during the heat treatment under the second-stage humidification condition, which is performed after the heat treatment under the first-stage non-humidification conditions, is preferably 60 to 140 ° C, and preferably 70 to 130 ° C. Is more preferable. The heating time is preferably 1 minute to 2 hours, more preferably 1 minute to 1 hour, and particularly preferably 1 minute to 30 minutes.
When the silver ink composition is attached to a substrate having low heat resistance and is heated (baked), the heat treatment under the first stage non-humidifying condition and the heat treatment under the second stage humidifying condition are performed. The heating temperature is preferably less than 130 ° C, more preferably 125 ° C or less, and particularly preferably 120 ° C or less.

As described above, the preferable method for producing metal silver includes, for example, one having a step of forming the metal silver using the silver ink composition. Among the preferred methods, for example, In the step of forming the metallic silver, the silver ink composition is heat-treated under non-humidified conditions, and further heat-treated under humidified conditions or in contact with a heated liquid. Can be mentioned.

The metallic silver formed using the silver ink composition of the present invention has excellent conductivity, and its volume resistivity is, for example, preferably 14.0 μΩ · cm or less, more preferably 13.5 μΩ · cm or less, particularly Preferably, it is 13.0 μΩ · cm or less. The lower limit value of the volume resistivity of the metallic silver is not particularly limited, but is, for example, 5.0 μΩ · cm.
For example, a silver ink composition having a storage period of 30 days immediately after production can also form metallic silver having the above volume resistivity.

The silver ink composition of the present invention can form metallic silver excellent in conductivity even when the storage period immediately after production is 1 day, and the volume resistivity is preferably, for example, 13.5 μΩ · It is possible to form metallic silver of cm or less, more preferably 13.0 μΩ · cm or less, particularly preferably 12.5 μΩ · cm or less. The lower limit value of the volume resistivity of the metallic silver is not particularly limited, but is, for example, 4.5 μΩ · cm.

The silver ink composition of the present invention has better storage stability than conventional silver ink compositions. Therefore, the metallic silver formed from the silver ink composition of the present invention after long-term storage has the same composition immediately after production, compared with the metallic silver formed from the silver ink composition of the present invention with a short storage period. There is no significant difference in conductivity (volume resistivity).
For example, the volume resistivity ρ ₁ (μΩ · cm) of metallic silver formed using a silver ink composition having a storage period of 1 day immediately after manufacture is the same as that immediately after manufacture, and immediately after manufacture. And the volume resistivity ρ ₂ (μΩ · cm) of metallic silver formed using a silver ink composition having a storage period of 30 days, and using the formula “(ρ ₂ −ρ ₁ ) / ρ ₁ × The change rate (%) of the volume resistivity of metallic silver calculated by “100” is preferably 20% or less, more preferably 15% or less, and particularly preferably 10% or less.

In order for metallic silver to exhibit the volume resistivity and the rate of change thereof as described above, the storage temperature of the silver ink composition is preferably 20 ° C. or less, and more preferably 15 ° C. or less. A temperature of 10 ° C. or lower is particularly preferable.

The metallic silver formed using the silver ink composition of the present invention is extremely high in purity, and the proportion of metallic silver is sufficiently high that it can be regarded as consisting solely of metallic silver, for example, preferably 99 mass. % Or more.
On the other hand, the metallic silver formed using the silver ink composition of the present invention has an upper limit of the metallic silver ratio, for example, 99.9 mass%, 99.8 mass%, 99.7 mass%, 99.99 mass%. It can be any of 6% by mass, 99.5% by mass, 99.4% by mass, 99.3% by mass, 99.2% by mass and 99.1% by mass.

The volume resistivity of the metallic silver can be adjusted by, for example, the purity and thickness of the metallic silver (silver layer).

FIG. 1 is a cross-sectional view schematically showing an embodiment of a laminate obtained using the silver ink composition of the present invention. For example, FIG. 1 may show an enlarged main part for convenience, and the dimensional ratios and the like of the respective constituent elements are not always the same. The same applies to the following drawings.
The laminated body 1 shown here is formed by laminating a silver layer 12 on the surface (one main surface) 11a of a base material 11.

[Base material]
The substrate 11 is not particularly limited as long as the silver ink composition can be used.
Specific examples of the material of the substrate 11 include polyethylene (PE); polypropylene (PP); polyvinyl chloride (PVC); polyvinylidene chloride (PVDC); polymethylpentene (PMP); polycycloolefin; PS); polyvinyl acetate (PVAc); acrylic resin such as polymethyl methacrylate (PMMA); AS resin; ABS resin; polyamide (PA) such as nylon 6,6, nylon 6, etc .; polyimide; polyamideimide (PAI); Polyacetal (POM); Polyethylene terephthalate (PET); Polybutylene terephthalate (PBT); Polytrimethylene terephthalate (PTT); Polyethylene naphthalate (PEN); Polybutylene naphthalate (PBN); Polyphenylene sulfide (PPS); Polysulfone (PSF); Polyethersulfone (PES); Polyetherketone (PEK); Polyetheretherketone (PEEK); Polycarbonate (PC); Polyurethane; Polyphenylene ether (PPE); Modified polyphenylene ether (m-PPE); Arylate; epoxy resin; melamine resin; phenol resin; synthetic resin such as urea resin.
In addition to the above, the material of the base material 11 includes, for example, ceramics such as glass and silicon; paper and the like.
The substrate 11 may be a combination of two or more materials such as a glass epoxy resin and a polymer alloy.

The base material 11 can select an arbitrary shape according to the purpose, and is preferably in the form of a film or a sheet, for example. The thickness of the substrate 11 in the form of a film or sheet is preferably 0.5 to 5000 μm, and more preferably 0.5 to 2500 μm. When the thickness of the base material 11 is equal to or greater than the lower limit value, the structure of the silver layer can be more stably maintained, and when the thickness of the base material 11 is equal to or less than the upper limit value, handling at the time of forming the silver layer The property becomes better.

The substrate 11 may be composed of a single layer, or may be composed of two or more layers. When the base material 11 consists of multiple layers, these multiple layers may be the same as or different from each other. That is, all the layers may be the same, all the layers may be different, or only some of the layers may be different. And when several layers differ from each other, the combination of these several layers is not specifically limited. Here, the plurality of layers being different from each other means that at least one of the material and the thickness of each layer is different from each other.
In addition, when the base material 11 consists of multiple layers, it is good to make it the thickness of the total of each layer be the thickness of said preferable base material 11.

[Silver layer]
The silver layer 12 is made of metallic silver formed using the silver ink composition.
The shape of the silver layer 12 when the laminate 1 is viewed in plan so that one main surface (surface) 11a of the substrate 11 is looked down from above can be arbitrarily set according to the purpose, and the surface of the substrate 11 The silver layer 12 may be provided on the entire surface of 11a, or the silver layer 12 may be provided on only a part of the surface 11a of the base material 11. In this case, the silver layer 12 is patterned. May be.
The patterned silver layer 12 is useful as a wiring, for example.

The thickness of the silver layer 12 can be arbitrarily set according to the purpose, but is preferably 0.01 to 5 μm, and more preferably 0.05 to 3 μm. When the thickness of the silver layer 12 is equal to or more than the lower limit value, the conductivity can be further improved, and the structure of the silver layer 12 can be more stably maintained. Moreover, the laminated body 1 can be made thinner by the thickness of the silver layer 12 being the said upper limit or less.

The silver layer 12 may be composed of a single layer or may be composed of two or more layers. When the silver layer 12 consists of a plurality of layers, these layers may be the same as or different from each other, and can be configured in the same manner as in the case of the substrate 11. For example, the silver layer 12 composed of a plurality of layers may be configured such that the total thickness of each layer is the thickness of the preferred silver layer 12 described above.

The laminated body is not limited to that shown in FIG. 1, and other configurations may be added or a part of the configuration may be appropriately changed within a range not impairing the effects of the present invention. For example, another layer other than the silver layer 12 may be provided on the base material 11, and the other layer may include a receiving layer (not shown) provided between the base material 11 and the silver layer 12, And an overcoat layer (not shown) for covering the silver layer 12. The receptor layer improves the adhesion between the silver layer and the substrate.
In addition, here, the laminate 1 is shown having a silver layer 12 on one main surface (surface) 11a of the base material 11, but the laminate of the present invention is the other main surface of the base material 11. Similarly, the surface (back surface) 11b may be provided with the silver layer 12 (on both main surfaces of the base material 11).

In the case of manufacturing a laminate in which a layer other than the silver layer 12 is provided on the substrate 11, a step of forming the other layer at a predetermined timing is added as appropriate in the above-described manufacturing method. You can do it.

<< Electronic equipment, transparent conductive film >>
The said laminated body is suitable for comprising various electronic devices, a transparent conductive film, etc.
For example, an electronic device can be configured to use the laminate and include the base material as a casing (exterior material). Such an electronic device can be configured in the same manner as a known electronic device except that at least a part of the casing (exterior material) is configured by the base material in the laminate. For example, a planar or curved surface portion of an exterior material in a communication device such as a cellular phone is used as the base material, and a thin wire (silver thin wire) made of the metallic silver is formed on the exterior material (base material). By doing so, the laminate can be used as a circuit board. For example, a cellular phone can be configured by combining a voice input unit, a voice output unit, an operation switch, a display unit, and the like in addition to the laminate. Further, by using the patterned silver layer as an antenna, the laminated body can be used as an antenna structure, and the configuration is the same as that of a known data transmitting / receiving body except that the antenna structure is used. Thus, a new data receiving / transmitting body can be obtained. For example, in the laminate, an IC chip electrically connected to the silver layer is provided on the base material to form an antenna portion, whereby a non-contact type data receiving / transmitting body can be configured.

Further, the transparent conductive film can be configured to use the laminate and include a silver layer as ultrafine wiring or ultrathin wiring. Such a transparent conductive film can have the same configuration as a known transparent conductive film except that the silver layer is provided as an ultrafine wiring or an ultrathin wiring. For example, a touch panel or an optical display can be configured by further combining the laminate with a transparent substrate or the like.
The line width of the ultrafine wiring is preferably 1 to 20 μm, more preferably 1.3 to 15 μm, and particularly preferably 1.5 to 13 μm.
In addition, the cross-sectional shape of the ultrafine wiring is preferably a semi-elliptical shape in which approximately half the region in the minor axis direction of the ellipse is cut off.
On the other hand, the thickness of the ultra-thin wiring is preferably 5 nm to 10 μm, more preferably 7 nm to 5 μm, and particularly preferably 10 nm to 1 μm.
The cross-sectional shape of the ultrathin wiring is the same as the cross-sectional shape of the ultrafine wiring.
In the transparent conductive film, the silver layer preferably satisfies at least one of such a line width and thickness. If the silver layer has such a line width or thickness, its presence is difficult to recognize by visual observation, which is preferable as a transparent conductive film.

In the laminate, the silver layer can be formed at a low temperature, and a wide range of materials such as a base material can be selected. Thus, the degree of freedom in design is greatly improved, and electronic devices, transparent conductive films, etc. Can be made more rational.
The above electronic devices, transparent conductive films, and the like can maintain high performance over a long period of time.

Hereinafter, the present invention will be described in more detail with reference to specific examples. However, the present invention is not limited to the following examples.

[Example 1]
<Manufacture of silver ink composition>
In a beaker, 2-ethylhexylamine (a 1.45-fold molar amount with respect to silver 2-methylacetoacetate described later) is added, and the mixture is stirred with a mechanical stirrer so that the liquid temperature is 50 ° C. or lower. Silver methyl acetoacetate was added. Next, after stirring for 10 minutes while flowing nitrogen gas into the beaker at a flow rate of 10 mL / min with the opening of the beaker covered with a cover, the beaker was placed in a water bath having a temperature of 25 ° C. While maintaining this state, formic acid (0.48-fold molar amount with respect to silver 2-methylacetoacetate) was added dropwise over 30 minutes using a syringe pump. Two hours after the start of the first operation (mixing of the ingredients), 3-ethyl-1-heptin-3-ol (0.036-fold molar amount with respect to silver 2-methylacetoacetate) was added over 1 minute. The solution was added dropwise and further stirred for 5 minutes to obtain a silver ink composition. Table 1 shows the types and blending ratios of each blending component. In Table 1, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mol of silver carboxylate ([number of moles of nitrogen-containing compound] / [silver carboxylate] Number of moles]). Similarly, the “reducing agent (molar ratio)” is the reductant compounding amount (mole number) per mol of silver carboxylate ([molar number of reducing agent] / [molar number of silver carboxylate]). means. Similarly, in the case of “acetylene alcohols (molar ratio)”, the blending amount (number of moles) of acetylenic alcohol per mole of silver carboxylate (number of moles of acetylene alcohol) / [number of moles of silver carboxylate ]).

<Manufacture of laminates>
The silver ink composition obtained above was placed in a light-shielding resin container in an air atmosphere and covered to prevent moisture from entering, and left at 5 ° C. for 1 day.
Next, a part of the silver ink composition is taken out from the resin container, and this silver ink composition is taken out by gravure offset printing on one main surface (surface) of the polycarbonate base material (thickness 2 mm). Was printed to form a print pattern.
Next, the substrate printed in an oven is dried at 100 ° C. for 10 minutes, and further, this substrate is placed in a steam atmosphere at 100 ° C. for 10 minutes to be heated (fired), whereby a thickness of 0. A linear silver thin wire having a thickness of 2 μm, a width of 200 μm, and a length of 25 mm was formed on the surface of the substrate to obtain a laminate. Hereinafter, this laminate is referred to as a first laminate.

Further, the remaining silver ink composition after taking out a part thereof was prevented from entering moisture in the resin container, and was left at 5 ° C. for 29 days, and stored for a total of 30 days.
Next, using this silver ink composition after storage for 30 days, a thin silver wire was formed on the surface of the substrate in the same manner as in the case of the first laminate described above to obtain a laminate. Hereinafter, this laminate is referred to as a second laminate.

<Evaluation of laminate>
(Measurement of change rate of volume resistivity of silver thin wire)
The silver thin line of the first laminate and the second laminate obtained above, line resistance value R (Omega), the cross-sectional area A ^(cm 2), and measure the line length L (= 2.5 cm), the formula By “ρ = R × A / L”, the volume resistivity ρ ₁₁ (μΩ · cm) of the silver fine wire of the first laminate and the volume resistivity ρ ₂₁ (μΩ · cm) of the silver fine wire of the second laminate are obtained. Each was calculated. The line resistance value R was measured by a two-terminal method using a digital multimeter (“7352” manufactured by ADC), and the cross-sectional area A was measured using a laser microscope (“VK-X100” manufactured by Keyence). .
Furthermore, the rate of change (%) in volume resistivity of the silver thin wire was calculated by the formula “(ρ ₂₁ −ρ ₁₁ ) / ρ ₁₁ × 100”. The results are shown in Table 2.

<Manufacture and evaluation of laminate>
[Example 2, Comparative Examples 1 to 3]
A silver ink composition, a first laminate, and a second laminate were produced in the same manner as in Example 1 except that the compounding components at the time of producing the silver ink composition were as shown in Table 1, and these laminates were produced. Evaluated. The results are shown in Table 2.

As is clear from the above results, in Examples 1 and 2, the volume resistivity (ρ ₁₁ and ρ ₂₁ ) of the silver fine wires is low and the volume of the silver fine wires is low in both the first laminate and the second laminate. It was confirmed that the change rate (%) of the resistivity was small and the storage stability of the silver ink composition was high.
On the other hand, in Comparative Examples 1 to 3, the volume resistivity (ρ ₂₁ ) of the silver thin wire of the second laminated body and the first laminated body were different by using a different type of acetylene alcohol from the above examples. The difference from the volume resistivity (ρ ₁₁ ) of the silver fine wire was large, and the rate of change (%) in the volume resistivity of the silver fine wire was large, confirming that the storage stability of the silver ink composition was low. In particular, in Comparative Example 3 in which acetylene alcohols having a structure significantly different from those of other Examples and Comparative Examples were used, the change rate (%) of the volume resistivity of the silver thin wire was remarkably large. -".

[Example 3]
<Manufacture of silver ink composition>
In a beaker, 2-ethylhexylamine (a 1.45-fold molar amount with respect to silver 2-methylacetoacetate described later) is added, and the mixture is stirred with a mechanical stirrer so that the liquid temperature is 50 ° C. or lower. Silver methyl acetoacetate was added. Next, after stirring for 10 minutes while flowing nitrogen gas into the beaker at a flow rate of 10 mL / min with the opening of the beaker covered with a cover, the beaker was placed in a water bath having a temperature of 25 ° C. While maintaining this state, formic acid (0.50-fold molar amount with respect to silver 2-methylacetoacetate) was added dropwise over 30 minutes using a syringe pump. Two hours after the start of the first operation (mixing of the ingredients), 4-ethyl-1-octyn-3-ol (0.004 times the molar amount with respect to silver 2-methylacetoacetate) and 3,5- Dimethyl-1-hexyn-3-ol (0.032-fold molar amount relative to silver 2-methylacetoacetate) was added dropwise over 1 minute, and the mixture was further stirred for 5 minutes to obtain a silver ink composition. Table 3 shows the types and mixing ratios of the respective components. In Table 3, “-” in the column of the blending component means that the component is not blended.

<Manufacture and evaluation of laminate>
Except the point which used the silver ink composition obtained above, the 1st laminated body and the 2nd laminated body were manufactured by the same method as Example 1, and these laminated bodies were evaluated. The results are shown in Table 4.

<Manufacture and evaluation of laminate>
[Examples 4 to 5]
A silver ink composition, a first laminate, and a second laminate were produced in the same manner as in Example 3 except that the compounding components at the time of producing the silver ink composition were as shown in Table 3, and these laminates were produced. Evaluated. The results are shown in Table 4.

<Manufacture and evaluation of laminate>
[Examples 6 to 7, Comparative Example 4]
A silver ink composition, a first laminate, and a second laminate were produced in the same manner as in Example 1 except that the blending components during production of the silver ink composition were as shown in Table 3, and these laminates were produced. Evaluated. The results are shown in Table 4.

As is clear from the above results, in Examples 3 to 7, the volume resistivity (ρ ₁₁ and ρ ₂₁ ) of the silver fine wires is low and the volume of the silver fine wires is low in both the first laminate and the second laminate. It was confirmed that the change rate (%) of the resistivity was small and the storage stability of the silver ink composition was high.
On the other hand, in Comparative Example 4, the volume resistivity (ρ ₂₁ ) of the silver thin wire of the second laminate and the silver fine wire of the first laminate were obtained by using acetylene alcohols in a form different from the above example. The volume resistivity (ρ ₁₁ ) was large, the volume resistivity change rate (%) of the silver thin wire was large, and it was confirmed that the storage stability of the silver ink composition was low.

In Examples 3 to 5, acetylene alcohol (20) and other acetylene alcohol (acetylene alcohol (21)) were used in combination, but in the case of Examples 6 to 7 where no other acetylene alcohol was used in combination. In comparison, in both the first laminated body and the second laminated body, fading of the silver thin wire was further suppressed. That is, it was confirmed that by using a silver ink composition in which acetylene alcohol (20) and another acetylene alcohol are used in combination, it is possible to form a print pattern in which fading is further suppressed.

The present invention can be used for various electronic devices having a silver layer on a base material such as a wiring board, an electromagnetic wave shield, a touch panel, and an antenna of a wireless communication device casing.

DESCRIPTION OF SYMBOLS 1 ... Laminated body, 11 ... Base material, 11a ... One main surface (front surface) of a base material, 11b ... The other main surface (back surface) of a base material, 12 ... Silver layer

Claims

Silver carboxylate having a group represented by the formula “—COOAg”;
An amine compound having a carbon number of 25 or less and a quaternary ammonium salt, ammonia, and one or more nitrogen-containing compounds selected from the group consisting of ammonium salts obtained by reacting the amine compound or ammonia with an acid;
One or more reducing agents selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5);
An acetylene alcohol having 9 or more carbon atoms represented by the following general formula (20);
A silver ink composition comprising:
HC (= O) -R 21 (5)
(Wherein R 21 represents an alkyl group having 20 or less carbon atoms, an alkoxy group, or an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

Wherein R ′ and R ″ are each independently a hydrogen atom, an alkyl group, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, provided that R ′ and R ′ At least one of 'is the alkyl group or the phenyl group.)
The silver ink composition according to claim 1, wherein the total number of carbon atoms of R ′ and R ″ is 6 to 9.
The silver ink composition according to claim 1 or 2, wherein the silver ink composition is blended with acetylene alcohol represented by the following general formula (21).

(Wherein R 9 ′ and R 9 ″ are each independently a hydrogen atom or an alkyl group, provided that the total number of carbon atoms of R 9 ′ and R 9 ″ is 0 to 5)
Silver carboxylate having a group represented by the formula “—COOAg”;
An amine compound having a carbon number of 25 or less and a quaternary ammonium salt, ammonia, and one or more nitrogen-containing compounds selected from the group consisting of ammonium salts obtained by reacting the amine compound or ammonia with an acid;
One or more reducing agents selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5);
An acetylene alcohol having 9 or more carbon atoms represented by the following general formula (20);
The manufacturing method of a silver ink composition which has the process of mix | blending.
HC (= O) -R 21 (5)
(Wherein R 21 represents an alkyl group having 20 or less carbon atoms, an alkoxy group, or an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

Wherein R ′ and R ″ are each independently a hydrogen atom, an alkyl group, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent, provided that R ′ and R ′ At least one of 'is the alkyl group or the phenyl group.)
A silver layer is laminated on the surface of the substrate,
A laminate in which the silver layer is formed using the silver ink composition according to any one of claims 1 to 3.