JP2014189680A - Silver ink composition and conductor - Google Patents

Abstract

Provided are a silver ink composition capable of forming metallic silver without performing heat treatment at a high temperature and suppressing a change in viscosity over time, and a conductor obtained using the silver ink composition.
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 are reacted with an acid. One or more nitrogen-containing compounds selected from the group consisting of ammonium salts and a reducing agent are blended to form a raw material composition, and further, the raw material composition, a hydrocarbon having 17 or less carbon atoms, and 11 or less carbon atoms One or more liquid diluents selected from the group consisting of: a hydroxyl group-containing compound, a carbonyl group-containing compound having 11 or less carbon atoms, an amide bond-containing compound having 15 or less carbon atoms, and an ether bond-containing compound having 20 or less carbon atoms; A silver ink composition comprising: a conductive material obtained by forming metallic silver using the silver ink composition.
[Selection figure] None

Description

  The present invention relates to a silver ink composition in which a change in viscosity during storage or printing is suppressed, and a conductor obtained using the silver ink composition.

Metallic silver is widely used as a recording material, a printing plate material, and a highly conductive material because of its excellent conductivity.
So far, as a method for producing metallic silver, a method for forming metallic silver by applying a silver ink composition onto a substrate by various printing methods and heat-treating it has been disclosed. For example, a silver compound such as silver acetate and an amine are mixed, and further a reducing agent is allowed to act to precipitate fine silver particles, followed by purification operations such as decantation and washing, and finally with a solvent. What was obtained by mixing is disclosed (Patent Document 1). In this method, in order to remove impurities remaining during the heat treatment and hindering the formation of metallic silver, the above-described purification operation is required, and the mixing with the solvent is finally performed. On the other hand, Patent Document 1 does not disclose any mixing of a solvent without performing a purification operation.

  As other silver ink compositions, those using organic acid silver such as silver behenate, silver stearate, silver α-ketocarboxylate, silver β-ketocarboxylate as a silver compound are disclosed. Among these, for example, silver β-ketocarboxylate rapidly forms metallic silver even when heat-treated at a low temperature of about 210 ° C. or less (see Patent Document 2).

  On the other hand, it is desired that the silver ink composition as described above is adjusted in viscosity so as to have good printability when subjected to a printing method. This is because when the solvent component in the silver ink composition volatilizes during storage or printing, the viscosity of the silver ink composition increases, making it difficult to print stably. When a silver ink composition having a high viscosity is used, not only process defects are likely to occur during printing, but also the shape of the printed pattern is disturbed, and as a result, metal silver having a desired shape may not be obtained. is there. Therefore, in order to solve such problems, a silver ink composition in which the viscosity is appropriately adjusted by blending a diluent such as various solvents, or by blending more components that also serve as the diluent. It is desirable to use it.

JP 2012-246560 A International Publication No. 2007/004437

  Since the silver ink composition using the above-mentioned organic acid silver, particularly a specific organic acid silver such as silver β-ketocarboxylate, can significantly reduce the amount of impurities remaining during heat treatment and inhibiting the formation of metallic silver, Although there is a possibility that metallic silver can be formed at a lower temperature without performing purification operations such as decantation and washing, the stability of the viscosity over time during storage or printing, and the method for stabilizing the viscosity, It has not been specifically studied so far. Therefore, a novel silver ink composition that can form metallic silver at a low temperature and suppresses a change in viscosity over time has been desired.

  The present invention has been made in view of the above circumstances, a silver ink composition capable of forming metallic silver without performing heat treatment at a high temperature, and a change in viscosity over time, and the silver ink composition. It is an object of the present invention to provide a conductor obtained using an object.

To solve the above problem,
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 reacting with an acid. One or more nitrogen-containing compounds selected from the group consisting of ammonium salts and a reducing agent are blended to form a raw material composition, and further, the raw material composition, a hydrocarbon having 17 or less carbon atoms, and 11 carbon atoms. One or more selected from the group consisting of a compound having the following hydroxyl group, a compound having a carbonyl group having 11 or less carbon atoms, a compound having an amide bond having 15 or less carbon atoms, and a compound having an ether bond having 20 or less carbon atoms The present invention provides a silver ink composition comprising a liquid diluent.

  In the silver ink composition of the present invention, the diluent is n-dodecane, cyclooctane, 2,2,4,4-tetramethylpentane, 2-methyloctane, di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl. Ether, diethylene glycol monoethyl ether, 2-ethyl-1-hexanol, 1-octanol, 1-hexanol, 2-propanol, ethylene glycol, cyclohexanol, 2-methyl-1-propanol, 1-pentanol, 2-butoxyethanol , 4-heptanone and N, N-dimethylformamide are preferable.

  The present invention also provides a conductor obtained by forming metallic silver using the silver ink composition.

  ADVANTAGE OF THE INVENTION According to this invention, the silver ink composition which can form metallic silver without performing heat processing at high temperature, the change of the viscosity with time was suppressed, and the conductor obtained using this silver ink composition Is provided.

<< Silver ink composition >>
The silver ink composition according to the present invention comprises a silver carboxylate having a group represented by the formula “—COOAg” (hereinafter sometimes simply referred to as “silver carboxylate”) and an amine compound having 25 or less carbon atoms. And one or more nitrogen-containing compounds selected from the group consisting of quaternary ammonium salts, ammonia, and ammonium salts obtained by reacting the amine compound or ammonia with an acid (hereinafter simply abbreviated as “nitrogen-containing compounds”). And a reducing agent are blended to form a raw material composition, and further, the raw material composition, a hydrocarbon having a carbon number of 17 or less, a compound having a hydroxyl group of a carbon number of 11 or less, a carbon number of 11 or less One or more liquids selected from the group consisting of a compound having a carbonyl group, a compound having an amide bond having 15 or less carbon atoms, and a compound having an ether bond having 20 or less carbon atoms Diluent (hereinafter, sometimes simply referred to as "diluent"), characterized in that is blended.

  The silver ink composition according to the present invention can form metallic silver (conductor) by post-treatment under milder conditions by using the silver carboxylate and the reducing agent in combination. Further, the silver ink composition according to the present invention suppresses a change in viscosity (especially an increase in viscosity) over time during storage or printing by using the diluent.

<Raw material composition>
In the present invention, the raw material composition is formed by blending the silver carboxylate, the nitrogen-containing compound and the reducing agent, and is blended together with the diluent in the next step.
Hereinafter, first, the silver carboxylate, the nitrogen-containing compound and the reducing agent will be described.

[Silver carboxylate]
The silver carboxylate is a metal silver forming material and is not particularly limited as long as it has a group represented by the formula “—COOAg”. For example, 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, the said carboxylate silver may be used individually by 1 type, and may use 2 or more types together. 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). It is preferably one or more selected from the group consisting of silver carboxylates (hereinafter sometimes abbreviated as “silver carboxylate (4)”).
In the present 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 ””.

（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１〜２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ^１−ＣＹ_２−」、「ＣＹ_３−」、「Ｒ^１−ＣＨＹ−」、「Ｒ^２Ｏ−」、「Ｒ^５Ｒ^４Ｎ−」、「（Ｒ^３Ｏ）_２ＣＹ−」若しくは「Ｒ^６−Ｃ（＝Ｏ）−ＣＹ_２−」で表される基であり；
Ｙはそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ^１は炭素数１〜１９の脂肪族炭化水素基又はフェニル基であり；Ｒ^２は炭素数１〜２０の脂肪族炭化水素基であり；Ｒ^３は炭素数１〜１６の脂肪族炭化水素基であり；Ｒ^４及びＲ^５はそれぞれ独立に炭素数１〜１８の脂肪族炭化水素基であり；Ｒ^６は炭素数１〜１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ−」で表される基であり；
Ｘはそれぞれ独立に水素原子、炭素数１〜２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ−フタロイル−３−アミノプロピル基、２−エトキシビニル基、又は一般式「Ｒ^７Ｏ−」、「Ｒ^７Ｓ−」、「Ｒ^７−Ｃ（＝Ｏ）−」若しくは「Ｒ^７−Ｃ（＝Ｏ）−Ｏ−」で表される基であり；
Ｒ^７は、炭素数１〜１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）

(In the formula, R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY” in which one or more hydrogen atoms may be substituted with a substituent. “ _2- ”, “CY ₃ —”, “R ¹ —CHY—”, “R ² O—”, “R ⁵ R ⁴ N—”, “(R ³ O) ₂ CY—” or “R ⁶ —C”. A group represented by (= O) —CY ₂ —;
Y is each independently a fluorine atom, chlorine atom, bromine atom or hydrogen atom; R ¹ is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms; R ² is an aliphatic group 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 carbon An aliphatic hydrocarbon group, a hydroxyl group or a group represented by the formula "AgO-" of formula 1-19;
X 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- A phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group, or a general formula “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. )

（式中、Ｒ^８は炭素数１〜１９の脂肪族炭化水素基、カルボキシ基又は式「−ＣＯＯＡｇ」で表される基であり、前記脂肪族炭化水素基がメチレン基を有する場合、１個以上の該メチレン基はカルボニル基で置換されていてもよい。）

(In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group or a group represented by the formula “—COOAg”, and when the aliphatic hydrocarbon group has a methylene group, The above methylene group may be substituted with a carbonyl group.)

(Silver β-ketocarboxylate (1))
The β-ketocarboxylate silver (1) is represented by the general formula (1).
In the formula, R represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY ₂ ” in which one or more hydrogen atoms may be substituted with a substituent. - "," CY ₃ - "," ^R 1 -CHY - "," ^{R 2} O - "," ^R 5 ^{R 4} N -, "" ^(R _{3 O)} 2 CY- "or" ^R 6 -C ( ═O) —CY 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 when it is cyclic, it may be monocyclic or polycyclic. . 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 represented by R include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 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, -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, -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 And pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group and icosyl group.
Examples of the cyclic alkyl group in R include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2- Examples thereof include an adamantyl group and a tricyclodecyl group.

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

  In the aliphatic hydrocarbon group having 1 to 20 carbon atoms in R, one or more hydrogen atoms may be substituted with a substituent, and preferred examples of the substituent include a fluorine atom, a chlorine atom, and a bromine atom. . Moreover, the number and position of 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.

The phenyl group in R may have one or more hydrogen atoms substituted with a substituent, and the preferred substituent is 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, a fluorine 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 can be exemplified, and the number and position of 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.
Examples of the aliphatic hydrocarbon group that 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 in R each independently represents a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. In the general formulas “R ¹ —CY ₂ —”, “CY ₃ —” and “R ⁶ —C (═O) —CY ₂ —”, a plurality of Y may be the same or different from each other. Good.

R ¹ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group (C ₆ H ₅ —), and the aliphatic hydrocarbon group in R ¹ has 1 to 19 carbon atoms. Except for this point, the same aliphatic hydrocarbon groups as those in R can be exemplified.
R ² in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof are the same as the aliphatic hydrocarbon group in R.
R ³ in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms, and examples thereof are the same as the aliphatic hydrocarbon group in R except that the carbon number 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 as or different from each other, and examples thereof are the same as the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 18.
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—”, and the aliphatic hydrocarbon group in R ⁶ has 1 to 1 carbon atoms. Except for being 19, the same aliphatic hydrocarbon groups as those described above for R can be exemplified.

Among these, R is preferably a linear or branched alkyl group, a group represented by the general formula “R ⁶ —C (═O) —CY ₂ —”, a hydroxyl group, or a phenyl group. . 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 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 benzyl. A 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 It is a group represented by “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 include those similar to the aliphatic hydrocarbon group in R.

Examples of the halogen atom in X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the phenyl group and benzyl group in X, one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), nitro group (-NO ₂₎ or the like can be exemplified, the number and position of the substituent is 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 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group (C ₄ H ₃ S—), or a phenyl group or diphenyl in which one or more hydrogen atoms may be substituted with a substituent. group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) it is. Examples of the aliphatic hydrocarbon group for R ⁷ include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 10 carbon atoms. Further, examples of the substituent of the phenyl group and a diphenyl group in R ^7, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) can be exemplified the like, the number and position of the substituent is 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, the bonding position of these with an adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X is not particularly limited. For example, the thienyl group may be a 2-thienyl group or a 3-thienyl group.

In the general formula (1), two Xs may be bonded as one group through a double bond with a carbon atom sandwiched between two carbonyl groups. A group represented by “═CH—C ₆ H ₄ —NO ₂ ” can be exemplified.

Among these, X 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) —”. It is preferable that at least one X is a hydrogen atom.

β-ketocarboxylate silver (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), isobutyryl silver 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 2-n-butylacetoacetate (CH ₃ —C (═O) —CH _{(CH 2 CH 2 CH 2 CH} 3) -C (= O) -OAg), 2- benzyl acetoacetate silver _(CH 3 -C ( _{= O) -CH (CH 2 C} 6 H 5) -C (= O) -OAg), silver benzoylacetate _{(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 isobutyryl acetoacetate ((CH ₃ ) _{2 CH-C (= O) -CH} 2 -C (= O) -CH 2 -C (= O) -OAg), 2- acetyl pivaloyl silver acetate _{((CH 3) 3 C-} C (= 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) -OAg), or acetone dicarboxylic silver _{(AgO-C (= O)} -CH 2 -C (= O) -CH 2 -C ( O) -OAg), preferably silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver 2-n-butylacetoacetate, 2-benzyl Silver acetoacetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, or silver acetone dicarboxylate is more preferable.

  The β-ketocarboxylate (1) can further reduce the concentration of the remaining raw materials and impurities in the conductor (metal silver) formed by post-treatment such as drying treatment or heating (firing) treatment. 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 described later, It is possible to form metallic silver. And by using together with the said reducing agent, it decomposes | disassembles at lower temperature and forms metallic silver.

  In this invention, (beta) -ketocarboxylate (1) may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

(Silver carboxylate (4))
The carboxylate silver (4) is represented by the general formula (4). In the formula, R ⁸ is represented by an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (—COOH) or the formula “—COOAg”. Group.
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 alkylene group 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) is 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), isobutyric acid silver _{((CH 3) 2 CH-} C (= O) -OAg), hexane silver 2-ethylhexyl _(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). Also, 2 of the silver oxalate (AgO-C (= O) -C (= O) -OAg) and malonic silver _{(AgO-C (= O)} -CH 2 -C (= O) -OAg) Of the groups represented by the formula “—COOAg”, one is a group represented by the formula “—COOH” (HO—C (═O) —C (═O) —OAg, HO) _{-C (= O) -CH 2 -C} (= O) -OAg) it is also preferred.

  As in the case of silver β-ketocarboxylate (1), silver carboxylate (4) is also a conductor (metal silver) formed by post-treatment such as drying treatment or heating (firing) treatment. The concentration can be further reduced. And by using together with the said reducing agent, it decomposes | disassembles at lower temperature and forms metallic silver.

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

[Nitrogen-containing compounds]
The nitrogen-containing compound is 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 abbreviated as “quaternary ammonium salt”). Ammonia, an ammonium salt formed by reacting 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 reacting with an acid. One or more selected from the group consisting of ammonium salts (hereinafter sometimes abbreviated as “ammonium salts derived from ammonia”). That is, the nitrogen-containing compound to be blended may be only one kind, or two or more kinds. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

(Amine compound, quaternary ammonium salt)
In the present invention, 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 thereof are the same as the alkyl group in R, and are linear or branched having 1 to 19 carbon atoms. It is preferably a chain alkyl group 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, sec-butylamine, tert-butylamine, 3-aminopentane, 3 Examples include -methylbutylamine, 2-aminooctane, 2-ethylhexylamine, and 1,2-dimethyl-n-propylamine.

  Examples of the aryl group constituting the monoarylamine include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like, and 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, and the heteroatom includes a nitrogen atom, a sulfur atom, an oxygen atom, and a boron atom. Can be illustrated. 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 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 pyrrolyl group, pyrrolinyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrimidyl group, pyrazinyl group, pyridazinyl group, triazolyl group, and tetrazolyl group. , A pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazolidinyl group, and a piperazinyl group are preferable, and a 3- to 8-membered ring is preferable, and a 5- to 6-membered ring is more preferable.
Examples of the monoaryl group having one oxygen atom as the heteroaryl group include a furanyl group, preferably a 3- to 8-membered ring, and more preferably a 5- to 6-membered ring.
Examples of the monoaryl group having one sulfur atom as the heteroaryl group include a thienyl group, preferably a 3- to 8-membered ring, and more preferably a 5- to 6-membered 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. It is preferable that it is 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, and a thiazolidinyl group, and a 3- to 8-membered ring. Preferably, it is a 5-6 membered ring.
Examples of the polyaryl group having 1 to 5 nitrogen atoms as the heteroaryl group include indolyl group, isoindolyl group, indolizinyl group, benzimidazolyl group, quinolyl group, isoquinolyl group, indazolyl group, benzotriazolyl group, tetra Examples include a zolopyridyl group, a tetrazolopyridazinyl group, and a dihydrotriazolopyridazinyl group, preferably a 7-12 membered ring, and more preferably a 9-10 membered ring.
Examples of the polyaryl group having 1 to 3 sulfur atoms as the heteroaryl group include a dithiaphthalenyl group and a benzothiophenyl group, preferably a 7 to 12 membered ring, preferably a 9 to 10 membered ring. More preferably, it is a ring.
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 benzooxadiazolyl group. It is preferable that it is 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 and a benzothiadiazolyl group, and is a 7 to 12 membered ring. Preferably, it is a 9-10 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, 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. The thing can be illustrated.
The diamine preferably has 1 to 10 carbon atoms, and more preferable examples include ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane.

  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 that constitutes the dialkylamine is the same as the alkyl group that constitutes the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms, or 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 dialkylamine 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.
Preferable examples of the trialkylamine include N, N-dimethyl-n-octadecylamine and N, N-dimethylcyclohexylamine.

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 and iodine.
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, a pyridine can be illustrated as a preferable thing.

  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, 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 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 Preferably, a cyclic alkyl group having 3 to 7 carbon atoms having an alkyl group having 1 to 5 carbon atoms is preferable, and specific examples of monoalkylamine having such a substituent include 2-phenylethylamine , Benzylamine, and 2,3-dimethylcyclohexylamine.
In addition, the aryl group and the alkyl group which are substituents may further have one or more hydrogen atoms substituted with halogen atoms, and as monoalkylamines having such substituents substituted with halogen atoms, And 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 the substituent, and monoaryl having such a substituent. Specific examples of the amine 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 preferably a linear or branched alkyl group having 1 to 9 carbon atoms and having a hydroxyl group or an aryl group as a substituent, Specific examples of the dialkylamine having such a substituent include diethanolamine and N-methylbenzylamine.

  The amine compound is n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-methyl. Butylamine, 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 is preferable.

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

(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, and 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 singly or in combination of two or more. . 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 by 1 type selected from the group which consists of said amine compound, quaternary ammonium salt, ammonium salt derived from an amine compound, and ammonium salt derived from ammonia, More than one species may be used in combination. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

In the silver ink composition, the blending amount of the nitrogen-containing compound is preferably 0.2 to 15 moles, more preferably 0.3 to 5 moles per mole of the silver carboxylate. .
By defining the blending amount of the nitrogen-containing compound as described above, the silver ink composition can form a conductor (metallic silver) more stably without performing a heat treatment at a high temperature.

[Reducing agent]
The reducing agent is a component that facilitates the formation of metallic silver by the silver ink composition. For example, the silver ink composition can be a metal having sufficient electrical conductivity even by heat treatment at low temperature or drying treatment at room temperature. Silver (conductor) can be formed.

The reducing agent is one or more reducing compounds selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5) (hereinafter sometimes abbreviated as “compound (5)”). (Hereinafter, sometimes simply abbreviated as “reducing compound”).
HC (= O) -R ²¹ (5)
(In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.)

(Reducing compounds)
The reducing compound is one or more selected from the group consisting of oxalic acid (HOOC-COOH), hydrazine (H ₂ N—NH ₂ ) and the compound represented by the general formula (5) (compound (5)). belongs to. That is, the reducing compound to be blended may be only one kind, or two or more kinds. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.
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, and is the same as the alkyl group in R of the general formula (1) The thing can be illustrated.

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include monovalent groups in which the alkyl group in R ²¹ is bonded to an oxygen atom.

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, Each alkyl group has 1 to 19 carbon atoms. However, the total value of the carbon number of these two alkyl groups is 2-20.
The alkyl group bonded to the nitrogen atom may be linear, branched or cyclic, respectively, and the alkyl in R of the general formula (1) except that it has 1 to 19 carbon atoms. The thing similar to group can be illustrated.

As the reducing compound, hydrazine may be a monohydrate (H ₂ N—NH ₂ .H ₂ O).

The reducing compound includes formic acid (HC (═O) —OH), methyl formate (HC—═O) —OCH ₃ ), ethyl formate (HC—═O) —OCH ₂ CH ₃ ). , Butyl formate (HC (═O) —O (CH ₂ ) ₃ CH ₃ ), propanal (HC (═O) —CH ₂ CH ₃ ), butanal (HC (═O) — ( CH _{2) 2} CH _3), hexanal (H-C (= O) - (CH 2) 4 CH 3), formamide _{(H-C (= O)} -NH 2), N, N- dimethylformamide (H- C (═O) —N (CH ₃ ) ₂ ) or oxalic acid is preferred.

  In the silver ink composition, the compounding amount of the reducing agent is preferably 0.04 to 3.5 mol, and preferably 0.06 to 2.5 mol per mol of the silver carboxylate. More preferred. By defining in this way, the silver ink composition can form a conductor more easily and more stably.

  For example, when the silver carboxylate and the reducing agent are blended together, the resulting mixture (raw material composition) is relatively easy to generate heat. And when the temperature at the time of compounding these is high, this mixture will be in the same state as at the time of the heat treatment of the silver ink composition to be described later, so that the carboxylate is promoted by the decomposition promoting action of the silver carboxylate by the reducing agent. It is speculated that the formation of metallic silver may be initiated in at least part of the acid silver. By using such a raw material composition containing metallic silver, the resulting silver ink composition also contains metallic silver, and the silver ink composition containing such metallic silver is composed of a conductor described later. At the time of manufacture, the conductor (metal silver) may be formed by performing post-treatment under conditions milder than those of the silver ink composition not containing metal silver. Further, even when the amount of the reducing agent is sufficiently large, the conductor may be formed by performing the post-treatment under the same mild conditions. In this way, by adopting the conditions that promote the decomposition of the silver carboxylate, the conductor can be obtained by post-treatment, by heat treatment at a lower temperature, or only by drying at room temperature without performing heat treatment. Sometimes it can be formed. 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.

[Other ingredients during production of raw material composition]
In addition to the silver carboxylate, the nitrogen-containing compound, and the reducing agent, the raw material composition may further include other components not corresponding to these within the range not impairing the effects of the present invention.
The said other component at the time of manufacture of a raw material composition is not specifically limited, According to the objective, it can select arbitrarily, 1 type may be used independently and 2 or more types may be used together. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

  At the time of manufacturing the raw material composition, the ratio of the blending amount of other components to the total blending component (total blending amount of the silver carboxylate, nitrogen-containing compound, reducing agent and other components) ([blending amount of other components (Mass part)] / [total amount of compounding ingredients (parts by mass)] × 100) is preferably 10% by mass or less, and more preferably 5% by mass or less. By prescribing in this way, the effect of suppressing the change in the viscosity of the silver ink composition over time becomes higher.

[Method for producing raw material composition]
The raw material composition can be obtained by blending the silver carboxylate, the nitrogen-containing compound, the reducing agent, and, if necessary, the other components.
At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of adding ultrasonic waves, and the like. .

  In the raw material composition, all of the compounding components may be dissolved, or a part of the components may be dispersed without dissolving, but it is preferable that all of the compounding components are dissolved and dissolved. It is preferable that the components not dispersed are uniformly dispersed.

The conditions at the time of blending are not particularly limited as long as each blended component does not deteriorate, but it is preferable to adjust so that the composition of the obtained raw material composition becomes uniform.
From such a viewpoint, the temperature during blending is preferably -5 to 60 ° C. Moreover, what is necessary is just to adjust a compounding time suitably according to the kind of compounding component, and the temperature at the time of a compounding, For example, it is preferable that it is 1 to 24 hours. And among these compounding time, it is preferable that the time which mixes after adding all the components is 0.1 to 10 hours.

<Silver ink composition>
The silver ink composition according to the present invention is obtained by further blending the raw material composition and a diluent. Next, the diluent will be described.

[Diluent]
The diluent is a component that suppresses the change in viscosity of the silver ink composition over time.
Specifically, the diluent is a hydrocarbon having 17 or less carbon atoms (hereinafter sometimes simply referred to as “hydrocarbon”), a compound having a hydroxyl group having 11 or less carbon atoms (hereinafter referred to as “hydroxyl-containing compound”). A compound having a carbonyl group having 11 or less carbon atoms (hereinafter sometimes abbreviated as “carbonyl group-containing compound”), a compound having an amide bond having 15 or less carbon atoms (hereinafter “amide bond”). One or more liquids selected from the group consisting of compounds having an ether bond having 20 or less carbon atoms (hereinafter sometimes abbreviated as “ether bond-containing compound”). Is. That is, the diluent to be blended may be only one kind, or two or more kinds. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

  The diluent may be liquid under the compounding conditions, and is preferably liquid at 20 to 25 ° C. under standard atmospheric pressure (101325 Pa, 1 atm).

(hydrocarbon)
The hydrocarbon may be linear, branched or cyclic, and may be any of saturated hydrocarbon and unsaturated hydrocarbon, and may be any of aliphatic hydrocarbon and aromatic hydrocarbon.

  The linear and branched saturated aliphatic hydrocarbon (alkane) preferably has 6 to 17 carbon atoms, and specifically includes n-hexane, 2-methylpentane, 3-methylpentane, 2 , 2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3, 3-dimethylpentane, 3-ethylpentane, 2,2,3-trimethylbutane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,3-dimethyl Hexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3-dimethylhexane, 3,4-dimethylhexane, 2,2,3-trimethyl N, 2,2,4-trimethylpentane (isooctane), 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 3-ethyl-2-methylpentane, 3-ethyl-3-methylpentane, 2,2,3,3-tetramethylbutane, n-nonane, 2-methyloctane, 3-methyloctane, 4-methyloctane, 2,2-dimethylheptane, 2,3-dimethylheptane, 2,4-dimethyl Heptane, 2,5-dimethylheptane, 2,6-dimethylheptane, 3,3-dimethylheptane, 3,4-dimethylheptane, 3,5-dimethylheptane, 4,4-dimethylheptane, 2,2,4, Examples include 4-tetramethylpentane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and heptadecane. It can be.

The cyclic saturated aliphatic hydrocarbon may be monocyclic or polycyclic, may be a cycloalkane, or one or more hydrogen atoms of the cycloalkane are linear, branched or cyclic monovalent saturated fat. It may be substituted with a group hydrocarbon group. Here, as the “linear, branched or cyclic monovalent saturated aliphatic hydrocarbon group”, one hydrogen atom from the above linear, branched or cyclic saturated aliphatic hydrocarbon is used. A group formed by removing can be exemplified.
The cyclic saturated aliphatic hydrocarbon is preferably monocyclic, preferably having 5 to 8 carbon atoms, and examples thereof include cyclopentane, cyclohexane, cycloheptane, and cyclooctane.

As the unsaturated aliphatic hydrocarbon, one or more single bonds (C—C) between carbon atoms of the linear, branched and cyclic saturated aliphatic hydrocarbons are unsaturated bonds (double bonds). Examples include those substituted by (C = C), triple bond (C≡C)).
The unsaturated aliphatic hydrocarbon may have only one or both of a double bond and a triple bond as an unsaturated bond between carbon atoms, and may have both. The number and position are not particularly limited, but the number of unsaturated bonds is preferably 1 or 2. When the unsaturated bond has a double bond, the unsaturated hydrocarbon may be either cis type or trans type.
The unsaturated aliphatic hydrocarbon is preferably an alkene or alkyne, and more preferably an alkene having 6 or more carbon atoms or an alkyne having 5 or more carbon atoms.

  The aromatic hydrocarbon may be monocyclic or polycyclic, and preferably has 6 to 8 carbon atoms. Preferred examples thereof include benzene, toluene, o-xylene (1,2-dimethylbenzene), m- Examples include xylene (1,3-dimethylbenzene) and p-xylene (1,4-dimethylbenzene). An aromatic hydrocarbon is a monovalent saturated or unsaturated fatty acid in which one or more hydrogen atoms bonded to carbon atoms forming the aromatic ring skeleton are linear, branched or cyclic. It may be substituted with an aromatic hydrocarbon group or a monovalent aromatic hydrocarbon group. Here, examples of the “linear, branched or cyclic monovalent saturated aliphatic hydrocarbon group” include the same ones as described above. In addition, the “linear, branched or cyclic monovalent unsaturated aliphatic hydrocarbon group” includes one hydrogen from the above-mentioned linear, branched or cyclic unsaturated aliphatic hydrocarbon. A group formed by removing atoms can be exemplified. Examples of the “monovalent aromatic hydrocarbon group” include groups obtained by removing one hydrogen atom from the above aromatic hydrocarbon.

(Hydroxyl-containing compound)
The hydroxyl group-containing compound has 11 or less carbon atoms and has at least a hydroxyl group (—OH), and may be either a chain or a ring, and in the case of a ring, it may be either a monocycle or a polycycle. . Further, the number of hydroxyl groups contained in the hydroxyl group-containing compound may be only one or two or more, and the position of the hydroxyl group is not particularly limited.
Of the hydroxyl group-containing compounds, the compound having only one hydroxyl group preferably has 11 or less carbon atoms, and the compound having 2 or more hydroxyl groups preferably has 5 or less carbon atoms.
The hydroxyl group-containing compound preferably has 3 or more carbon atoms.
Alcohol can be illustrated as a hydroxyl-containing compound.

Examples of the alcohol include one or more hydrocarbons exemplified as the diluent and saturated aliphatic hydrocarbons having 3 to 5 carbon atoms such as n-propane, n-butane, 2-methylpropane, and n-pentane. A compound in which a hydrogen atom is substituted with a hydroxyl group can be exemplified.
Preferred alcohols include 2-propanol, 2-methyl-1-propanol, 1-pentanol, 1-hexanol, 1-octanol, 2-ethyl-1-hexanol (2-ethylhexyl alcohol), 1-decanol, Examples thereof include monohydric alcohols such as 1-undecanol and cyclohexanol; polyhydric alcohols such as ethylene glycol and 1,5-pentanediol.

The hydroxyl group-containing compound may have a group other than a hydroxyl group and a hydrocarbon group (hereinafter sometimes abbreviated as “other group”) in the molecule.
The other group in the hydroxyl group-containing compound is not particularly limited as long as the effects of the present invention are not impaired, and may be an atomic group composed of a plurality of atoms or a single atom. In addition, the other group in the hydroxyl group-containing compound may be only one, may be two or more, and the two or more other groups may be the same or different from each other, and the positions of the other groups are particularly limited. Not.
The other group in the hydroxyl group-containing compound is preferably a group other than an amino group (—NH ₂ ), and preferred examples include a carbonyl group, an amide group (amide bond), and an ether group (ether bond).

(Carbonyl group-containing compound)
The carbonyl group-containing compound has 11 or less carbon atoms and has at least a carbonyl group (—C (═O) —). However, in this specification, unless otherwise specified, the “carbonyl group” does not include an amide bond (—C (═O) —N (—) —). That is, the carbonyl group-containing compound is not a compound having only an amide bond (—C (═O) —N (−) —) as a carbonyl group, but does not constitute an amide bond as a carbonyl group. It is a compound having one or more things.

The carbonyl group-containing compound may be either chain-like or cyclic, and when it is cyclic, it may be either monocyclic or polycyclic. Further, the number of carbonyl groups contained in the carbonyl group-containing compound may be only one or two or more, and the position of the carbonyl group is not particularly limited.
The carbonyl group-containing compound preferably has 4 or more carbon atoms.
Examples of the carbonyl group-containing compound include ketones.

Examples of ketones include those in which two monovalent hydrocarbon groups are bonded to a carbon atom of one carbonyl group. Here, the two monovalent hydrocarbon groups may be bonded to each other to form a ring structure together with the carbonyl group to which they are bonded. Here, examples of the “monovalent hydrocarbon group” include groups obtained by removing one hydrogen atom from the hydrocarbons exemplified as the diluent.
Preferred examples of the ketone include methyl ethyl ketone (2-butanone), 2-pentanone, 4-heptanone, 2,6-dimethyl-4-heptanone, 2-decanone, 2-undecanone and cyclohexanone.

The carbonyl group-containing compound may have a group other than the carbonyl group and the hydrocarbon group (hereinafter sometimes abbreviated as “other group”) in the molecule.
The other groups in the carbonyl group-containing compound are not particularly limited as long as the effects of the present invention are not impaired, and may be an atomic group composed of a plurality of atoms or a single atom. In addition, the other group in the carbonyl group-containing compound may be only one, or may be two or more, and the two or more other groups may be the same or different from each other. It is not limited.
The other group in the carbonyl group-containing compound is preferably a group other than an amino group (—NH ₂ ), and preferred examples include a hydroxyl group, an amide group (amide bond), and an ether group (ether bond).

(Amide bond-containing compound)
The amide bond-containing compound has 15 or less carbon atoms and has at least an amide bond (-C (= O) -N (-)-), which may be either a chain or a ring, and is cyclic May be either monocyclic or polycyclic. Further, the number of amide bonds contained in the amide bond-containing compound may be only one or two or more, and the position of the amide bond is not particularly limited.
The amide bond-containing compound has 1 or more carbon atoms.

  As the amide bond-containing compound, an amide bond “—C (═O) —N (—) —” in which the bond partner is not specified “−”, that is, one bond extending from a carbon atom. Examples include those in which a hydrogen atom or a monovalent hydrocarbon group is independently bonded to a hand (—C) and two bonds (N (−) —) extending from a nitrogen atom. Here, two or more monovalent hydrocarbon groups may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded, or the nitrogen atom and the carbon atom. Here, the “monovalent hydrocarbon group” may be linear, branched or cyclic, but is preferably linear or branched and has 1 to 10 carbon atoms. More preferable examples of such a group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and n-pentyl group. , Isopentyl group, neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethyl Rupenchiru group, 3-ethylpentyl group, 2,2,3-trimethyl butyl group, n- octyl group, an isooctyl group, a nonyl group, a decyl group and the like.

  Preferred examples of the amide bond-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpropionamide, N, N-dimethylpropionamide, N, N-diethyl. An example is dodecanamide.

The amide bond-containing compound may have a group other than a hydrogen atom and a hydrocarbon group (hereinafter sometimes abbreviated as “other group”) in the molecule.
The other group in the amide bond-containing compound is not particularly limited as long as the effects of the present invention are not impaired, and may be an atomic group composed of a plurality of atoms or a single atom. In addition, the other group in the amide bond-containing compound may be only one, two or more, and the two or more other groups may be the same or different from each other. It is not limited.
The other group in the amide bond-containing compound is preferably a group other than an amino group (—NH ₂ ), and preferred examples include a hydroxyl group, a carbonyl group, and an ether group (ether bond).

(Ether bond-containing compound)
The ether bond-containing compound has 20 or less carbon atoms and has at least an ether bond, and may be either a chain or a ring, and in the case of a ring, it may be either a monocycle or a polycycle. Further, the number of ether bonds contained in the ether bond-containing compound may be only one or two or more, and the position of the ether bond is not particularly limited.
The ether bond-containing compound preferably has 6 or more carbon atoms.
Examples of ether bond-containing compounds include various ethers.

Examples of the ether include those in which one or more methylene groups (—CH ₂ —) of a hydrocarbon are substituted with an oxygen atom (—O—), and a monovalent or divalent hydrocarbon group constituting the ether May be bonded to each other to form a ring structure together with the oxygen atom to which they are bonded. Here, the “monovalent or divalent hydrocarbon group” may be linear, branched or cyclic, and may be monocyclic or polycyclic when it is cyclic. The “monovalent or divalent hydrocarbon group” preferably has 1 to 10 carbon atoms.
Examples of the “monovalent hydrocarbon group” include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and isopentyl group. , Neopentyl group, tert-pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl Group, 2-methylhexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethylpentyl group Group, 2,2,3-trimethylbutyl group, n-octyl group, isooctyl group, nonyl group, decyl group, cyclopropyl group, cyclobutyl group, cyclyl Pentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecyl group, phenyl group, methylphenyl group (o- (Tolyl group, m-tolyl group, p-tolyl group), dimethylphenyl group, and the “divalent hydrocarbon group” is one from the above-mentioned monovalent hydrocarbon groups such as ethylene group and propylene group. The group formed by removing the hydrogen atom can be exemplified.

  Examples of preferred ethers include diisopropyl ether, di-n-butyl ether, diheptyl ether, didecyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and anisole.

The ether bond-containing compound may have a group other than a hydrocarbon group in the molecule (hereinafter sometimes abbreviated as “other group”).
The other groups in the ether bond-containing compound are not particularly limited as long as the effects of the present invention are not impaired, and may be an atomic group composed of a plurality of atoms or a single atom. In addition, the other group in the ether bond-containing compound may be only one, or two or more, and the two or more other groups may be the same or different from each other. It is not limited.
The other group in the ether bond-containing compound is preferably a group other than an amino group (—NH ₂ ), and preferred examples include a hydroxyl group, a carbonyl group, and an amide group (amide bond).

  Any of the hydrocarbon, the hydroxyl group-containing compound, the carbonyl group-containing compound, the amide bond-containing compound, and the ether bond-containing compound may simultaneously correspond to two or more of these. For example, 2-butoxyethanol, diethylene glycol monoethyl ether (carbitol) is a compound having both a hydroxyl group and an ether bond, and corresponds to both a hydroxyl group-containing compound and an ether bond-containing compound. It can be illustrated as an agent.

  The diluent is n-dodecane, cyclooctane, 2,2,4,4-tetramethylpentane, 2-methyloctane, di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, 2-ethyl. -1-hexanol, 1-octanol, 1-hexanol, 2-propanol, ethylene glycol, cyclohexanol, 2-methyl-1-propanol, 1-pentanol, 2-butoxyethanol, 4-heptanone and N, N-dimethyl One or more selected from the group consisting of formamide is preferred.

  The diluent may correspond to the reducing agent that is a blending component at the time of manufacturing the raw material composition, but is preferably not the same component as the reducing agent used at the time of manufacturing the raw material composition.

  In the silver ink composition, the blending amount of the diluent may be appropriately adjusted, for example, so that the silver ink composition has a desired viscosity, but the blending amount of the diluent with respect to the blending amount of the raw material composition The ratio ([diluent blending amount (mass)] / [raw material composition blending amount (mass)] × 100) is preferably 1 to 50% by mass, more preferably 2 to 30% by mass. The content is preferably 2 to 15% by mass. When the ratio of the blending amount of the diluent is equal to or more than the lower limit value, the effect of suppressing the change in viscosity of the silver ink composition over time is further increased. Moreover, when the ratio of the blending amount of the diluent is not more than the above upper limit value, the components contained in the silver ink composition are more uniformly dissolved or dispersed, and the properties are improved.

[Other ingredients during production of silver ink composition]
In addition to the raw material composition and the diluent, the silver ink composition may further be blended with other components that do not fall within the scope of the effects of the present invention.
The other components at the time of producing the silver ink composition (at the time of blending the raw material composition and the diluent) are not particularly limited and can be arbitrarily selected according to the purpose, but are the blended components at the time of producing the raw material composition. What does not correspond to any of the said silver carboxylate, a nitrogen-containing compound, and a reducing agent is preferable.
The other components at the time of producing the silver ink composition may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio can be adjusted arbitrarily.

  Ratio of the blending amount of other components with respect to the total amount of blending components (total blending amount of the raw material composition, diluent and other components) during the production of the silver ink composition (when blending the raw material composition and the diluent) [Amount of other components (parts by mass)] / [Total amount of components (parts by mass)] × 100) is preferably 10% by mass or less, and more preferably 5% by mass or less. By prescribing in this way, the effect of suppressing the change in the viscosity of the silver ink composition over time becomes higher.

[Method for producing silver ink composition]
The silver ink composition can be obtained by blending the raw material composition, the diluent, and, if necessary, the other components.
At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
The mixing method is not particularly limited, and may be appropriately selected from known methods such as a method of mixing by rotating a stirrer or a stirring blade, a method of mixing using a mixer, a method of adding ultrasonic waves, and the like. .

  In the silver ink composition, all of the compounding components may be dissolved, or a part of the components may be dispersed without dissolving, but it is preferable that all of the compounding components are dissolved. It is preferable that the components not dispersed are uniformly dispersed.

  The temperature at the time of blending is not particularly limited as long as each blending component does not deteriorate, but is preferably −5 to 60 ° C. Moreover, what is necessary is just to adjust suitably according to the kind of compounding component, and the temperature at the time of a mixing | blending, but it is preferable that it is 1 minute-12 hours, for example.

The silver ink composition according to the present invention has an excellent effect that, when the raw material composition and the diluent are blended, a change in viscosity over time is suppressed. On the other hand, when the total amount of the diluent is not blended with the raw material composition, for example, when blended with any of the silver carboxylate, nitrogen-containing compound and reducing agent, the silver carboxylate, nitrogen-containing compound and When blended together with all of the reducing agents, the obtained silver ink composition does not have the above effects or becomes low.
Thus, at the time of manufacture of a silver ink composition, the essential component (the said carboxylic acid silver, a nitrogen-containing compound, and a reducing agent) was mixed after adding, and the formulation made into the state without the remarkable bias | inclination in the distribution of a containing component is prepared. It is important to use it as the raw material composition. In other words, for example, even if the diluent corresponds to the reducing agent, there is no problem even if such a diluent is used as long as it is blended after obtaining the raw material composition.

  What is necessary is just to measure the viscosity of a silver ink composition by a well-known method, for example, can measure it using a B-type viscosity meter or a vibration-type viscosity meter. When the viscosity of the silver ink composition may change depending on the shear rate, it is preferable to use a device that can accurately grasp the shear rate. Examples of such a device include a viscoelasticity measuring device (rheometer), cone A plate viscometer can be exemplified. In the present specification, the viscosity at a specific shear rate may be abbreviated as “shear viscosity”.

The silver ink composition according to the present invention measures, for example, a shear viscosity when the shear rate is 1000 s ⁻¹ at 25 ° C. (hereinafter sometimes abbreviated as “shear viscosity (1000 s ⁻¹ )”), The change rate (%) of the shear viscosity after storage calculated by the following formula (I) is preferably −30 to 30%, more preferably −25 to 25%.
[Change rate of shear viscosity of silver ink composition (%)] = {[Shear viscosity of silver ink composition after storage at 20 ° C. for 7 days (1000 s ⁻¹ ) (Pa · s)] − [silver immediately after production Shear viscosity of ink composition (1000 s ⁻¹ ) (Pa · s)]} / [Shear viscosity of silver ink composition immediately after production (1000 s ⁻¹ ) (Pa · s)] × 100 (I)

  The silver carboxylate is extremely excellent in that high-purity metallic silver (conductor) can be formed by post-treatment at a lower temperature than other metallic silver forming materials. On the other hand, the stability of the viscosity over time has not been studied so far in the silver ink composition using the silver carboxylate and the reducing agent in combination. In contrast, when the silver ink composition according to the present invention is used in combination with the silver carboxylate and the reducing agent, a specific type of diluent is further used in combination, and the blending order thereof is limited. The viscosity stability is significantly improved.

<Conductor and production method thereof>
The conductor according to the present invention is obtained by forming metallic silver using the silver ink composition, and is composed mainly of metallic silver. Here, “having metallic silver as a main component” means that the ratio of metallic silver is sufficiently high so that it can be regarded as being composed solely of metallic silver. For example, the ratio of metallic silver in a conductor Is preferably 99% by mass or more.

The conductor can be produced, for example, by attaching a silver ink composition on a substrate and appropriately performing post-treatment such as drying or heating (firing). The heat treatment may be performed also as a drying treatment.
The substrate is preferably in the form of a film or a sheet, and preferably has a thickness of 10 to 5000 μm.

The material of the base material is not particularly limited, and may be selected according to the purpose. However, a material having heat resistance that does not deteriorate during formation of the conductor by heat treatment of the silver ink composition is preferable.
Specifically, the material of the base material is polyethylene (PE), polypropylene (PP), polycycloolefin, polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer, polyvinyl alcohol, vinylon, polyvinylidene chloride (PVDC). , Polymethylpentene (PMP), polystyrene (PS), polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polybutyl methacrylate (PBMA), polymethyl acrylate (PMA) ), Polyethyl acrylate (PEA), polybutyl acrylate (PBA), AS resin, ABS resin, polyamide (PA), polyimide (PI), polyamideimide (PAI), polyacetal, polyethylene terephthalate (PET), glycol modified Polyeth Terephthalate (PET-G), 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), polyarylate, epoxy resin, Examples thereof include synthetic resins such as melamine resin, phenol resin, and urea resin.
In addition to the above, examples of the material for the substrate include ceramics such as glass and silicon; papers such as fine paper, thin paper, glassine paper, and sulfuric acid paper.
The base material may be a combination of two or more materials such as glass epoxy resin and polymer alloy.

The substrate may be composed of a single layer, or may be composed of two or more layers. When a base material 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 a base material consists of multiple layers, it is good to make it the total thickness of each layer be the thickness of said preferable base material.

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, gravure printing method, gravure offset printing method, pad printing method and the like.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, and other methods such as wire bars. It can be illustrated.

  The silver ink composition may be dried by a known method. For example, the silver ink composition may be dried under normal pressure, reduced pressure, or air blowing conditions, and may be performed in the air or in an inert gas atmosphere. Good. 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, a method of drying in the atmosphere at 18 to 30 ° C. can be exemplified.

When the silver ink composition is heat-treated, the temperature during the heat treatment is preferably 100 ° C. or lower, more preferably 90 ° C. or lower. Although the lower limit of the temperature at the time of heat processing is not specifically limited as long as metallic silver can be formed efficiently, it is preferable that it is 50 degreeC.
Moreover, what is necessary is just to adjust a heating time suitably according to heating temperature, for example, can be 0.1 to 6 hours.

  The conductor may be sufficiently formed of metallic silver and have high conductivity, that is, low volume resistivity. For example, the volume resistivity is preferably 20 μΩ · cm or less, more preferably 15 μΩ · cm. Hereinafter, it is particularly preferably 12 μΩ · cm.

  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.

<Manufacture of silver ink composition and evaluation thereof, manufacture of conductor and evaluation thereof>
[Example 1]
(Manufacture of silver ink composition)
2-ethylhexylamine (manufactured by Guangei Chemical Co., Ltd.) (84.7 g, 0.66 mol) in a 1000 mL beaker so that silver 2-methylacetoacetate (365.3 g, 1.64 mol) is 50 ° C. or lower. And stirred for 20 minutes. Next, formic acid (manufactured by Wako Pure Chemical Industries, Ltd.) (60.3 g, 1.31 mol) was added dropwise over 30 minutes so as to be 50 ° C. or lower and stirred for 2 hours to obtain a raw material composition. .
About the obtained raw material composition, the shear viscosity (shear viscosity (1000s < ^-1 >)) in case a shear rate is 1000 s- ¹ was measured at 25 degreeC using the rheometer ("MCR301" made by Anton Paar). However, it was 1.68 Pa · s. At this time, in the rheometer, CP25-2 (diameter 25 mm, cone angle 2 °) was used as the cone plate.
Next, n-dodecane in an amount of 6% by mass (0.6 g) of the raw material composition was added to the obtained raw material composition (10 g) in a plastic container, and a stirrer (Ryutaro Awatori ( AR-250)), the mixture was stirred at 20 ° C. for 30 seconds and then defoamed for 30 seconds to obtain a silver ink composition.

(Evaluation of silver ink composition)
About the obtained silver ink composition, it was 0.42 Pa.s when the shear viscosity (1000 s < ^-1 >) immediately after manufacture was measured by the same method as the said raw material composition.
Furthermore, after the obtained silver ink composition was left and stored in an incubator at 20 ° C. for 7 days, the shear viscosity (1000 s ⁻¹ ) was measured by the same method as that of the raw material composition, and was found to be 0.44 Pa · s. there were.
From these measured values, the change rate (%) of the shear viscosity of the silver ink composition after storage was calculated according to the formula (I), and it was 5%. The results are shown in Table 4.

(Manufacture of conductors)
Screen printing was performed on a film made of polyethylene terephthalate (PET) (“Lumirror S10” manufactured by Toray Industries, Inc., 100 μm thick) using the silver ink composition after standing still at 20 ° C. for 7 days. As the screen plate, a stainless steel 500 mesh was used, and printing was performed under the condition of an emulsion thickness of 10 μm.
Subsequently, the obtained printed pattern was post-processed by baking (heat treatment) at 80 ° C. for 2 hours to form a conductor (metal silver) pattern.

(Evaluation of conductor)
About the formed conductor pattern, the line resistance value R (Ω), the cross-sectional area A (cm ² ), and the line length L (cm) are measured, and the volume of the pattern is calculated by the equation “ρ = R × A / L”. The resistivity ρ (Ω · cm) was calculated to be 8 Ω · cm. The wire resistance value R is measured using a digital multimeter ("PC5000a" manufactured by Sanwa Denki Keiki Co., Ltd.), and the cross-sectional area A is measured using a shape measurement laser microscope ("VK-X100" manufactured by Keyence Corporation). did. The results are shown in Table 4.

[Examples 2 to 19, Comparative Examples 1 to 11]
A silver ink composition was produced and evaluated in the same manner as in Example 1 except that the types of blending components and the blending amounts thereof were as shown in Tables 1 to 3. Further, a conductor was produced and evaluated. The results are shown in Table 4.

  In Tables 1 to 3, the “molar ratio” of the nitrogen-containing compound is the compounding amount (number of moles) of the nitrogen-containing compound per mol of the carboxylate silver (the compounding amount of the nitrogen-containing compound (mole)). ] / [Amount of silver carboxylate (mole)]). The “molar ratio” of the reducing agent is the amount of the reducing agent blended per mole of silver carboxylate (number of moles) ([the amount of the reducing agent blended (mol)] / [the amount of silver carboxylate blended]. (Mol)]). In addition, “the amount% of raw material composition material” of the diluent is the ratio of the blending amount (mass) of the diluent to the blending amount (mass) of the raw material composition (the blending amount (mass) of the diluent) / [raw material composition Compounded amount (mass)] × 100).

  As is clear from the above results, in the silver ink compositions of Examples 1 to 19, the change in viscosity during storage from immediately after production to 7 days later was suppressed by using the diluent in the present invention. Moreover, the conductor manufactured using this silver ink composition had a low volume resistivity and excellent conductivity.

  On the other hand, the silver ink compositions of Comparative Examples 1 to 11 have a large change in viscosity during storage from immediately after production to 7 days after the use of a diluent different from that in the present invention. It was inferior to manufacturing aptitude (printing aptitude) at the time of manufacturing.

  The present invention can be used for pattern formation of highly conductive metallic silver such as a conductive circuit to which a printing method is applied.

Claims (3)

A silver carboxylate having a group represented by the formula “—COOAg”;
One or more nitrogen-containing compounds selected from the group consisting of an amine compound having a carbon number of 25 or less and a quaternary ammonium salt, ammonia, and an ammonium salt obtained by reacting the amine compound or ammonia with an acid;
A reducing agent,
Is blended into a raw material composition,
Furthermore, the raw material composition,
A hydrocarbon having 17 or less carbon atoms, a compound having 11 or less hydroxyl groups, a compound having 11 or less carbonyl groups, a compound having an amide bond having 15 or less carbon atoms, and an ether bond having 20 or less carbon atoms A silver ink composition comprising: one or more liquid diluents selected from the group consisting of compounds.   The diluent is n-dodecane, cyclooctane, 2,2,4,4-tetramethylpentane, 2-methyloctane, di-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether, 2-ethyl. -1-hexanol, 1-octanol, 1-hexanol, 2-propanol, ethylene glycol, cyclohexanol, 2-methyl-1-propanol, 1-pentanol, 2-butoxyethanol, 4-heptanone and N, N-dimethyl The silver ink composition according to claim 1, wherein the silver ink composition is one or more selected from the group consisting of formamide.   A conductor obtained by forming metallic silver using the silver ink composition according to claim 1.