WO2013111856A1

WO2013111856A1 - Silver ink composition

Info

Publication number: WO2013111856A1
Application number: PCT/JP2013/051590
Authority: WO
Inventors: 久美廣瀬; 真里奈今井
Original assignee: トッパン・フォームズ株式会社
Priority date: 2012-01-27
Filing date: 2013-01-25
Publication date: 2013-08-01

Abstract

A silver ink composition which is characterized by being obtained by blending a silver carboxylate having a group represented by formula -COOAg, an aliphatic primary amine or secondary amine having 2-10 carbon atoms, an acetylene alcohol represented by general formula (2), and a hydrocarbon having 6-20 carbon atoms. This silver ink composition is also characterized by having a viscosity at 27˚C of 40 mPa·s or less. (In general formula (2), each of R' and R'' independently represents an alkyl group having 1-20 carbon atoms or a phenyl group wherein one or more hydrogen atoms may be substituted by substituents.)

Description

Silver ink composition

The present invention relates to a silver ink composition suitable for application to an inkjet printing method.
This application is filed on January 27, 2012, Japanese Patent Application No. 2012-15581 filed in Japan, January 27, 2012, Japanese Patent Application No. 2012-15582 filed in Japan, December 27, 2012 The priority is claimed based on Japanese Patent Application No. 2012-284711 filed in Japan and Japanese Patent Application No. 2012-284712 filed on December 27, 2012, 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. Usually, when metallic silver is applied to such applications, a silver ink composition containing metallic silver or a component that forms the metallic silver is prepared, and this composition is attached to a substrate by various printing methods. Accordingly, in order to form a metallic silver film, a method of heating (firing) the deposited composition is employed. In order to form a fine metallic silver pattern, an inkjet printing method is widely used as the printing method.
As a silver ink composition suitable for application to such an ink jet printing method, those obtained by dispersing silver nanoparticles in various organic solvents are disclosed (see Patent Documents 1 and 2).

Special table 2010-504409 JP 2010-196150 A

However, the silver ink compositions described in Patent Documents 1 and 2 require an operation of preparing silver nanoparticles as a raw material by reducing silver nitrate using a reducing agent. Has a problem that a complicated process is involved.

The present invention has been made in view of the above circumstances, and provides a silver ink composition that can be produced by a simple method, is suitable for application to an inkjet printing method, and can form a practical amount of metallic silver. This is the issue.

To solve the above problem,
The present invention relates to a silver carboxylate having a group represented by the formula “—COOAg”, an aliphatic primary amine or secondary amine having 2 to 10 carbon atoms, and an acetylene alcohol represented by the following general formula (2): And a silver ink composition characterized by having a viscosity at 27 ° C. of 40 mPa · s or less.
In the silver ink composition of the present invention, a hydrocarbon having 6 to 14 carbon atoms is preferably blended, and the dynamic surface tension at 27 ° C. is preferably 56 mN / m or less.

(In the formula, R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)

In the silver ink composition of the present invention, the silver carboxylate is preferably silver β-ketocarboxylate represented by the following general formula (1).

(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 _2- "," 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 — ”;
Y is independently a fluorine atom, a chlorine atom, a bromine atom or a 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 a carbon group; An aliphatic hydrocarbon group of formula 1 to 19, a hydroxyl group or a group represented by the formula “AgO—”;
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. )

In the silver ink composition of the present invention, the R is represented by a linear or branched alkyl group, a phenyl group, or the general formula “R ⁶ —C (═O) —CY ₂ —”. And X is preferably a hydrogen atom, a linear or branched alkyl group, or a benzyl group.
In the silver ink composition of the present invention, the silver β-ketocarboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, 2-n- One or more selected from the group consisting of silver butyl acetoacetate, silver 2-benzylacetoacetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate and silver acetone dicarboxylate is preferred.
In the silver ink composition of the present invention, the aliphatic hydrocarbon group bonded to the nitrogen atom of the primary amine or secondary amine is preferably a linear or branched alkyl group. .
In the silver ink composition of the present invention, the primary amine or secondary amine is 2-ethylhexylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine. , N-octylamine, N-methylhexylamine, and N-ethylhexylamine are preferable.
In the silver ink composition of the present invention, R ′ and R ″ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
In the silver ink composition of the present invention, the acetylene alcohols are 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyne- It is preferably at least one selected from the group consisting of 3-ols.

According to the present invention, there is provided a silver ink composition that can be produced by a simple method, is suitable for application to an ink jet printing method, and can form a practical amount of metallic silver.

<Silver ink composition>
The silver ink composition of the present invention is a silver carboxylate having a group represented by the formula “—COOAg” (hereinafter sometimes simply referred to as “silver carboxylate”), an aliphatic group having 2 to 10 carbon atoms. Primary amine or secondary amine (hereinafter sometimes abbreviated as “amine compound”), acetylene alcohol represented by the following general formula (2) (hereinafter sometimes abbreviated as “acetylene alcohol”) And a hydrocarbon having 6 to 20 carbon atoms (hereinafter sometimes abbreviated as “hydrocarbon”), and the viscosity at 27 ° C. is 40 mPa · s or less.

[Silver carboxylate]
The silver carboxylate 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 one, or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.
The silver carboxylate is decomposed by heating or the like to form metallic silver.

In the present invention, the silver carboxylate 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.

The silver carboxylate is preferably a silver β-ketocarboxylate represented by the following general formula (1) (hereinafter sometimes abbreviated as “silver β-ketocarboxylate”).
In the present specification, unless otherwise specified, the term “silver carboxylate” includes not only “silver β-ketocarboxylate” but also a group represented by the formula “—COOAg”. Means silver carboxylate ".

(Silver β-ketocarboxylate)
In the present invention, the silver β-ketocarboxylate is represented by the general formula (1).
In the formula, R is 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 ₂ -"," 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 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 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, -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, isooctyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 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 the 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), etc. ) 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.

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, 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.

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 for 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—”. The aliphatic hydrocarbon group in R ⁶ has 1 to 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 phenyl group, or a group represented by the general formula “R ⁶ —C (═O) —CY ₂ —”. 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 Examples include a group (—NO ₂ ), 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.

R ^{7 in} X represents 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 either 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.

X is preferably a hydrogen atom, a linear or branched alkyl group, or a benzyl group, and at least one X is preferably a hydrogen atom.

The silver β-ketocarboxylate 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 2-n-butylacetoacetate (CH ₃ —C (═O) —CH (CH 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), pivaloylacetate Silver acetate ((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), or silver acetone dicarboxylate (AgO—C (═O) —CH ₂ —C (═O) —CH ₂ —C (═O) —OAg) is preferred. Among these silver β-ketocarboxylates, among those represented by the general formula (1), the concentration of the remaining raw materials and impurities can be further reduced in the metallic silver formed by the 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.

As will be described later, the silver β-ketocarboxylate decomposes 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. Form.

In the present invention, silver β-ketocarboxylate 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.

In the silver ink composition, the silver content in the silver carboxylate is preferably 17% by mass or more, and more preferably 18% by mass or more. By setting it as such a range, the metal silver formed with the method mentioned later becomes favorable in electroconductivity, and becomes more excellent in quality. The upper limit of the silver content is not particularly limited as long as the effect of the present invention is not hindered, but it is preferably 25% by mass in consideration of handleability and the like.

[Amine compound]
In the present invention, the amine compound is an aliphatic primary amine or an aliphatic secondary amine, and is not particularly limited as long as the total number of carbon atoms is 2 to 10, but is preferably bonded to a nitrogen atom. Examples are those in which the aliphatic hydrocarbon group is an alkyl group (alkylamine, dialkylamine). The alkyl group may be linear, branched or cyclic.
Examples of the linear or branched alkyl group include an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an isopentyl group. , Neopentyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, nonyl group, decyl group and the like.
The cyclic alkyl group may be monocyclic or polycyclic, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, isobornyl group, adamantyl group Group, tricyclodecyl group and the like.

Among them, the amine compound is preferably one in which the alkyl group bonded to the nitrogen atom is linear or branched. The amine preferably has 2 to 9 carbon atoms, more preferably 3 to 8 carbon atoms, specifically, n-propylamine, n-butylamine, n-pentylamine, n- Examples include hexylamine, n-heptylamine, 2-ethylhexylamine, n-octylamine, N-methylhexylamine, N-ethylhexylamine and the like.

The amine compounds may be used alone or in combination of two or more. When using 2 or more types together, the combination and ratio may be appropriately selected according to the purpose.

In the silver ink composition, the compounding amount of the amine compound is preferably 1 to 6 mol, and more preferably 1.5 to 5 mol, per mol of the carboxylate silver. By making the compounding quantity of an amine compound more than a lower limit, the use effect of an amine compound becomes higher, and metallic silver of better quality can be formed by making it the upper limit or less.

[Acetylene alcohols]
In the present invention, acetylene alcohols are represented by the general formula (2).
In the general formula (2), R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group having 1 to 20 carbon atoms in R ′ and R ″ may be any of linear, branched and cyclic (aliphatic cyclic group). When cyclic, it may be any of monocyclic or polycyclic But you can. Examples of the alkyl group in R ′ and R ″ include the same alkyl groups as in R.

Examples of the substituent in which the hydrogen atom of the phenyl group in R ′ and R ″ may be substituted include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the aliphatic carbon A monovalent group in which a hydrogen group is bonded to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, etc. can be exemplified, and the hydrogen atom of the phenyl group in R may be substituted Same as the group. 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.

R ′ and R ″ are preferably an alkyl group having 1 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 10 carbon atoms.

Preferable examples of the acetylene alcohols include 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, and 3-methyl-1-pentyn-3-ol.

In the present invention, acetylene alcohols may be used alone or in combination of two or more. When two or more kinds are used in combination, the combination and ratio can be arbitrarily adjusted.

In the silver ink composition, the blending amount of acetylene alcohols is preferably 0.03 to 0.7 mole, and preferably 0.06 to 0.3 mole, per mole of the above-mentioned silver carboxylate. More preferred. By making the compounding quantity of acetylene alcohol more than a lower limit, the use effect of acetylene alcohol becomes higher, and metallic silver of better quality can be formed by making it the upper limit or less.

(hydrocarbon)
In the present invention, the hydrocarbon has 6 to 20 carbon atoms, and may be linear, branched or cyclic, and may be any of saturated hydrocarbon and unsaturated hydrocarbon. The hydrocarbon is preferably liquid at 15 to 37 ° C., and more preferably liquid at 15 to 30 ° C.

Examples of the linear or branched saturated hydrocarbon include n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methyl Hexane, 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-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,3- Dimethylhexane, 3,4-dimethylhexane, 2,2,3-trimethylpentane, 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-dimethylheptane, 2,5-dimethylheptane, 2,6-dimethyl Heptane, 3,3 dimethylheptane, 3,4-dimethylheptane, 3,5-dimethylheptane, 4,4-dimethylheptane, 2,2,4,4, -tetramethylpentane, decane, undecane, dodecane, tridecane, Examples include tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonacan, and eicosane.

The cyclic saturated hydrocarbon may be monocyclic or polycyclic, but is preferably monocyclic, preferably has 8 or less carbon atoms, and examples thereof include cyclohexane, cycloheptane, and cyclooctane.

As the unsaturated hydrocarbon, one or more single bonds (C—C) between carbon atoms of the saturated hydrocarbon are unsaturated bonds (double bonds (C═C), triple bonds (C≡C)). ) Can be exemplified.
The unsaturated hydrocarbon may have either a double bond or a triple bond as an unsaturated bond between carbon atoms, or may have both, and the number of unsaturated bonds. And the position is 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 hydrocarbon is preferably an alkene or alkyne.

In the present invention, the hydrocarbons may be used singly or in combination of two or more. 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 hydrocarbon is preferably 0.05 to 2 mol, more preferably 0.1 to 1.5 mol, per mol of the carboxylate silver. . By setting the blending amount of the hydrocarbon to the lower limit value or more, the viscosity of the silver ink composition can be adjusted to a more suitable low value, and by setting it to the upper limit value or less, metallic silver of better quality can be formed.

[Other ingredients]
In addition to the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons, the silver ink composition may be further blended with other components not corresponding to these within a range not impeding the effects of the present invention. .
In the silver ink composition, the total blending amount of the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons in the total blending component is preferably 85% by mass or more, and 90% by mass or more. Is more preferably 95% by mass or more, and may be 100% by mass.

[Viscosity of silver ink composition]
The viscosity at 27 ° C. of the silver ink composition is 40 mPa · s or less, preferably 37 mPa · s or less, and more preferably 33 mPa · s or less. By being below the upper limit, the silver ink composition has physical properties suitable for the ink jet printing method.
The lower limit of the viscosity is not particularly limited, but is preferably 5 mPa · s in consideration of the handleability of the silver ink composition.

The viscosity of the silver ink composition can be measured according to a known method, for example, an ultrasonic viscometer.

The viscosity of the silver ink composition can be adjusted by, for example, the type and amount of the blending component, but can be easily adjusted by the type of the hydrocarbon.

Here, the viscosity at 27 ° C. of the silver ink composition has been described, but the temperature at the time of use of the silver ink composition is not limited to 27 ° C. and can be arbitrarily selected. When the viscosity at 27 ° C. is in the above range, the silver ink composition exhibits an excellent effect under normal use conditions.

[Surface tension of silver ink composition]
The silver ink composition has a dynamic surface tension at 27 ° C. of 56 mN / m or less, and preferably 53 mN / m or less. With such a range, the silver ink composition is suitable for the inkjet printing method. It will have the physical properties.
The lower limit value of the dynamic surface tension is not particularly limited, but is preferably 28 mN / m in consideration of the handleability of the silver ink composition.
In the present invention, the “dynamic surface tension” is calculated using, for example, a so-called “maximum value” that is calculated using the maximum value of the pressure that the bubbles receive from the silver ink composition when bubbles are generated in the silver ink composition. It is calculated | required by the "bubble pressure method. In the maximum bubble pressure method, for example, the dynamic surface tension may be obtained when the bubble frequency is any of 9 to 11 Hz.

Further, the silver ink composition preferably has a static surface tension at 27 ° C. of 30 mN / m or less, and more preferably 28 mN / m or less. By being in such a range, the silver ink composition has physical properties more suitable for the ink jet printing method.
The lower limit value of the static surface tension is not particularly limited, but is preferably 14 mN / m in consideration of the handleability of the silver ink composition.
In the present invention, for example, the surface tension when the bubble frequency is any of 0.05 to 0.2 Hz by the maximum bubble pressure method may be set to “static surface tension”.

The silver ink composition preferably has a surface tension at a bubble frequency of 1 Hz at 27 ° C. in the maximum bubble pressure method of 45 mN / m or less, more preferably 40 mN / m or less. By being in such a range, the silver ink composition has physical properties more suitable for the ink jet printing method.
The lower limit value of the surface tension at 1 Hz is not particularly limited, but is preferably 21 mN / m in consideration of the handleability of the silver ink composition.

The surface tension (dynamic surface tension, static surface tension, etc.) of the silver ink composition can be adjusted by, for example, the type and amount of the blending component, but can be easily adjusted by the type of the hydrocarbon.

Although the surface tension at 27 ° C. of the silver ink composition has been described here, the temperature at the time of use of the silver ink composition is not limited to 27 ° C. and can be arbitrarily selected. When the surface tension at 27 ° C. is in the above range, the silver ink composition exhibits an excellent effect under normal use conditions.

[Production of silver ink composition]
The silver ink composition can be obtained by blending the silver carboxylate, amine compound, acetylene alcohols and hydrocarbons, 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. .

The blending component may be dissolved in the silver ink composition, or a part of the components may be dispersed without being dissolved.

The temperature at the time of blending is not particularly limited as long as each blended component does not deteriorate, but is preferably −5 to 30 ° C.

[Metallic silver]
The silver ink composition of the present invention can easily form metallic silver by thermally decomposing silver carboxylate by heating (firing) treatment at a temperature of 60 to 200 ° C., for example. Therefore, a silver metal composition can be formed by applying the silver ink composition to various printing methods such as an ink jet printing method suitable for the viscosity and heat-treating the obtained print pattern.

The heating temperature at the time of forming metallic silver may be appropriately adjusted according to the type of silver carboxylate. The silver carboxylate is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. to form metallic silver. Therefore, reflecting such a decomposition temperature, the silver ink composition of the present invention has a lower temperature than the conventional metal silver forming material as described above, without using a reducing agent known in the art. Metal silver can be formed. The heating time may be adjusted as appropriate according to the heating temperature.

The substrate to be inkjet-printed with the silver ink composition may be a known one, and examples thereof include an ink receiving layer provided on a substrate, but are not limited thereto.

The material of the substrate is not particularly limited, and may be selected according to the purpose. Specifically, paper such as base paper, art paper, coated paper, cast coated paper, resin coated paper, synthetic paper; polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, acrylic resin, AS resin, ABS resin , Polyamide, polyacetal, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polyphenylene sulfide, polysulfone, polycarbonate, epoxy resin, melamine resin, phenol resin, urea resin, polyurethane, polyimide, etc. Examples of the synthetic resin are as follows. Two or more kinds of materials may be laminated.

The base material is preferably in the form of a sheet or a film, and preferably has a thickness of 20 to 1000 μm. By setting the thickness of the base material to the lower limit value or more, the structure of the ink receiving layer can be more stably maintained, and by setting the thickness to the upper limit value or less, the handleability as a printed material becomes better.

The ink receiving layer preferably has a thickness of 1 to 20 μm. By setting the thickness of the ink receiving layer in such a range, the structure of the ink receiving layer can be more stably maintained, and the quality of the printed matter is further improved.

The silver ink composition of the present invention is suitable for application to an ink jet printing method because the viscosity is in the above numerical range. It can be produced by an extremely simple method in which each component is simply blended at a predetermined temperature. Moreover, the obtained silver ink composition can form a practical amount of metallic silver very easily by heat treatment without using the reducing agent or the like.
In the present invention, “plurality” means that the number may be at least two or more.

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.

<Production and Evaluation of Silver Ink Composition>
[Example 1]
(Manufacture of silver ink composition)
2-ethylhexylamine (3.1 g), 3,5-dimethyl-1-hexyn-3-ol (“Surfinol 61” manufactured by Air Products Japan) (0.17 g) and n-octane (0.8 g) A silver ink composition was obtained by adding the mixture into a 13.5 mL vial and stirring, and further adding silver 2-methylacetoacetate (3.0 g) under ice cooling and stirring for 30 minutes. . Table 1 shows the amount of each component.

(Evaluation of silver ink composition)
・ Viscosity In the obtained silver ink composition (7 g), a sensor (vibrating body) of an ultrasonic viscometer (“VISCOMATE VM-10A” manufactured by CBC) was immersed, and silver was used in an environment at a temperature of 27 ° C. The viscosity of the ink composition was measured. The results are shown in Table 2.
・ Surface tension In the obtained silver ink composition (7 g), a sensor of a surface tension meter (“Portable Surface Tension Meter Theta t60” manufactured by Eihiro Seiki Co., Ltd.) is immersed, and the bubble frequency is measured in an environment at a temperature of 27 ° C. The surface tension of the silver ink composition at 0.1 Hz (static surface tension), the surface tension at 1 Hz, and the surface tension at 10 Hz (dynamic surface) by changing from 0 Hz to 10 Hz and using the maximum bubble pressure method. Tension) was measured. The results are shown in Table 2.

<Manufacture and evaluation of metallic silver>
(Manufacture of metallic silver)
The silver ink composition obtained above was discharged and applied onto a polyethylene terephthalate (PET) base material (“Lumirror S10” manufactured by Toray Industries, Inc., thickness 100 μm). The coating amount of the silver ink composition on the substrate at this time was adjusted to 15 ± 1 g / m ² .
Next, this silver ink composition is sequentially subjected to heat treatment by hot air blowing at 80 ° C. for 30 minutes, and further by heat treatment by hot air blowing at 150 ° C. for 30 minutes or 60 minutes to form metallic silver in two ways. It was.

(Evaluation of metallic silver)
In the obtained metallic silver, the surface resistance value (Ω / □) was measured in accordance with JIS K 7194 (ASTM D 991) using an electrical resistance measuring device “Loresta MCP-T610 (manufactured by Mitsubishi Chemical Analytic Co., Ltd.)”. Was measured. The results are shown in Table 2.

<Manufacture and evaluation of silver ink composition, and manufacture and evaluation of metallic silver>
[Examples 2 to 17, Comparative Examples 1 to 3]
A silver ink composition was produced and evaluated in the same manner as in Example 1 except that the types and blending amounts of the components were as shown in Table 1. The results are shown in Table 2. In Table 1, “-” indicates that the component is not blended.
Further, metallic silver was produced and evaluated in the same manner as in Example 1 using the obtained silver ink composition. The results are shown in Table 2. In Table 2, “OL” indicates that the value is too large to be measured (overload).

Each abbreviation shown in Table 1 means the following.
(A) Silver carboxylate (a) -1: Silver 2-methylacetoacetate (b) Amine compound (b) -1: 2-ethylhexylamine (c) Acetylene alcohols (c) -1: 3,5-dimethyl- 1-hexyn-3-ol (c) -2: 3-methyl-1-pentyn-3-ol (“Orphine P” manufactured by Nissin Chemical Industry Co., Ltd.)
(C) -3: 3-Methyl-1-butyn-3-ol (“Orphine B” manufactured by Nissin Chemical Industry Co., Ltd.)

As is clear from the above results, the silver ink composition of the present invention has a viscosity of 31 mPa · s or less, can be easily ejected, and can be confirmed to be suitable for application to the ink jet printing method. Further, a sufficient amount of metallic silver was formed, and its resistance value was as small as 0.4Ω / □ or less, and it was stable even when the heat treatment time changed, and was suitable as a conductive material.
On the other hand, the silver ink composition of Comparative Example 1 was not suitable for application to the ink jet printing method because it had a high viscosity and was difficult to discharge because it did not contain hydrocarbons.
Further, the silver ink composition of Comparative Example 2 was not suitable for application to the ink jet printing method due to the high viscosity, difficulty in ejection due to the inadequate type of the blended hydrocarbon. Further, the formed metallic silver had a remarkably high resistance value, and the value could not be measured.
In addition, the silver ink composition of Comparative Example 3 did not contain hydrocarbons, whereas the amount of silver carboxylate was less than that of Comparative Example 1 and the amount of amine compound was increased. Although the viscosity was low, the formed metallic silver had a high resistance value.

<Manufacture and evaluation of silver ink composition, and manufacture and evaluation of metallic silver>
[Examples 18 to 23]
A silver ink composition was produced and evaluated in the same manner as in Example 1 except that the types and blending amounts of the components were as shown in Table 3. The results are shown in Table 4.
Further, metallic silver was produced and evaluated in the same manner as in Example 1 using the obtained silver ink composition. The results are shown in Table 4.

Each abbreviation shown in Table 3 means the following.
(A) Silver carboxylate (a) -2: Silver acetoacetate (a) -3: Silver pivaloyl acetate (a) -4: Silver isobutyryl acetate (a) -5: Silver acetone dicarboxylate

As is clear from the above results, the silver ink composition of the present invention has a viscosity of 25.6 mPa · s or less, can be easily ejected, and can be confirmed to be suitable for application to the ink jet printing method. It was. Further, a sufficient amount of metallic silver was formed, its resistance value was as small as 5.2 Ω / □ or less, and it was stable even when the heat treatment time was changed, and was suitable as a conductive material.

The present invention can be used as an ink for ink-jet printing, and is particularly useful for forming a fine metallic silver pattern.

Claims

Silver carboxylate having a group represented by the formula —COOAg, aliphatic primary amine or secondary amine having 2 to 10 carbon atoms, acetylene alcohol represented by the following general formula (2), and carbon number 6 A silver ink composition comprising ˜20 hydrocarbons and a viscosity at 27 ° C. of 40 mPa · s or less.

(In the formula, R ′ and R ″ are each independently an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)
The silver ink composition according to claim 1, comprising a hydrocarbon having 6 to 14 carbon atoms and a dynamic surface tension at 27 ° C of 56 mN / m or less.
The silver ink composition according to claim 1 or 2, wherein the silver carboxylate is a β-ketocarboxylate silver represented by the following general formula (1).

(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 2 —, 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 — Is;
Y is independently a fluorine atom, a chlorine atom, a bromine atom or a 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 a carbon group; An aliphatic hydrocarbon group having a number of 1 to 19, a hydroxyl group or a group represented by the formula AgO—;
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 group represented by the general formula R 7 O—, R 7 S—, R 7 —C (═O) — or R 7 —C (═O) —O— A group to be
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. )
R is a linear or branched alkyl group, a phenyl group, or a group represented by the general formula R 6 —C (═O) —CY 2 —, wherein X is a hydrogen atom, a linear chain The silver ink composition according to claim 3, which is a linear or branched alkyl group or a benzyl group.
The silver β-ketocarboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver 2-n-butylacetoacetate, silver 2-benzylacetoacetate The silver ink composition according to claim 3 or 4, which is one or more selected from the group consisting of silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate and silver acetone dicarboxylate.
The aliphatic hydrocarbon group bonded to the nitrogen atom of the primary amine or the secondary amine is a linear or branched alkyl group according to any one of claims 1 to 5. Silver ink composition.
The primary amine or secondary amine is 2-ethylhexylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, N-methylhexyl. The silver ink composition according to any one of claims 1 to 6, wherein the silver ink composition is at least one selected from the group consisting of an amine and N-ethylhexylamine.
The silver ink composition according to any one of claims 1 to 7, wherein R 'and R' 'are linear or branched alkyl groups having 1 to 10 carbon atoms.
The acetylene alcohol is selected from the group consisting of 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol and 3-methyl-1-pentyn-3-ol. The silver ink composition according to any one of claims 1 to 8, wherein the silver ink composition is one or more.