JP6953241B2 - Silver ink composition and laminate - Google Patents

Description

The present invention relates to silver ink compositions and laminates.

Among the silver ink compositions containing an organic silver compound, those using silver β-ketocarboxylate as the organic silver compound (see Patent Document 1) have excellent conductivity and gloss by heat treatment. It is highly useful because it can form a dense film made of metallic silver.
Further, such a silver ink composition is also suitable for application to, for example, an inkjet printing method because the viscosity can be easily adjusted and particulate insoluble matter can be reduced or eliminated.

However, since the ink composition used in the inkjet printing method usually has a low viscosity, it tends to bleed when printed on an object to be printed. Therefore, in the inkjet printing method, a method is disclosed in which a solvent component in an ink composition is volatilized before the printed ink composition bleeds by heating the object to be printed (see Patent Document 2). ..

Japanese Patent No. 5393988 Japanese Patent No. 4889059

However, in the inkjet printing method, when printing is performed while heating the object to be printed using a silver ink composition containing an organic silver compound, the present inventors certainly bleed the silver ink composition. However, it was found that the metallic silver film finally formed by the heat treatment of the silver ink composition was inferior in glossiness to the case where the printed matter was not heated.

The present invention has been made in view of the above circumstances, and is a silver ink composition containing an organic silver compound, which has glossiness even when printing is performed while heating an object to be printed. It is an object of the present invention to provide a silver ink composition capable of forming a high metallic silver and a laminate having a highly glossy metallic silver layer formed by using the silver ink composition.

In order to solve the above problems, the present invention provides a silver ink composition in which an organic silver compound and a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms are blended.
Further, the present invention is a laminate including a base material and a metallic silver layer formed on the base material, and the metallic silver layer is formed by using the silver ink composition of the present invention. Provided is a laminated body of the metallic silver layer having a reflectance of light having a wavelength of 550 nm of 50% or more.

According to the present invention, silver is a silver ink composition containing an organic silver compound, and can form metallic silver having high gloss even when printing is performed while heating an object to be printed. An ink composition and a laminate having a highly glossy metallic silver layer formed by using the silver ink composition are provided.

It is sectional drawing which shows one Embodiment of the laminated body of this invention schematically.

<< Silver ink composition >>
The silver ink composition of the present invention may be abbreviated as an organic silver compound and a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms (in the present specification, it is abbreviated as "branched chain saturated aliphatic carboxylic acid". There is) and is mixed.
The silver ink composition of the present invention contains the branched-chain saturated aliphatic carboxylic acid, so that even when printing is performed while heating the object to be printed, metallic silver having high gloss can be obtained. Can be formed.

In addition, this specification describes not only the case where the metallic silver layer (metallic silver) is formed by printing the silver ink composition but also the case where it is formed by coating (coating). That is, the application target of the silver ink composition of the present invention is not limited to the printing method, and the coating method described later can also be mentioned. Then, the silver ink composition of the present invention can form metallic silver having high glossiness even when the object to be coated is coated while being heated, as in the case of the printing method.

The organic silver compound is a compound having an organic group and a silver atom in one molecule and producing metallic silver by a structural change such as decomposition.
Examples of such an organic silver compound include silver salts of organic acids and organic silver complexes.
In the present invention, one type of organic silver compound may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted. ..

Preferred silver ink compositions include the silver ink composition (I) and the silver ink composition (II) shown below. These silver ink compositions will be described below.

〇 Silver ink composition (I)
The silver ink composition (I) is preferably a compound containing silver carboxylate (silver salt of carboxylic acid) as the organic silver compound. That is, a preferable silver ink composition (I) is a mixture of silver carboxylate and the branched-chain saturated aliphatic carboxylic acid.

[Silver carboxylate]
The silver carboxylate has a group represented by the formula "-COOAg".
In the present invention, one type of silver carboxylate may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted. ..
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 only one or two or more. Further, the position of the group represented by the formula "-COOAg" in silver carboxylate is not particularly limited.

The silver carboxylate is represented by silver β-ketocarboxylate represented by the following general formula (1) (hereinafter, may be abbreviated as “silver β-ketocarboxylate (1)”) and the following general formula (4). It is preferably one or more selected from the group consisting of silver carboxylate (hereinafter, may be abbreviated as "silver carboxylate (4)").
In this specification, the description of "silver carboxylate" is not limited to "silver β-ketocarboxylate (1)" and "silver carboxylate (4)" unless otherwise specified. Inclusive, it shall 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^１ _２−」、「ＣＹ^１ _３−」、「Ｒ^１−ＣＨＹ^１−」、「Ｒ^２Ｏ−」、「Ｒ^５Ｒ^４Ｎ−」、「（Ｒ^３Ｏ）_２ＣＹ^１−」若しくは「Ｒ^６−Ｃ（＝Ｏ）−ＣＹ^１ _２−」で表される基であり；
Ｙ^１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^１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 is an aliphatic hydrocarbon group or phenyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a hydroxyl group, an amino group, or the general formula "R ^1- CY". ¹ ₂ − ”,“ CY ¹ ₃ − ”,“ R ¹ − CHY ¹ − ”,“ R ² O − ”,“ R ⁵ R ⁴ N − ”,“ (R ³ O) ₂ CY ¹ − ”or“ It is a group represented by "R ^6- C (= O) -CY ¹ _2-";
Y ¹ is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R ¹ is an aliphatic hydrocarbon group or a phenyl group having 1 to 19 carbon atoms; R ² is a fat having 1 to 20 carbon atoms. Group hydrocarbon groups; R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are independently aliphatic hydrocarbon groups having 1 to 18 carbon atoms; R ⁶ is an aliphatic hydrocarbon group having 1 to 18 carbon atoms. An aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula "AgO-";
X ¹ is an independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and a phenyl group or a benzyl group, a cyano group, N in which one or more hydrogen atoms may be substituted with a substituent. -Phenyl-3-aminopropyl group, 2-ethoxyvinyl group, or general formula "R ⁷ O-", "R ⁷ S-", "R ^7- C (= O)-" or "R ^7- C ( = O) -O- "is a group represented by;
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or a 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「−Ｃ（＝Ｏ）−ＯＡｇ」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個以上の前記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 "-C (= O) -OAg", and the aliphatic hydrocarbon group is a methylene group. If, one or more of the methylene groups may be substituted with a carbonyl group.)

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

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may be linear, branched chain or cyclic (aliphatic cyclic group), and when 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 aliphatic hydrocarbon groups in R include, for example, an alkyl group, an alkenyl group, an alkynyl group and the like.

Examples of the linear or branched alkyl group in R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , N-Pentyl group, Isopentyl group, Neopentyl group, tert-Pentyl group, 1-methylbutyl group, 2-Methylbutyl group, n-hexyl group, 1-Methylpentyl group, 2-Methylpentyl group, 3-Methylpentyl group, 4-Methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3- Ethylbutyl group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 5-methylhexyl group, 1, 1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group Group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group, n-octyl group, isooctyl group, 1-methylheptyl group, 2-Methylheptyl group, 3-Methylheptyl group, 4-Methylheptyl group, 5-Methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4-ethylhexyl group, 5-ethylhexyl group, 1 , 1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1,2,3-trimethylpentyl group, 1, , 2,4-trimethylpentyl group, 2,3,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 3,4,4-trimethylpentyl group, 1 , 1,2-trimethylpentyl group, 1,1,3-trimethylpentyl group, 1,1,4-trimethylpentyl group, 1,2,2-trimethylpentyl group, 2,2,3-trimethylpentyl group, 2 , 2,4-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,3,3-trimethylpentyl group, 3,3,4-trimethylpentyl group, 1-propylpentyl group, 2-propylpentyl group , Nonyl group, decyl group, c Examples thereof include an indecyl group, a dodecyl group, a tridecylic group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecylic group, and an icosyl group.
Examples of the cyclic alkyl group in R include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, an isobornyl group and a 1-adamantyl group. Examples thereof include a 2-adamantyl group and a tricyclodecyl group.

Examples of the alkenyl group in R include a group in which one single bond (CC) between carbon atoms of the alkyl group in R is replaced with a double bond (C = C).
Examples of such an alkenyl group include a vinyl group (ethenyl group, -CH = CH ₂ ), an allyl group (2-propenyl group, -CH ₂ -CH = CH ₂ ), and a 1-propenyl group (-CH =). CH-CH ₃ ), isopropenyl group (-C (CH ₃ ) = CH ₂ ), 1-butenyl group (-CH = CH-CH _{2 -CH 3} ), 2-butenyl group (-CH ₂ -CH = CH) -CH _3), 3- butenyl group _{(-CH 2 -CH 2 -CH = CH} 2), cyclohexenyl, cyclopentenyl group and the like.

Examples of the alkynyl group in R include a group in which one single bond (CC) between carbon atoms of the alkyl group in R is replaced with a triple bond (C≡C).
Examples of such an alkynyl group include an ethynyl group (-C≡CH) and a propargyl group (-CH _2- C≡CH).

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may have one or more hydrogen atoms substituted with a substituent. Preferred substituents include, for example, a fluorine atom, a chlorine atom, a bromine atom and the like. Further, in the aliphatic hydrocarbon group, the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same 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. Preferred substituents include, for example, 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, and fluorine. Examples thereof include an atom, a chlorine atom, a bromine atom, a hydroxyl group (-OH), a cyano group (-C≡N), and a phenoxy group (-OC ₆ H ₅ ). In the phenyl group having a substituent, the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.
Examples of the aliphatic hydrocarbon group as a substituent include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 16.

^{Y 1 in} R is independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom. Then, the general formula ^"R ₁ ^-CY 1 ₂ -", ^"CY _{1 3} -" and ^{"R 6 -C (= O) -CY} 1 2 - " In a plurality of ^{Y 1} are each, also identical to one another It may be different.

^{R 1} in R is an aliphatic hydrocarbon group or a phenyl group (C ₆ H _5- ) having 1 to 19 carbon atoms. Examples of the aliphatic hydrocarbon group in R ¹ include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 19.
^{R 2} in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the same group as the aliphatic hydrocarbon group in R.
^{R 3} in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms. Examples of the aliphatic hydrocarbon group in R ³ include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 16.
^{R 4} and R ⁵ in R are aliphatic hydrocarbon groups having 1 to 18 carbon atoms independently. That is, R ⁴ and R ⁵ may be the same as or different from each other, and the ^{aliphatic hydrocarbon group in R 4 and R 5} includes, for example, the above-mentioned in R except that the number of carbon atoms is 1 to 18. Examples are similar to aliphatic hydrocarbon groups.
^{R 6} in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group, or a group represented by the formula “AgO−”. Examples of the aliphatic hydrocarbon group in R ⁶ include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 19.

R is, among these, a linear or branched alkyl group, the general formula ^{"R 6 -C (= O) -CY} 1 2 - " group represented by be a hydroxyl group or a phenyl group preferable. R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group, or a group represented by the formula “AgO−”.

In the general formula (1), X ¹ is an independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. A benzyl group (C ₆ H _5- CH _2- ), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C ₂ H _5- O-CH = CH-), or the general formula "R". ^{It is a group represented by "7} O-", "R ⁷ S-", "R ^7- C (= O)-" or "R ^7- C (= O) -O-".
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X ^{1 include the same group as the aliphatic hydrocarbon group in R.}

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

^{R 7} in X ¹ is an aliphatic having 1 to 10 carbon atoms hydrocarbon group, a thienyl group _{(C 4} H 3 S-), or one or more hydrogen atoms is a phenyl group or optionally substituted with a substituent diphenyl group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) is. Examples of the aliphatic hydrocarbon group in R ⁷ include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 10. Further ^{, examples of the substituent contained in the phenyl group and the diphenyl group in R 7} include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. In the phenyl group and the diphenyl group having a substituent, the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.
When R ⁷ is thienyl or diphenyl group, these adjacent group or atom in X ¹ (oxygen atom, a sulfur atom, a carbonyl group, carbonyloxy group) bonding position to 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 X ¹ may be bonded as one group through a carbon atom and double bond sandwiched between two carbonyl groups. Examples of such X ¹ include a group represented by the formula "= CH-C ₆ H _4- NO _2".

X ^1, among the above, a hydrogen atom, a linear or branched alkyl group, a benzyl group, or formula "R ⁷ -C (= O) -" it is a group represented by preferably , It is preferable that at least one X ¹ is a hydrogen atom.

The silver β-ketocarboxylate (1) is silver 2-methylacetate acetate (CH _3- C (= O) -CH (CH ₃ ) -C (= O) -OAg), silver acetoacetate (CH _3- C (=)). O) -CH _2- C (= O) -OAg), 2-ethylacetate silver (CH _3- C (= O) -CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver propionyl acetate (CH ₃ CH _2- C (= O) -CH _2- C (= O) -OAg), silver isobutyryl acetate ((CH ₃ ) ₂ CH-C (= O) -CH _2- C (= O)- OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C-C (= O) -CH _2- C (= O) -OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH _2- C (= O) ) -CH _2- C (= O) -OAg), 2-n-silver acetate butylacetate (CH _3- C (= O) -CH (CH ₂ CH ₂ CH ₂ CH ₃ ) -C (= O) -OAg ), 2-benzylacetate silver acetate (CH _3- C (= O) -CH (CH ₂ C ₆ H ₅ ) -C (= O) -OAg), silver benzoyl acetate (C ₆ H _{5-C (= O))} ) -CH _2- C (= O) -OAg), silver pivaloylacetate acetate ((CH ₃ ) ₃ C-C (= O) -CH _2- C (= O) -CH _2- C (= O) -OAg ), Silver Isobutyrylacetate Acetate ((CH ₃ ) ₂ CH-C (= O) -CH _2- C (= O) -CH _2- C (= O) -OAg), 2-Acetylpyvaloyl Acetate Silver ((CH ₃ ) ₃ C-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg), 2-acetylisobutyryl silver acetate ((CH ₃ )) ₂ CH-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg) or silver acetate dicarboxylate (AgO-C (= O) -CH _2- C ( = O) -CH _2- C (= O) -OAg) is preferable.

Residual in the conductor (light reflector, metallic silver) formed by solidification treatment such as drying treatment and heating (baking) treatment of the silver ink composition (I) using silver β-ketocarboxylate (1). The concentration of raw materials and impurities can be further reduced. In such a conductor, the smaller the amount of raw materials and impurities, the better the contact between the formed metallic silver, for example, the easier the conduction, and the lower the resistivity.

As will be described later, silver 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 or the like known in the art. Metallic silver can be formed. Then, silver β-ketocarboxylate (1) is decomposed at a lower temperature to form metallic silver when used in combination with a reducing agent.

In the present invention, one type of silver β-ketocarboxylate (1) may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof shall be different. , Can be adjusted arbitrarily.

(Silver carboxylate (4))
The silver carboxylate (4) is represented by the general formula (4).
In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (-COOH) or a group represented by the formula "-C (= O) -OAg".
Examples of the aliphatic hydrocarbon group in R ⁸ include those similar to the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 19. However, the aliphatic hydrocarbon group for ^{R 8} is preferably a carbon number of 1 to 15, and more preferably from 1 to 10.

When the aliphatic hydrocarbon group in 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 which may be substituted with a carbonyl group are not particularly limited, and all the methylene groups may be substituted with a carbonyl group. Here, the "methylene group", alone of formula _- not only a group represented by the formula "-CH 2" _- one alkylene in radicals group represented is continuous plurality in "-CH 2" It shall also include the group represented by the formula "-CH _{2-" of.}

The 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), silver isobutyrate ((CH ₃ ) ₂ CH-C (= O) -OAg), silver 2-ethylhexanoate (CH _3- (CH ₂₎₎ ) _3- CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver neodecanoate, silver oxalate (AgO-C (= O) -C (= O) -OAg), or silver malonate (AgO-C (= O) -C (= O) -OAg) AgO-C (= O) -CH _2- C (= O) -OAg) is preferable. 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 of which is the group represented by the formula "-COOH" (HO-C (= O) -C (= O) -OAg, HO -C (= O) -CH _2- C (= O) -OAg) is also preferable.

Even when the silver carboxylate (4) is used, as in the case where the β-ketosilver carboxylate (1) is used, the silver ink composition (I) is subjected to a solidification treatment such as a drying treatment or a heating (baking) treatment. In the formed conductor (light reflector, metallic silver), the concentration of residual raw materials and impurities can be further reduced. Then, silver carboxylate (4) is decomposed at a lower temperature to form metallic silver when used in combination with a reducing agent.

In the present invention, one type of silver carboxylate (4) may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof are arbitrary. Can be adjusted to.

The silver carboxylate is silver 2-methylacetate acetate, silver acetoacetate, silver 2-ethylacetate acetate, silver propionyl acetate, silver isobutyryl acetate, silver pivaloyl acetate, silver caproyl acetate, silver 2-n-butylacetate acetate, 2-benzylacetate. Silver acetate, benzoyl silver acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, silver acetone dicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, shu It is preferably one or more selected from the group consisting of silver acid acid and silver malonate.
Among these silver carboxylates, silver 2-methylacetate acetate, silver acetoacetate, silver isobutyryl acetate and silver pivaloyl acetate are excellent in compatibility with nitrogen-containing compounds (among them, amine compounds) described later, and are silver ink compositions. It is mentioned as particularly suitable for increasing the concentration of (I).

In the silver ink composition (I), the content of silver derived from the organic silver compound is preferably 5% by mass or more, and more preferably 8% by mass or more. When the silver content is in such a range, the formed conductor (light reflector, metallic silver) is superior in quality. The upper limit of the silver content is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 25% by mass in consideration of the handleability of the silver ink composition (I) and the like.
In the present specification, "silver derived from an organic silver compound" is synonymous with silver in the organic silver compound blended at the time of producing the silver ink composition (I), and is blended, unless otherwise specified. After that, the silver that constitutes the organic silver compound, the silver in the decomposition product generated by the decomposition of the organic silver compound after compounding, and the silver itself (metal silver) produced by the decomposition of the organic silver compound after compounding, It is a concept that includes everything.

<Branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms>
The silver ink composition (I) contains a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms in addition to the organic silver compound. Since the silver ink composition (I) contains the branched-chain saturated aliphatic carboxylic acid, metallic silver having high gloss is produced even when printing is performed while heating the object to be printed. Can be formed.

The branched saturated aliphatic carboxylic acid has a structure in which one or more hydrogen atoms of the branched saturated aliphatic hydrocarbon having 8 to 10 carbon atoms are substituted with a carboxy group. In other words, the branched saturated aliphatic carboxylic acid has 8 to 10 carbon atoms in one molecule, and one or more carboxy groups are bonded to the branched saturated aliphatic hydrocarbon group. It is a compound.

The branched saturated aliphatic carboxylic acid is either a monovalent (mono) carboxylic acid having only one carboxy group in one molecule or a polyvalent carboxylic acid having two or more carboxy groups in one molecule. You may.
The number of carboxy groups contained in one molecule of the branched-chain saturated aliphatic carboxylic acid is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. ..

In the branched-chain saturated aliphatic carboxylic acid, the position of the carbon atom to which the carboxy group is bonded is not particularly limited. For example, the carbon atom to which the carboxy group is bonded may be a carbon atom at the end of the molecule or a carbon atom other than the end of the molecule.
When the branched saturated aliphatic carboxylic acid is a polyvalent carboxylic acid, all the carboxy groups may be bonded to different carbon atoms, or two or three carboxy groups are the same carbon atom. May be combined with.

In the branched-chain saturated aliphatic carboxylic acid, the position of the carbon atom in the main chain to which the branched chain is bonded is not particularly limited. For example, the carbon atom to which the branched chain is bonded may be the carbon atom at the end of the side to which the carboxy group of the main chain is bonded, or the side to which the carboxy group of the main chain is bonded. It may be a carbon atom adjacent to the carbon atom at the end on the opposite side (the second carbon atom from the end on the opposite side), the carbon atom at the end on the side to which the above-mentioned carboxy group is bonded, and the above-mentioned. It may be a carbon atom in the main chain located between the carbon atom adjacent to the terminal carbon atom on the side opposite to the side to which the carboxy group is bonded.
Here, the "main chain" means a chain structure in a branched-chain saturated aliphatic carboxylic acid having the largest number of carbon atoms. When there are a plurality of chain structures having the maximum number of carbon atoms, any chain structure may be treated as the main chain. The carbon number of the main chain is always greater than or equal to the carbon number of the branched chain.

The branched saturated aliphatic carboxylic acid is preferably a monocarboxylic acid represented by the following general formula (6) (in this specification, it may be abbreviated as "monocarboxylic acid (6)"). ..
R ^31- C (= O) -OH ... (6)
(In the formula, R ³¹ is a branched-chain alkyl group having 7 to 9 carbon atoms.)

Examples of the branched alkyl group (monovalent saturated aliphatic hydrocarbon group) having 7 to 9 carbon atoms of R ³¹ include a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, and 4 -Methylhexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group , 4,4-Dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 4-ethylpentyl group, 2,2,3-trimethylbutyl group, 1-propylbutyl group, etc. Branched chain alkyl group with 7 carbon atoms;
Isooctyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 5-methylheptyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 4- Ethylhexyl group, 5-ethylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group, 4,4-dimethylhexyl group, 5,5-dimethylhexyl group, 1, 2,3-trimethylpentyl group, 1,2,4-trimethylpentyl group, 2,3,4-trimethylpentyl group, 2,4,4-trimethylpentyl group, 1,4,4-trimethylpentyl group, 3, 4,4-trimethylpentyl group, 1,1,2-trimethylpentyl group, 1,1,3-trimethylpentyl group, 1,1,4-trimethylpentyl group, 1,2,2-trimethylpentyl group, 2, 2,3-trimethylpentyl group, 2,2,4-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,3,3-trimethylpentyl group, 3,3,4-trimethylpentyl group, 1- A branched alkyl group having 8 carbon atoms such as a propylpentyl group and a 2-propylpentyl group;
1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group, 4-methyloctyl group, 5-methyloctyl group, 6-methyloctyl group, 7-methyloctyl group, 6,6-dimethylheptyl group, 5,5-dimethylheptyl group, 4,4-dimethylheptyl group, 3,3-dimethylheptyl group, 2,2-dimethylheptyl group, 1,1-dimethylheptyl group, 1,2-dimethylheptyl group, 1, 3-Dimethylheptyl group, 1,4-dimethylheptyl group, 1,5-dimethylheptyl group, 1,6-dimethylheptyl group, 2,3-dimethylheptyl group, 2,4-dimethylheptyl group, 2,5- Dimethylheptyl group, 2,6-dimethylheptyl group, 3,4-dimethylheptyl group, 3,5-dimethylheptyl group, 3,6-dimethylheptyl group, 4,5-dimethylheptyl group, 4,6-dimethylheptyl Group, 5,6-dimethylheptyl group, 1,2,3-trimethylhexyl group, 1,2,4-trimethylhexyl group, 1,2,5-trimethylhexyl group, 2,3,4-trimethylhexyl group, 2,3,5-trimethylhexyl group, 3,4,5-trimethylhexyl group, 1,1,2-trimethylhexyl group, 1,1,3-trimethylhexyl group, 1,1,4-trimethylhexyl group, 1,1,5-trimethylhexyl group, 1,2,2-trimethylhexyl group, 2,2,3-trimethylhexyl group, 2,2,4-trimethylhexyl group, 2,2,5-trimethylhexyl group, 1,3,3-trimethylhexyl group, 2,3,3-trimethylhexyl group, 3,3,4-trimethylhexyl group, 3,3,5-trimethylhexyl group, 1,4,4-trimethylhexyl group, 2,4,4-trimethylhexyl group, 3,4,4-trimethylhexyl group, 4,4,5-trimethylhexyl group, 1,5,5-trimethylhexyl group, 2,5,5-trimethylhexyl group, 3,5,5-trimethylhexyl group, 4,5,5-trimethylhexyl group, 1,2,3,4-tetramethylpentyl group, 1,1,2,3-tetramethylpentyl group, 1,1, 2,4-Tetramethylpentyl group, 1,1,3,4-tetramethylpentyl group, 1,2,2,3-tetramethylpentyl group, 1,2,2,4-tetramethylpentyl group, 2, 2,3,4-Tetramethylpentyl group, 1,2,3,3-tetramethylpentyl group, 2,3,3,4-tetramethylpentyl group, 1,3,3,4 -Tetramethylpentyl group, 1,2,4,4-tetramethylpentyl group, 2,3,4,5-tetramethylpentyl group, 1,3,4,5-tetramethylpentyl group, 1-ethyl-1 -Methylhexyl group, 1-ethyl-2-methylhexyl group, 1-ethyl-3-methylhexyl group, 1-ethyl-4-methylhexyl group, 1-ethyl-5-methylhexyl group, 2-ethyl-1 -Methylhexyl group, 2-ethyl-2-methylhexyl group, 2-ethyl-3-methylhexyl group, 2-ethyl-4-methylhexyl group, 2-ethyl-5-methylhexyl group, 3-ethyl-1 -Methylhexyl group, 3-ethyl-2-methylhexyl group, 3-ethyl-3-methylhexyl group, 3-ethyl-4-methylhexyl group, 3-ethyl-5-methylhexyl group, 4-ethyl-1 -Methylhexyl group, 4-ethyl-2-methylhexyl group, 4-ethyl-3-methylhexyl group, 4-ethyl-4-methylhexyl group, 4-ethyl-5-methylhexyl group, 1,1-diethyl Pentyl group, 1,2-diethylpentyl group, 1,3-diethylpentyl group, 2,2-diethylpentyl group, 2,3-diethylpentyl group, 3,3-diethylpentyl group, 1-ethyl-1-propyl Examples thereof include branched alkyl groups having 9 carbon atoms such as butyl groups and 2-ethyl-1-propylbutyl groups.

The number of branched chains in one molecule of the branched saturated aliphatic carboxylic acid is preferably 1 to 3, not limited to the monocarboxylic acid (6).
The number of carbon atoms in one branched chain of the branched-chain saturated aliphatic carboxylic acid is preferably 1 to 3, not limited to the monocarboxylic acid (6).
Not limited to the monocarboxylic acid (6), the branched-chain saturated aliphatic carboxylic acid satisfies both of these conditions, that is, the number of branched chains in one molecule is 1 to 3 and one. It is more preferable that the branched chain of No. 1 has 1 to 3 carbon atoms.

The branched saturated aliphatic carboxylic acid has an appropriate reactivity that suppresses a decrease in the glossiness of metallic silver, and is difficult to volatilize from the silver ink composition (I), while the silver ink composition ( It has an appropriate boiling point that is easily vaporized during the solidification treatment of I), and has particularly suitable properties as it exhibits the effects of the present invention.
For example, the boiling point of the branched chain saturated aliphatic carboxylic acid is preferably 180 to 270 ° C, more preferably 200 to 260 ° C, and particularly preferably 215 to 255 ° C. When the boiling point of the branched saturated aliphatic carboxylic acid is equal to or higher than the lower limit, the volatilization of the branched saturated aliphatic carboxylic acid from the silver ink composition (I) is suppressed, and the branched saturated aliphatic carboxylic acid is suppressed. The effect of using the group carboxylic acid is more remarkable. Further, when the boiling point of the branched chain saturated aliphatic carboxylic acid is not more than the above upper limit value, the branched chain saturated aliphatic carboxylic acid in the metallic silver obtained by the solidification treatment of the silver ink composition (I) Metallic silver having more preferable properties such as residual residue is suppressed and high glossiness, conductivity and the like can be obtained.

Branched-chain saturated aliphatic carboxylic acids (e.g., monocarboxylic acid (6)) As a particularly preferred, neodecanoic acid _{(C 9} H 19 COOH), 2-propyl valerate (2-propyl pentanoic acid, (CH ₃ CH ₂ CH ₂ CH (CH ₃ CH ₂ CH ₂ ) COOH), 3,5,5-trimethylhexanoic acid ((CH ₃ ) ₃ CCH ₂ CH (CH ₃ ) CH ₂ COOH) and the like can be mentioned.
In the present specification, neodecanoic acid means a mixture of isomers of a saturated aliphatic monocarboxylic acid having 10 carbon atoms, and a branched chain saturated aliphatic monocarboxylic acid having 10 carbon atoms is always included in the mixture. included. As described above, neodecanoic acid does not mean only one kind of compound.
Then, the combination and ratio of two or more kinds of saturated aliphatic monocarboxylic acids having 10 carbon atoms in neodecanoic acid can be arbitrarily adjusted.

One type of branched-chain saturated aliphatic carboxylic acid may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof are arbitrarily adjusted. can.

As described above, the silver ink composition (I) contains the branched-chain saturated aliphatic carboxylic acid, so that the silver ink composition (I) has glossiness even when printing is performed while heating the object to be printed. Can form high metallic silver. The reason is not clear, but it is presumed as follows.
That is, in the silver ink composition (I) printed on the object to be printed, silver ions (Ag ⁺ ) are generated from the organic silver compound. In this case, oxygen is coordinated to the silver ions by heating the object to be printed (Ag ⁺ ... O). _{Next, silver oxide (Ag 2} O) is generated from the oxygen-coordinated silver ions by a solidification treatment such as a drying treatment or a heating (baking) treatment of the silver ink composition (I) for forming metallic silver. Here, in the case of a silver ink composition that does not contain a branched saturated aliphatic carboxylic acid, silver oxide produced as a by-product is contained in the metallic silver finally produced by the solidification treatment of the silver ink composition. It is presumed that it will be mixed as an impurity and the glossiness of metallic silver will decrease. On the other hand, in the case of the silver ink composition (I) containing the branched saturated aliphatic carboxylic acid, the branched saturated aliphatic carboxylic acid reacts with silver oxide to have 8 to 8 carbon atoms. A silver salt of 10 branched chain saturated aliphatic carboxylic acids (sometimes abbreviated as "branched chain saturated aliphatic carboxylic acid silver" in the present specification) is produced. This branched chain saturated aliphatic carboxylate silver is the above-mentioned silver carboxylate (4), that is, an organic silver compound, and the silver ink composition (I) is solidified in the same manner as the organic silver compound compounded from the beginning. The treatment finally produces metallic silver. As described above, by using the silver ink composition (I) of the present invention, the silver oxide generated due to the heating of the printing object becomes glossy of metallic silver due to the action of the branched chain saturated aliphatic carboxylic acid. It is presumed that metallic silver with high gloss can be formed by converting to metallic silver itself instead of impurities that cause deterioration of properties.

In the silver ink composition (I), the blending amount of the branched chain saturated aliphatic carboxylic acid is preferably 0.01 to 1 mol per 1 mol of the silver atom in the organic silver compound, and is 0. It is more preferably 0.02 to 0.7 mol, and particularly preferably 0.03 to 0.4 mol. When the amount of the branched-chain saturated aliphatic carboxylic acid is in such a range, the effect of forming metallic silver having high gloss is obtained even when printing is performed while heating the object to be printed. It will be higher.

Similar to the branched saturated aliphatic carboxylic acid, metallic silver having high glossiness can be applied to carboxylic acids other than the branched saturated aliphatic carboxylic acid even when printing is performed while heating the object to be printed. There is something that allows the formation of.
The carboxylic acid other than the branched saturated aliphatic carboxylic acid (sometimes referred to as “other carboxylic acid” in the present specification) may be a monovalent carboxylic acid or a divalent or higher carboxylic acid. It may be a polyvalent carboxylic acid, an aliphatic carboxylic acid, or an aromatic carboxylic acid.

The other carboxylic acid preferably does not contain a group having a reducing power such as a formyl group (-C (= O) -H). The silver ink composition (I) containing another carboxylic acid containing no such group suppresses the formation of insoluble matter derived from the organic silver compound during its storage, and has higher handleability at the time of printing. ..

The carbon number of the other carboxylic acid is preferably 5 to 17, and may be, for example, any of 5 to 15, 5 to 13 and 5 to 11.

The boiling point of the other carboxylic acid is preferably 150 to 290 ° C, and may be, for example, any of 155 to 280 ° C, 160 to 270 ° C and 160 to 260 ° C. When the boiling point of the other carboxylic acid is equal to or higher than the lower limit, the volatilization of the other carboxylic acid from the silver ink composition (I) is suppressed, and the effect of using the other carboxylic acid is more remarkable. Obtained in. Further, when the boiling point of the other carboxylic acid is equal to or lower than the upper limit value, the residual of the other carboxylic acid in the metallic silver obtained by the solidification treatment of the silver ink composition (I) is suppressed, and the glossiness is increased. Metallic silver having more preferable characteristics such as high conductivity can be obtained.

As the other carboxylic acids, one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

In the silver ink composition (I), the blending amount of the other carboxylic acid can be the same as the blending amount of the branched-chain saturated aliphatic carboxylic acid described above.

<Nitrogen-containing compound>
The silver ink composition (I) is preferably one in which a nitrogen-containing compound is further blended in addition to the organic silver compound, particularly when the organic silver compound is the silver carboxylate.
The nitrogen-containing compound is an amine compound having 25 or less carbon atoms (hereinafter, may be abbreviated as "amine compound") and 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 with 25 or less carbon atoms with an acid (hereinafter, may be abbreviated as "amine salt derived from an amine compound"), and ammonia reacting with an acid. One or more selected from the group consisting of ammonium salts (hereinafter, may be abbreviated as "ammonia-derived ammonium salts"). That is, the nitrogen-containing compound to be blended may be only one kind, may be two or more kinds, and when two or more kinds are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

[Amine compound, quaternary ammonium salt]
The amine compound has 1 to 25 carbon atoms and may be any of a primary amine, a secondary amine and a tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either chain-like or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or the 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, diamines, etc., in which one or more hydrogen atoms may be substituted with substituents.

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

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

The heteroaryl group constituting the mono (heteroaryl) amine has a hetero atom as an atom constituting the aromatic ring skeleton, and the hetero atom includes, for example, a nitrogen atom, a sulfur atom, an oxygen atom, and the like. Examples include a boron atom. Further, the number of the hetero atoms constituting the aromatic ring skeleton is not particularly limited, and may be one or two or more. 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, all may be different, or only some may be 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 it is preferably a 3 to 12 member ring.

Examples of the heteroaryl group having 1 to 4 nitrogen atoms as a monocyclic group include a pyrrolyl group, a pyrrolinyl group, an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, a pyridazinyl group and a triazolyl group. Examples thereof include a tetrazolyl group, a pyrrolidinyl group, an imidazolidinyl group, a piperidinyl group, a pyrazolydinyl group, a piperazinyl group and the like, and such a heteroaryl group preferably has a 3- to 8-membered ring, and preferably has a 5- to 6-membered ring. More preferred.
Examples of the heteroaryl group that is monocyclic having one oxygen atom include a furanyl group, and such a heteroaryl group preferably has a 3- to 8-membered ring, and 5 to 6 members. It is more preferably a member ring.
Examples of the heteroaryl group having a monocyclic structure having one sulfur atom include a thienyl group, and such a heteroaryl group preferably has a 3- to 8-membered ring, and 5 to 6 members. It is more preferably a member ring.
Examples of the heteroaryl group having a monocyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include an oxazolyl group, an isooxazolyl group, an oxadiazolyl group, a morpholinyl group and the like. The heteroaryl group is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring.
Examples of the heteroaryl group having a monocyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms include a thiazolyl group, a thiadiazolyl group, a thiazolidinyl group and the like, and such a heteroaryl group. Is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring.
Examples of the heteroaryl group having 1 to 5 nitrogen atoms as a polycyclic group include an indolyl group, an isoindryl group, an indridinyl group, a benzimidazolyl group, a quinolyl group, an isoquinolyl group, an indazolyl group and a benzotriazolyl group. , Tetrazolopyridyl group, tetrazolopyridadynyl group, dihydrotriazolopyridadinyl group and the like, and such a heteroaryl group preferably has a 7 to 12-membered ring and 9 to 10-membered rings. It is more preferably a ring.
Examples of the heteroaryl group having 1 to 3 sulfur atoms as a polycyclic group include a dithianaphthalenyl group and a benzothiophenyl group, and such a heteroaryl group has 7 to 12 members. It is preferably a ring, more preferably a 9-10 membered ring.
Examples of the heteroaryl group having a polycyclic group having 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms include a benzoxazolyl group and a benzoxaziazolyl group. The heteroaryl group is preferably a 7-12-membered ring, more preferably a 9-10-membered ring.
Examples of the heteroaryl group having a polycyclic group having 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms include a benzothiazolyl group and a benzothiazolyl group, and such a heteroaryl group can be mentioned. Is preferably a 7 to 12-membered ring, and more preferably a 9 to 10-membered ring.

The diamine may have two amino groups, and the positional relationship between the two amino groups is not particularly limited. As the preferred diamine, for example, in the monoalkylamine, monoarylamine or mono (heteroaryl) amine, one hydrogen atom other than the hydrogen atom constituting the _{amino group (-NH 2) is replaced with an amino group.} Examples include those that have been used.
The diamine preferably has 1 to 10 carbon atoms, and more preferable diamines include, for example, ethylenediamine, 1,3-diaminopropane, and 1,4-diaminobutane.

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

The alkyl group constituting the dialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms or having 3 to 7 carbon atoms. It is preferably a cyclic alkyl group. Further, the two alkyl groups in one molecule of dialkylamine may be the same or different from each other.
Specific examples of the preferred 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. Further, the two aryl groups in one molecule of diallylamine 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 to 12-membered ring. Also, the two heteroaryl groups in a molecule of di (heteroaryl) amine may be the same or different from each other.

Examples of the tertiary amine include trialkylamines and dialkylmonoarylamines 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 a carbon number of 3 to 7 carbon atoms. It is preferably a cyclic alkyl group of. Further, the three alkyl groups in one molecule of trialkylamine may be the same or different from each other. That is, the three alkyl groups may be all the same, all may be different, or only some may be different.
Specific examples of the preferred trialkylamine include N, N-dimethyl-n-octadecylamine, N, N-dimethylcyclohexylamine and the like.

The alkyl group constituting the dialkyl monoarylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 6 carbon atoms or 3 to 6 carbon atoms. It is preferably a cyclic alkyl group of 7. Further, the 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 tetraalkylammonium halide 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 tetraalkylammonium halide may be the same or different from each other. That is, the four alkyl groups may be all the same, all may be different, or only some may be different.
Examples of the halogen constituting the halogenated tetraalkylammonium include fluorine, chlorine, bromine, iodine and the like.
Specific examples of the preferred tetraalkylammonium halide include dodecyltrimethylammonium bromide.

Up to this point, the chain amine compound and the quaternary organic ammonium salt have been mainly described, but the amine compound and the quaternary ammonium salt have a ring-skeleton structure (the nitrogen atom constituting the amine moiety or the ammonium salt moiety). It may be a heterocyclic compound which is a part of the heterocyclic skeleton structure). That is, the amine compound may be a cyclic amine, and the quaternary ammonium salt may be a cyclic ammonium salt. The ring (ring containing nitrogen atoms constituting the amine moiety or ammonium salt moiety) structure at this time may be either monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is particularly limited. However, it may be either an aliphatic ring or an aromatic ring.
If it is a cyclic amine, preferred examples thereof include pyridine and the like.

In the primary amine, secondary amine, tertiary amine and quaternary ammonium salt, the "hydrogen atom which may be substituted with a substituent" is a nitrogen atom constituting an amine moiety or an ammonium salt moiety. It is a hydrogen atom other than the hydrogen atom bonded to. The number of substituents at this time is not particularly limited, and may be one, two or more, and all of the hydrogen atoms may be substituted with substituents. When the number of substituents is plural, these plurality of substituents may be the same or different from each other. That is, the plurality of substituents may all be the same, all may be different, or only some of them 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, an iodine atom and the like.

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

When the aryl group constituting the monoarylamine has a substituent, the aryl group is preferably an aryl group having a halogen atom as a substituent and having 6 to 10 carbon atoms. Specific examples of the monoarylamine having such a substituent include bromophenylamine and the like. 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 the substituent. Specific examples of the dialkylamine having such a substituent include diethanolamine and N-methylbenzylamine.

The amine compounds include n-propylamine, n-butylamine, n-hexylamine, n-octylamine, n-dodecylamine, n-octadecylamine, isobutylamine, sec-butylamine, tert-butylamine, 3-aminopentane, 3-Methylbutylamine, 2-heptylamine, 2-aminooctane, 2-ethylhexylamine, 2-phenylethylamine, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, N-methyl-n-hexylamine, Diisobutylamine, N-methylbenzylamine, di (2-ethylhexyl) amine, 1,2-dimethyl-n-propylamine, N, N-dimethyl-n-octadecylamine or N, N-dimethylcyclohexylamine. Is preferable.
Among these amine compounds, 2-ethylhexylamine has excellent compatibility with the silver carboxylate, is particularly suitable for increasing the concentration of the silver ink composition (I), and further has a surface roughness of metallic silver. It is mentioned as particularly suitable for reduction.

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

[Ammonia-derived ammonium salt]
In the present invention, the ammonium salt derived from ammonia is an ammonium salt formed by reacting ammonia with an acid. Here, as the acid, the same acid as in the case of the ammonium salt derived from the amine compound can be mentioned.
Examples of the ammonium salt derived from ammonia include, but are not limited to, ammonium chloride.

In the present invention, the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from ammonia may be used alone or in combination of two or more. Well, when two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.
Then, as the nitrogen-containing compound, one selected from the group consisting of the amine compound, the quaternary ammonium salt, the ammonium salt derived from the amine compound and the ammonium salt derived from ammonia may be used alone. Two or more kinds may be used in combination, and when two or more kinds are used in combination, their combinations and ratios can be adjusted arbitrarily.

In the present invention, for example, as the nitrogen-containing compound, a first nitrogen-containing compound having 8 or more carbon atoms and a second nitrogen-containing compound having 7 or less carbon atoms may be used in combination.
When the first nitrogen-containing compound and the second nitrogen-containing compound are used in combination, the ratio of the blending amount of the second nitrogen-containing compound to the blending amount of the first nitrogen-containing compound in the silver ink composition (I) is 0 mol%. It is larger, preferably less than 18 mol%, more preferably 1 to 17 mol%. When the ratio is in such a range, for example, a fine linear silver layer can be formed more stably.

When the nitrogen-containing compound is used, in the silver ink composition (I), the blending amount of the nitrogen-containing compound is preferably 0.3 to 15 mol per 1 mol of the blended amount of the organic silver compound, and 0. It is more preferably 3 to 12 mol, particularly preferably 0.3 to 8 mol, and may be any of, for example, 1 to 8 mol, 2.5 to 8 mol, and 4 to 8 mol. good. When the blending amount of the nitrogen-containing compound is in such a range, the stability of the silver ink composition (I) is further improved, and the quality of metallic silver is further improved.

<Alcohol>
The silver ink composition (I) is preferably one in which alcohol is further blended in addition to the organic silver compound.

The alcohol is preferably acetylene alcohols represented by the following general formula (2) (hereinafter, may be abbreviated as "acetylene alcohol (2)").

（式中、Ｒ’及びＲ’’は、それぞれ独立に水素原子、炭素数１〜２０のアルキル基、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である。）

(In the formula, R'and R'' are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or phenyl groups in which one or more hydrogen atoms may be substituted with substituents, respectively.)

[Acetylene alcohol (2)]
The acetylene alcohol (2) is represented by the general formula (2).
In the formula, R'and R'' are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or phenyl groups in which one or more hydrogen atoms may be substituted with substituents, respectively.
The alkyl group having 1 to 20 carbon atoms in R'and R'' may be linear, branched chain or cyclic, and when cyclic, it may be monocyclic or polycyclic. Examples of the alkyl group in R'and R'' include the same as the alkyl group 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 and the fat. Examples thereof include a monovalent group in which a group hydrocarbon 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 and the like. These substituents are the same as the substituents in which the hydrogen atom of the phenyl group in R may be substituted. The number and position of the substituents in the phenyl group having a substituent are not particularly limited, and when the number of the substituents is a plurality, the plurality of the substituents may be the same or different from each other.

R'and R'' are preferably hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and preferably hydrogen atoms or linear or branched alkyl groups having 1 to 10 carbon atoms. More preferred.

Preferred acetylene alcohols (2) include, for example, 3,5-dimethyl-1-hexin-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 2 -Propyne-1-ol, 4-ethyl-1-octyne-3-ol, 3-ethyl-1-heptin-3-ol and the like can be mentioned.

When the acetylene alcohol (2) is used, in the silver ink composition (I), the blending amount of the acetylene alcohol (2) may be 0.01 to 0.7 mol per 1 mol of the organic silver compound. It is preferably 0.02 to 0.5 mol, more preferably 0.02 to 0.3 mol. When the blending amount of the acetylene alcohol (2) is in such a range, the stability of the silver ink composition (I) is further improved.

As for the alcohol, one kind may be used alone, two or more kinds may be used in combination, and when two or more kinds are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

<Other ingredients>
The silver ink composition (I) may be a mixture of other components other than the organic silver compound, the branched saturated aliphatic carboxylic acid, the nitrogen-containing compound and the alcohol.
The other components in the silver ink composition (I) can be arbitrarily selected depending on the intended purpose, and are not particularly limited. Among the other components, preferable ones include, for example, a solvent other than alcohol, which can be arbitrarily selected according to the type and amount of the compounding component.
As the other components in the silver ink composition (I), one kind may be used alone, two or more kinds may be used in combination, and when two or more kinds are used in combination, the combination and ratio thereof shall be , Can be adjusted arbitrarily.

[solvent]
The solvent is not particularly limited as long as it is other than alcohol (those having no hydroxyl group).
However, the solvent is preferably liquid at room temperature. In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

Examples of the solvent include aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; pentane, hexane, cyclohexane, heptane, octane, cyclooctane, nonane, decane, undecane, dodecane, tridecane, and the like. Aliper hydrocarbons such as tetradecane, pentadecane and decahydronaphthalene; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, monomethyl glutarate, dimethyl glutarate; diethyl ether, tetrahydrofuran (THF), 1,2- Ethers such as dimethoxyethane (dimethyl cellosolve); ketones such as acetone, methyl ethyl ketone (MEK), cyclohexanone; nitriles such as acetonitrile; amides such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide and the like. ..

The blending amount of the other component in the silver ink composition (I) may be appropriately selected according to the type of the other component.
For example, when the other component is a solvent other than alcohol, the blending amount of the solvent may be selected according to the purpose such as the viscosity of the silver ink composition (I). However, usually, in the silver ink composition (I), the ratio of the blending amount of the solvent to the total blending component is preferably 25% by mass or less, more preferably 20% by mass or less, and 15% by mass. It is particularly preferable that it is% or less.
When the other component is a component other than the solvent, the ratio of the compounding amount of the other component to the total amount of the compounding component in the silver ink composition (I) is preferably 10% by mass or less. More preferably, it is 5% by mass or less.
The ratio of the blending amount of the other component to the total blending component is 0 mass, that is, the silver ink composition (I) sufficiently exhibits its effect even if the other component is not blended.

In the silver ink composition (I), all the compounding components may be dissolved, or some or all the components may be dispersed without being dissolved, but all the compounding components are dissolved. It is preferable that the components are uniformly dispersed.

○ Method for Producing Silver Ink Composition (I) The silver ink composition (I) contains the organic silver compound, a branched saturated aliphatic carboxylic acid, and, if necessary, components other than these. can get. After blending each component, the obtained product may be used as it is as the silver ink composition (I), or the product obtained by continuously performing a known purification operation as necessary may be used as the silver ink (I) composition. May be good. In the present invention, particularly when silver β-ketocarboxylate (1) is used as the organic silver compound, impurities that reduce glossiness and conductivity are not generated when each of the above components is blended, or such. The amount of impurities produced can be suppressed to an extremely small amount. Therefore, even if the silver ink composition (I) that has not been refined is used, metallic silver having sufficient glossiness and conductivity can be obtained.

The blending order of each component is not particularly limited. As an example of a preferable blending method of each component, a method of blending the branched chain saturated aliphatic carboxylic acid at the end can be mentioned. That is, as an example of a preferable production method of the silver ink composition (I), a production in which all the components other than the branched-chain saturated aliphatic carboxylic acid are blended and then the branched-chain saturated aliphatic carboxylic acid is finally blended. The method can be mentioned.

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all components may be added sequentially and mixed. good.
The mixing method is not particularly limited, and a method of rotating and mixing a stirrer or a stirring blade or the like; a method of mixing using a mixer, a three-roll roll, a kneader or a bead mill or the like; a method of adding ultrasonic waves and the like, etc. It may be appropriately selected from known methods.
In the silver ink composition (I), when the undissolved components are uniformly dispersed, it is preferable to apply, for example, the method of dispersing using the above-mentioned three rolls, a kneader, a bead mill or the like.

The temperature at the time of compounding is not particularly limited as long as each compounding component is not deteriorated, but is preferably −5 to 60 ° C. Then, the temperature at the time of blending may be appropriately adjusted according to the type and amount of the blending component so that the mixture obtained by blending has a viscosity that makes it easy to stir.
The blending time is also not particularly limited as long as each blending component is not deteriorated, but is preferably 10 minutes to 36 hours.

<Carbon dioxide>
The silver ink composition (I) may be further supplied with carbon dioxide. Such a silver ink composition (I) has a high viscosity, and for example, a flexographic printing method, a screen printing method, a gravure printing method, a gravure offset printing method, a pad printing method, or the like, which requires thickening of ink. Suitable for application to law.

Carbon dioxide may be supplied at any time during the production of the silver ink composition (I).
The carbon dioxide (CO ₂ ) supplied may be either gaseous or solid (dry ice), or both gaseous and solid. It is presumed that the supplied carbon dioxide dissolves in the object to be supplied and acts on any of the contained components to increase the viscosity of the obtained silver ink composition (I).

The carbon dioxide gas may be supplied by various known methods of blowing the gas into the liquid, and a suitable supply method may be appropriately selected. For example, a method of immersing one end of a pipe in a supply target, connecting the other end to a carbon dioxide gas supply source, and supplying carbon dioxide gas to the supply target through this pipe can be mentioned. At this time, carbon dioxide gas may be supplied directly from the end of the pipe, but for example, a large number of voids that can serve as gas flow paths such as porous ones are provided to diffuse the introduced gas. A gas diffusion member capable of being released as minute bubbles may be connected to the end of the pipe, and carbon dioxide gas may be supplied through the gas diffusion member. Further, carbon dioxide gas may be supplied while stirring the object to be supplied. By doing so, carbon dioxide can be efficiently supplied.

The amount of carbon dioxide gas supplied may be appropriately adjusted according to the amount of the object to be supplied, the viscosity of the target silver ink composition (I), and the like, and is not particularly limited. For example, in order to obtain about 100 to 1000 g of a silver ink composition (I) having a viscosity at 20 to 25 ° C. of 5 Pa · s or more, it is preferable to supply 100 L or more of carbon dioxide gas, and 200 L or more may be supplied. More preferred. Although the viscosity of the silver ink composition (I) at 20 to 25 ° C. has been described here, the temperature when the silver ink composition (I) is used is not limited to 20 to 25 ° C. and is arbitrary. Can be selected. In addition, in this specification, "viscosity" means what was measured using an ultrasonic vibration viscometer unless otherwise specified.

The flow rate of carbon dioxide gas may be appropriately adjusted in consideration of the required supply amount of carbon dioxide gas, but is preferably 0.5 mL / min or more per 1 g of the object to be supplied, and is preferably 1 mL / min or more. More preferably. The upper limit of the flow rate is not particularly limited, but it is preferably 40 mL / min per 1 g of the supply object in consideration of handleability and the like.
Then, the carbon dioxide gas supply time may be appropriately adjusted in consideration of the required carbon dioxide gas supply amount and the flow rate.

The temperature of the object to be supplied when the carbon dioxide gas is supplied is preferably 5 to 70 ° C, more preferably 7 to 60 ° C, and particularly preferably 10 to 50 ° C. When the temperature is at least the lower limit value, carbon dioxide can be supplied more efficiently, and when the temperature is at least the upper limit value, the silver ink composition (I) having better quality with less impurities can be obtained. can get.

The flow rate and supply time of the carbon dioxide gas, and the temperature at the time of supplying the carbon dioxide gas may be adjusted within an appropriate range while mutually considering their respective values. For example, even if the temperature is set low, carbon dioxide gas flow rate is set high, carbon dioxide gas supply time is set long, or both are performed efficiently. Can supply carbon. Further, even if the flow rate of carbon dioxide gas is set to be small, carbon dioxide can be efficiently produced by raising the temperature, setting the supply time of carbon dioxide gas to be long, or both. Can be supplied. That is, by flexibly combining the values in the above numerical range exemplified as the flow rate of carbon dioxide gas and the temperature at the time of supplying carbon dioxide gas while considering the supply time of carbon dioxide gas, silver ink of good quality is obtained. The composition (I) is efficiently obtained.

The carbon dioxide gas is preferably supplied while stirring the object to be supplied. By doing so, the supplied carbon dioxide gas can be more uniformly diffused into the supply target, and carbon dioxide can be supplied more efficiently.
The stirring method at this time may be the same as the case of the mixing method at the time of producing the silver ink composition (I) without using carbon dioxide.

Dry ice (solid carbon dioxide) may be supplied by adding dry ice to the object to be supplied. The whole amount of dry ice may be added all at once, or may be divided and added stepwise (continuously with a time zone during which the addition is not performed).
The amount of dry ice used may be adjusted in consideration of the above-mentioned amount of carbon dioxide gas supplied.
During and after the addition of dry ice, it is preferable to stir the object to be supplied. For example, it is preferable to stir the silver ink composition (I) in the same manner as in the production of the above silver ink composition (I) without using carbon dioxide. By doing so, carbon dioxide can be efficiently supplied.
The temperature at the time of stirring may be the same as that at the time of supplying carbon dioxide gas. Further, the stirring time may be appropriately adjusted according to the stirring temperature.

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

In the silver ink composition (I) having a viscosity higher than usual due to the supply of carbon dioxide as described above, metallic silver may be formed from at least a part of the organic silver compound, and the metallic silver may be precipitated. .. At this time, when the viscosity of the silver ink composition (I) is high, the aggregation of the precipitated metallic silver is suppressed, and the dispersibility of the metallic silver in the obtained silver ink composition (I) is improved. The metallic silver obtained by forming metallic silver by the method described later using such a silver ink composition (I) has a low viscosity, that is, a silver ink composition (I) to which carbon dioxide is not supplied. It has higher glossiness, higher conductivity (lower volume resistivity), smaller surface roughness, and more preferable characteristics than metallic silver when.

〇 Silver ink composition (II)
In the silver ink composition (II), an organic silver complex is blended as the organic silver compound, and a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms (the branched saturated aliphatic carboxylic acid) and It is made by blending a nitrogen-containing compound.
As such a silver ink composition (II), for example, the organic silver complex is formed by the reaction of the precursor compound of the organic silver complex and the other nitrogen-containing compound, and the excess nitrogen-containing compound is formed. Examples thereof include a reaction solution containing the remaining reaction solution and a branched chain saturated aliphatic carboxylic acid. More specifically, such a silver ink composition (II) includes a silver ink composition (II) in which a branched chain saturated aliphatic carboxylic acid is further blended with the one described in Japanese Patent No. 5243409.
That is, as the silver ink composition (II), for example, a silver compound represented by the following general formula (91) (in this specification, it may be abbreviated as “silver compound (91)”) and the following. A compound represented by the general formula (92) (in the present specification, it may be abbreviated as “nitrogen-containing compound (92)”) and a compound represented by the following general formula (93) (in the present specification). , Which may be abbreviated as "nitrogen-containing compound (93)"), and further contains an organic silver complex obtained by reacting with one or more kinds of nitrogen-containing compounds selected from the group. , A liquid composition containing the nitrogen-containing compound and a branched chain saturated aliphatic carboxylic acid.

（式中、ｎ_１０１は、１〜３の整数であり；Ｘ^１０１は、酸素原子、硫黄原子、ハロゲン原子、シアノ基、シアネート基、カーボネート基、ニトレート基、ニトライト基、サルフェート基、ホスフェート基、チオシアネート基、クロレート基、パークロレート基、テトラフルオロボレート基、アセチルアセトネート基、カルボキシレート基、及びこれらの誘導体からなる群よから選択される基であり；Ｒ^１０１〜Ｒ^１１１は、それぞれ独立に、水素原子、炭素数１〜３０の脂肪族若しくは脂環族アルキル基又はアリール基、官能基が置換されたアルキル基又はアリール基、及びヘテロ環式基からなる群から選択される基であり、ただし、Ｒ^１０１〜Ｒ^１１１がすべて水素原子になることはない。）

(In the formula, n ₁₀₁ is an integer from 1 to 3; X ¹⁰¹ is an oxygen atom, a sulfur atom, a halogen atom, a cyano group, a cyanate group, a carbonate group, a nitrate group, a nitrite group, a sulfate group, a phosphate group, It is a group selected from the group consisting of a thiocyanate group, a chlorate group, a perchlorate group, a tetrafluoroborate group, an acetylacetonate group, a carboxylate group, and derivatives thereof; R ^{101 to} R ¹¹¹ are each independently. , A group selected from the group consisting of hydrogen atoms, aliphatic or alicyclic alkyl or aryl groups having 1 to 30 carbon atoms, alkyl or aryl groups substituted with functional groups, and heterocyclic groups. However, ^{not all R 101 to} R ¹¹¹ become hydrogen atoms.)

Examples of the organic silver complex include a compound represented by the following general formula (95) -1 (in the present specification, it may be abbreviated as "organic silver complex (95) -1"), and the following general. Examples thereof include a compound represented by the formula (95) -2 (in this specification, it may be abbreviated as "organic silver complex (95) -2").

（式中、Ｒ^１０１〜Ｒ^１１１は、上記と同じであり；ｍ_１０１及びｍ_１０２は、それぞれ独立に、０．５〜１．５である。）

(In the formula, R ^{101 to} R ¹¹¹ are the same as above; m ₁₀₁ and m ₁₀₂ are independently 0.5 to 1.5, respectively.)

[Silver compound (91)]
Examples of the silver compound (91) include silver oxide, silver thiocyanate, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, and silver tetrafluoride. Examples thereof include silver acetylacetonated, silver acetate, silver lactate, and silver oxalate.

As the silver compound (91), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

In the silver ink composition (II), the content of silver derived from the silver compound (91) is preferably 2% by mass or more, and more preferably 4% by mass or more. When the silver content is in such a range, the formed conductor (light reflector, metallic silver) is superior in quality. The upper limit of the silver content is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 20% by mass in consideration of the handleability of the silver ink composition (II) and the like.
Here, "silver derived from the silver compound (91)" is synonymous with silver in the silver compound (91) blended at the time of producing the silver ink composition (II) unless otherwise specified. , Silver in the reaction product produced by the reaction of the silver compound (91) after compounding, and silver produced by the reaction of the silver compound (91) after compounding. It is a concept that includes all of itself (metal silver).

[Nitrogen-containing compound (92)]
The nitrogen-containing compound (92) is an ammonium carbamate-based compound.
In the nitrogen-containing compound (92), R ^{101 to} R ¹⁰⁵ independently represent a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, and a pentyl. Group, hexyl group, heptyl group, octyl group, isooctyl group, ethylhexyl group, nonyl group, decyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxyethyl group, methoxypropyl group, cyanoethyl group, methoxyethoxyethyl Group, methoxyethoxyethoxyethyl group, hexamethyleneiminyl group, morpholino group, piperidinyl group, piperazinyl group, pyrrolyl group, imidazolyl group, pyridinyl group, carboxymethyl group, trimethoxysilylpropyl group, triethoxysilylpropyl group, phenyl group , A methoxyphenyl group, a cyanophenyl group, a trill group, a benzyl group, or a group in which a part of these groups is substituted is preferable. However, ^{not all of R 101 to} R ¹⁰⁵ become hydrogen atoms.

Examples of the nitrogen-containing compound (92) include ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, tert-butylammonium tert-butylcarbamate, and 2-ethylhexylammonium 2-. Ethylhexyl Carbamate, Octadecyl Ammonium Octadecyl Carbamate, 2-methoxyethyl Ammonium 2-methoxyethyl Carbamate, 2-Cyanoethyl Ammonium 2-Cyanoethyl Carbamate, Dibutylammonium Dibutyl Carbamate, Dioctadecyl Ammonium Dioctadecyl Carbamate, Methyl Decyl Ammonium Methyl Decyl Carbamate, Hexamethylene Imine Ammonium hexamethyleneimine carbamate, morpholinoammonum morpholinocarbamate, pyridinium ethylhexyl carbamate, benzylammonium benzyl carbamate, triethoxysilylpropylammonium triethoxysilylpropyl carbamate and the like can be mentioned.
Among these nitrogen-containing compounds (92), 2-ethylhexyl ammonium 2-ethylhexyl carbamate has excellent compatibility with the silver compound (91) and is particularly suitable for increasing the concentration of the silver ink composition (II). Further, it is mentioned as being particularly suitable for reducing the surface roughness of metallic silver.

As the nitrogen-containing compound (92), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

The nitrogen-containing compound (92) can be produced by a known method, for example, the method described in US Pat. No. 4,542,214.

[Nitrogen-containing compound (93)]
The nitrogen-containing compound (93) is an ammonium carbonate-based compound.
In the nitrogen-containing compound (93), R ^{106 to} R ¹¹¹ are the same as those ^{in R 101 to} R ¹⁰⁵ in the nitrogen-containing compound (92). However, ^{not all of R 106 to} R ¹¹¹ become hydrogen atoms.

Examples of the nitrogen-containing compound (93) include ethylammonium ethyl carbonate, isopropylammonium isopropylcarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, tert-butylammonium tert-butylcarbonium, and 2-ethylhexylammonium 2-. Ethylhexyl carbonate, 2-methoxyethylammonium 2-methoxyethyl carbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, octadecylammonium octadecyl carbonate, dibutylammonium dibutyl carbonate, dioctadecylammonium dioctadecyl carbonate, methyldecylammonium methyldecyl carbonate, hexamethylene i Minylammonium hexamethyleneiminyl carbonate, morpholinoammonium morpholinocarbonate, benzylammonium benzylcarbonate, triethoxysilylpropylammonium triethoxysilylpropylcarbonate and the like can be mentioned.

As the nitrogen-containing compound (93), one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

The nitrogen-containing compound (93) can be produced by a known method, for example, the method described in US Pat. No. 4,542,214.

The nitrogen-containing compound to be reacted with the silver compound (91) may be only one or more nitrogen-containing compounds (92), or only one or two or more nitrogen-containing compounds (93). It may be both one or more nitrogen-containing compounds (92) and one or two or more nitrogen-containing compounds (93).

The reaction of the silver compound (91) with one or more selected from the group consisting of the nitrogen-containing compound (92) and the nitrogen-containing compound (93) is, for example, in a normal pressure state under a nitrogen atmosphere. It can be carried out with or under pressure without using a solvent.

[solvent]
The reaction may be carried out using a solvent. Examples of the solvent at this time include water; alcohols such as methanol, ethanol, isopropanol and butanol; glycols such as ethylene glycol and glycerin; acetates such as ethyl acetate, butyl acetate and carbitol acetate; diethyl ether, tetrahydrofuran, dioxane and the like. Ethers; ketones such as methyl ethyl ketone and acetone; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride.
As the solvent, one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

The solvent may be a compounding component of the silver ink composition (II).

At the time of the reaction, the total amount of the nitrogen-containing compound (92) and the nitrogen-containing compound (93) used is 1 to 4 times the molar amount of the amount of silver atoms in the silver compound (91) used (). The value of [total amount of nitrogen-containing compound (92) and nitrogen-containing compound (93) used (mol)] / [amount of silver atoms in silver compound (91) used (mol)] is 1 to 4). Is preferable.

[Branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms]
The branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms in the silver ink composition (II) is a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms in the silver ink composition (I) (the branched). It is the same as the chain saturated aliphatic carboxylic acid).
It is presumed that the branched-chain saturated aliphatic carboxylic acid in the silver ink composition (II) exhibits the same action as the branched-chain saturated aliphatic carboxylic acid in the silver ink composition (I).

In the silver ink composition (II), the blending amount of the branched saturated aliphatic carboxylic acid is preferably 0.01 to 1 mol per 1 mol of the silver atom in the organic silver complex, and is 0. It is more preferably 0.02 to 0.7 mol, and particularly preferably 0.03 to 0.4 mol. When the amount of the branched-chain saturated aliphatic carboxylic acid is in such a range, the effect of forming metallic silver having high gloss is obtained even when printing is performed while heating the object to be printed. It will be higher.
When the precursor compound of the organic silver complex is used in the production of the silver ink composition (II), the branched chain saturated aliphatic carboxylic acid is added per 1 mol of the amount of silver atoms in the precursor compound. The blending amount can be in the above-mentioned numerical range.

As described above, the silver ink composition (II) contains the branched-chain saturated aliphatic carboxylic acid, so that the silver ink composition (II) has glossiness even when printing is performed while heating the object to be printed. Can form high metallic silver. The reason is not clear, but it is presumed to be the same as in the case of the silver ink composition (I) described above.

The silver ink composition of the present invention is as described above.
Next, a method of using the silver ink composition will be described.

<< How to use the silver ink composition >>
The silver ink composition is not limited to the silver ink composition (I) and the silver ink composition (II), and the silver ink composition is suitable for applying a printing method as a method for adhering to an object, but is applied. It is also suitable for applying a method other than the printing method such as the method.
The silver ink composition is particularly suitable for application to a method of adhering to an object, which requires heating of the object to be adhered (object).

Examples of the printing method include a screen printing method, a flexo printing method, an offset printing method, a dip printing method, an inkjet printing method, a dispenser printing method, a jet dispenser printing method, a gravure printing method, and a gravure offset printing method. Pad printing method and the like can be mentioned.
Among these, the printing method is preferably an inkjet printing method.

As the coating method, for example, various coaters such as a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, and a gravure coater, a wire bar, and the like are used. The method and the like can be mentioned.

When metallic silver is formed by printing the silver ink composition and solidifying treatment such as drying treatment and heating (baking) treatment of the printed silver ink composition, the silver ink composition on the printing object is formed. The thickness of metallic silver can be adjusted by adjusting the amount or the blending amount of the organic silver compound in the silver ink composition.
Similarly, when the coating method is adopted instead of the printing method, metallic silver is similarly adjusted by adjusting the amount of the silver ink composition on the object to be coated or the blending amount of the organic silver compound in the silver ink composition. You can adjust the thickness of the ink.

When the silver ink composition is dried, it may be carried out by a known method. That is, the drying treatment may be performed, for example, under normal pressure, reduced pressure, or blowing conditions, and may be performed under any of an atmosphere and an inert gas atmosphere. The drying temperature is not particularly limited, and either heat drying or room temperature drying may be used. A preferred drying method when heat treatment is not required includes, for example, a method of drying in the air at 18 to 30 ° C.

When the silver ink composition is heated (baked), the conditions may be appropriately adjusted according to the type of the compounding components of the silver ink composition. Usually, the heating temperature is preferably 60 to 370 ° C, more preferably 70 to 280 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 24 hours, more preferably 1 minute to 12 hours. Among the organic silver compounds, the silver carboxylate, particularly β-ketosilver (1), is different from the material for forming metallic silver such as silver oxide, and does not use a reducing agent known in the art. Also decomposes at low temperatures. Then, reflecting such a decomposition temperature, the silver ink composition can form metallic silver at an extremely lower temperature than the conventional one, as described above.

When the silver ink composition is attached to an object having low heat resistance and heated (baked), the heating temperature is preferably less than 130 ° C, more preferably 125 ° C or lower, and 120 ° C or lower. Is particularly preferable.

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

In the present specification, "humidification" means artificially increasing the humidity unless otherwise specified, and preferably the relative humidity is 5% or more. It can be said that the relative humidity of 5% is clearly artificially increased because the humidity in the treatment environment becomes extremely low due to the high treatment temperature during the heat treatment.

When the heat treatment of the silver ink composition is performed under humidified conditions, the relative humidity is preferably 10% or more, more preferably 30% or more, further preferably 50% or more, and 70%. The above is particularly preferable, and it may be 90% or more or 100%. Then, the heat treatment under the humidifying condition may be performed by spraying high-pressure steam heated to 100 ° C. or higher. By heat-treating under humidifying conditions in this way, higher-purity metallic silver can be formed in a short time.

The heat treatment of the silver ink composition may be performed in two steps. For example, in the first-step heat treatment, the silver ink composition is mainly dried instead of forming metallic silver, and in the second-step heat treatment, metallic silver is formed to the end. In this case, the first step of the heat treatment includes, for example, heating of the silver ink composition by the print object when printing is performed with the silver ink composition while heating the print object as described above. May be applicable.

In the first stage heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding component of the silver ink composition, but is preferably 60 to 120 ° C, and may be 70 to 110 ° C. .. The heating time may be adjusted according to the heating temperature, but is usually preferably 5 seconds to 12 hours, more preferably 30 seconds to 2 hours.
In the second stage heat treatment, the heating temperature may be appropriately adjusted according to the type of the compounding components of the silver ink composition so that metallic silver is formed well, but it may be 60 to 280 ° C. It is preferably 70 to 260 ° C., more preferably 70 to 260 ° C. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 12 hours, more preferably 1 minute to 10 hours.
When the silver ink composition is attached to an object having low heat resistance and heat (baked), the heating temperature in the first and second heat treatments is preferably less than 130 ° C., 125. It is more preferably ° C. or lower, and particularly preferably 120 ° C. or lower.

The heat treatment of the silver ink composition described so far is performed in the gas phase, but when the heat treatment of the silver ink composition is performed in two steps, the heat treatment of the second step is the gas phase. It may be done in the liquid phase instead of inside. The silver ink composition that has been completely or to some extent dried after the first-step heat treatment can be brought into contact with the heated liquid to perform the second-step heat treatment without damaging its shape. The heat treatment of the silver ink composition in the liquid phase of the second stage after the heat treatment of the first step is preferably performed by immersing the silver ink composition in the heated liquid. The heating temperature and heating time in the heat treatment in this liquid phase are the same as the heating temperature and heating time in the second stage heat treatment described above.
The heated liquid is preferably hot water (heated water), and the second-step heat treatment is performed by immersing the silver ink composition subjected to the first-step heat treatment in hot water, that is, by boiling water. It is preferable to do so.
When the second step heat treatment is performed in the liquid phase, the metallic silver formed by this heat treatment may be further dried.

When the second step heat treatment of the silver ink composition is carried out in the liquid phase, it is preferable that the first step heat treatment of the silver ink composition is carried out under non-humidified conditions.
In addition, in this specification, "non-humidifying" means that the above-mentioned "humidifying" is not performed, that is, the humidity is not artificially increased, and the relative humidity is preferably less than 5%. ..

When the heat treatment under humidifying conditions is adopted, it is particularly preferable that the heat treatment of the silver ink composition is carried out by the following two-step method. That is, in the first-stage heat treatment, the silver ink composition is mainly dried under non-humidifying conditions instead of forming metallic silver as described above, and in the second-stage heat treatment, under humidifying conditions. It is particularly preferable to heat-treat the silver ink composition by forming the metallic silver to the end as described above.

When the second stage heat treatment is performed under humidified conditions, the heating temperature during the first stage heat treatment under non-humidified conditions is preferably 60 to 120 ° C., even if it is 70 to 110 ° C. good. The heating time is preferably 5 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and particularly preferably 30 seconds to 15 minutes.
The heating temperature during the heat treatment under the second stage humidifying condition, which is performed after the heat treatment under the first stage non-humidifying condition, is preferably 60 to 140 ° C., preferably 70 to 130 ° C. Is more preferable. The heating time is preferably 1 minute to 2 hours, more preferably 1 minute to 1 hour, and particularly preferably 1 minute to 30 minutes.
When the silver ink composition is attached to an object having low heat resistance and heated (baked), the first stage heat treatment under non-humidified conditions and the second stage heat treatment under humidified conditions are performed. The heating temperature is preferably less than 130 ° C., more preferably 125 ° C. or lower, and particularly preferably 120 ° C. or lower.

The material of the target object (base material) to be adhered (printed) to the silver ink composition is not particularly limited and can be arbitrarily selected according to the purpose.
Preferred materials for the target product include, for example, polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polymethylpentene (PMP), polycycloolefin, polystyrene (PS), and the like. Acrylic resin such as polyvinyl acetate (PVAC), polymethyl methacrylate (PMMA), AS resin, ABS resin, polyamide (PA), polyimide, polyamideimide (PAI), polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PET) PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylensulfide (PPS), polysulfone (PSF), polyethersulfone (PES), polyetherketone (PEK) ), Polyetheretherketone (PEEK), Polycarbonate (PC), Polyurethane, Polyphenylene ether (PPE), Modified polyphenylene ether (m-PPE), Polyallylate, Epoxy resin, Melamine resin, Phenolic resin, Urea resin and other synthetic resins. Can be mentioned.
In addition to the above, preferred materials for the target product include ceramics such as glass and silicon, and paper.
Further, the target product may be a combination of two or more kinds of materials such as a glass epoxy resin and a polymer alloy.

The thickness of the target object (base material) to be adhered (printed) to the silver ink composition is not particularly limited, but is preferably 10 to 5000 μm, more preferably 10 to 3000 μm.

<< Metallic silver, laminate >>
The silver ink composition of the present invention can form a highly glossy light reflector by a solidification treatment such as a drying treatment or a heating (baking) treatment. This light reflector contains metallic silver produced from the organic silver compound as a main component. That is, by using the silver ink composition of the present invention, metallic silver having high gloss can be formed. Then, even if printing is performed while heating the object to be printed using this silver ink composition, metallic silver having high gloss can be formed.
The silver ink composition of the present invention is a laminate comprising a base material and a metallic silver layer formed on the substrate, for producing a laminate having high gloss of the metallic silver layer. It is suitable for use in.

The metallic silver obtained by using the silver ink composition of the present invention has excellent light reflectance, for example, light reflectance having a wavelength of 400 to 700 nm.
For example, even when printing is performed while heating the object to be printed at 60 ° C., the reflectance of light having a wavelength of 550 nm of metallic silver can be preferably 50% or more, for example, 55% or more and 60%. As mentioned above, it can be any of 65% or more, 70% or more, 75% or more, etc., but these are examples.
Further, the upper limit of the reflectance of light having a wavelength of 550 nm of the above-mentioned metallic silver is not particularly limited and may be, for example, 90%, which is an example.

As described above, when printing is performed using the silver ink composition of the present invention while heating the object to be printed at 60 ° C. to form metallic silver, the reflectance of light having a wavelength of 550 nm of the metallic silver is , It can be appropriately adjusted so as to be within a range set by arbitrarily combining any of the above-mentioned preferable lower limit values and upper limit values. For example, the reflectance of the light can be preferably 50 to 90%, such as 55 to 90%, 60 to 90%, 65 to 90%, 70 to 90%, 75 to 90%, and the like. can do. However, these are just examples.

In the light reflector obtained by using the silver ink composition of the present invention, the ratio of metallic silver can be sufficiently high that the light reflector can be regarded as apparently composed only of metallic silver, and light reflection can be achieved. The ratio of metallic silver in the body is preferably 97% by mass or more, more preferably 98% by mass or more, and particularly preferably 99% by mass or more. The upper limit of the ratio of metallic silver in the light reflector is, for example, 100% by mass, 99.9% by mass, 99.8% by mass, 99.7% by mass, 99.6% by mass, 99.5% by mass, and so on. It can be, but is not limited to, 99.4% by mass, 99.3% by mass, 99.2% by mass, and 99.1% by mass.

FIG. 1 is a cross-sectional view schematically showing an embodiment of the laminated body of the present invention.
The laminate 1 shown here includes a base material 11 and a metallic silver layer 12 formed on the base material 11.
The metallic silver layer 12 is formed by using the silver ink composition of the present invention described above. The reflectance of light having a wavelength of 550 nm of the metallic silver layer 12 is 50% or more.
The metallic silver layer 12 is laminated only on one surface of the base material 11 (sometimes referred to as a "first surface" in the present specification) 11a.

In the laminate 1 shown here, a metallic silver layer is placed on the surface (sometimes referred to as “second surface” in the present specification) 11b on the side opposite to the first surface 11a of the base material 11. Although (not shown) is not laminated, a metallic silver layer may be laminated on the second surface 11b.
In this case, the metallic silver layer on the second surface 11b of the base material 11 may be formed by using the silver ink composition of the present invention, or a silver ink composition different from the present invention may be used. It may be formed by. The metal silver layer 12 on the first surface 11a of the base material 11 and the metal silver layer on the second surface 11b of the base material 11 may be the same or different from each other.

As described above, by using the silver ink composition of the present invention, even when printing is performed while heating the object to be printed, or when coating is performed while heating the object to be coated. Next, a metallic silver (metal silver layer) having high gloss can be formed by separately performing a solidification treatment such as a drying treatment or a heating (baking) treatment of the silver ink composition.
The heating temperature of the printed object at the time of printing or the object to be coated at the time of coating is not particularly limited, but is preferably 45 to 70 ° C, more preferably 55 to 65 ° C. When the heating temperature is at least the lower limit value, bleeding of the silver ink composition during printing or coating is further suppressed. When the heating temperature is equal to or lower than the upper limit value, deterioration of the printing object or the coating object is further suppressed.

The heating time of the printing object or the coating object is not particularly limited, and can be appropriately adjusted according to, for example, the heating temperature. Usually, the heating time is preferably 5 seconds to 10 minutes.

Printing with the above-mentioned silver ink composition or application of the silver ink composition, which is carried out while heating the object, may be carried out in an air atmosphere or an inert gas atmosphere. Examples of the inert gas include nitrogen gas, helium gas, argon gas and the like. In particular, by performing the printing or coating in an inert gas atmosphere, metallic silver (metal silver layer) having higher gloss may be obtained.

The thickness of the metallic silver layer formed on the base material using the silver ink composition of the present invention can be arbitrarily set according to the intended purpose, and is not particularly limited.
For example, the thickness of the metallic silver layer is preferably 0.04 to 1 μm, more preferably 0.05 to 0.5 μm. When the thickness of the metallic silver layer is at least the above lower limit value, the light reflectance of the metallic silver layer becomes higher. On the other hand, the metallic silver layer having a thickness equal to or less than the upper limit value can be formed more easily.

The laminate obtained by forming a metallic silver layer (metal silver) on a base material using the silver ink composition of the present invention can be used for various purposes by utilizing the highly glossy properties of the metallic silver layer. Available at. For example, if the metallic silver layer is patterned, the laminate is useful as a constituent member of various decorative or decorative products. Further, if the metallic silver layer is in the form of a film, the laminate is useful as a constituent member of various products using the surface of the film as a mirror surface.
Preferred examples of the laminated body having a metallic silver layer on a base material include those having a light reflectance of the metallic silver layer having a wavelength of 550 nm of 50% or more (for example, 50% 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 examples shown below.

[Example 1]
<Manufacturing of silver ink composition>
2-Ethylhexylamine (78.18 g, 6.53 times the molar amount of silver 2-methylacetate acetate described later) and 3,5-dimethyl-1-hexin-3-ol (hereinafter, "DMHO") in a beaker. (1.17 g, 0.10 times the molar amount of silver 2-methylacetate) and the mixture are added and mixed, and the mechanical stirrer is rotated to stir, and the liquid is further added here. Silver 2-methylacetate acetate (20.65 g) was added so that the temperature became 40 ° C. or lower to dissolve each compounding component, and stirring was continued for 1 day as it was at room temperature.
Next, neodecanoic acid (0.13 times the molar amount of silver 2-methylacetoacetate) was added dropwise to the stirred solution so that the solution temperature was 30 ° C. or lower, and the mixture was stirred to obtain silver as a silver ink composition. The ink composition (I) was obtained.
As the DMHO, "Surfinol 61" manufactured by Nisshin Kagaku Co., Ltd. was used, and as the neodecanoic acid, "Versatic 10" manufactured by Japan Chemtech Co., Ltd. was used. This also applies to the following Examples, Reference Examples, and Comparative Examples.

Table 1 shows the types and ratios of each compounding ingredient. In Table 1, the “nitrogen-containing compound (molar ratio)” refers to the amount of the nitrogen-containing compound (number of moles) per mole of the amount of the organic silver compound ([number of moles of the nitrogen-containing compound] / [organic silver compound]. Number of moles]). Similarly, "alcohol (molar ratio)" means the amount of alcohol compounded (number of moles) per mole of the amount of organic silver compound compounded ([number of moles of alcohol] / [number of moles of organic silver compound]). Similarly, the "molar ratio of branched saturated aliphatic carboxylic acid" is also the amount (number of moles) of the branched saturated aliphatic carboxylic acid per mol of the blended amount of the organic silver compound ([branched chain saturated aliphatic carboxylic acid]. [Number of moles of carboxylic acid] / [Number of moles of organic silver compound]). Further, the description of "-" in the column of the compounding component / blending amount of the silver ink composition means that the component is not compounded. The same applies to the tables after Table 1, which show the types and mixing ratios of the compounding components.
In this example, the "organic silver compound" is "silver β-ketocarboxylate (1)".

<Evaluation of silver ink composition>
(Formation of metallic silver layer)
The silver ink composition obtained above was applied onto one surface of a polyethylene terephthalate base material (Toray Industries, Inc. "Lumirror (registered trademark) S10", thickness 100 μm, size 50 mm × 50 mm) using a spin coater. After coating, the coated substrate was immediately placed on a hot plate and heated at 60 ° C. for 5 minutes. The rotation conditions during coating by the spin coater were 1000 rpm for 5 seconds and then 2000 rpm for 10 seconds.
Next, immediately using a dryer (“HAS-42” manufactured by Taketsuna Seisakusho), the coated material (coating film) on the substrate after heating is heated (baked) at 100 ° C. for 15 minutes. , Metallic silver layer (metal silver film) (1) -1 was formed.
Further, the metallic silver layer (1) -1R is formed by the same method as in the case of the metallic silver layer (1) -1, except that the base material is not heated separately after the silver ink composition is applied. bottom.
Further, separately, the heating (baking) treatment condition of the coated material is changed to 15 minutes at 120 ° C. instead of 15 minutes at 100 ° C., except that the method is the same as that for the metallic silver layer (1) -1. , Metallic silver layer (1) -2 was formed.
Further, the metallic silver layer (1) -2R is formed in the same manner as in the case of the metallic silver layer (1) -2, except that the base material is not heated separately after the silver ink composition is applied. bottom.
Table 2 shows the heating conditions for the base material after coating and the heating (firing) treatment conditions for the coated product. In Table 2, the description of "-" in the process condition column means that the process is not performed. This also applies to the tables after Table 2 showing the heating conditions of the above-mentioned base material and the heating (baking) treatment conditions of the coated material.

(Measurement of light reflectance of metal silver layer)
With respect to the metallic silver layers (1) -1, (1) -1R, (1) -2 and (1) -2R obtained above, the integrating sphere spectrophotometer "X" was obtained at three different locations on the respective surfaces. -Rite model SP60 "was used, the measurement mode was SCI (including positively reflected light), the light source was D65, the reflectance of light having a wavelength of 550 nm was measured, and the average value was calculated. The results are shown in Table 2.

[Example 2]
<Manufacturing of silver ink composition>
2-Ethylhexylamine (75.61 g, 6.32 times the molar amount of silver pivaloyl acetate, which will be described later) and DMHO (1.17 g, 0.10 times the molar amount of silver pivaloyl acetate) in a beaker. Is added and mixed, and while stirring the mechanical stirrer, silver pivaloyl acetate (23.23 g) is further added thereto so that the liquid temperature becomes 40 ° C. or lower to dissolve each compounding component. Stirring was continued for 1 day at room temperature.
Next, neodecanoic acid (0.13 times the molar amount with respect to silver pivaloyl acetate) was added dropwise to the stirring liquid so that the liquid temperature was 30 ° C. or lower, and the mixture was stirred to prepare a silver ink composition as a silver ink composition. I got the thing (I).

<Evaluation of silver ink composition>
The silver ink composition obtained above was applied onto one surface of a polyethylene terephthalate base material (Toray Industries, Inc. "Lumirror (registered trademark) S10", thickness 100 μm, size 50 mm × 50 mm) using a spin coater. After coating, the coated substrate was immediately placed on a hot plate and heated at 60 ° C. for 5 minutes. The rotation conditions during coating by the spin coater were 1000 rpm for 5 seconds and then 2000 rpm for 10 seconds.
Next, immediately using a dryer (“HAS-42” manufactured by Taketsuna Seisakusho), the coated material (coating film) on the substrate after heating is heated (baked) at 120 ° C. for 15 minutes. , Metallic silver layer (metal silver film) (2) -1 was formed.
Table 2 shows the heating conditions for the base material after coating and the heating (firing) treatment conditions for the coated material.
Then, with respect to the metallic silver layer (2) -1 obtained above, the reflectance of light having a wavelength of 550 nm was measured by the same method as in Example 1, and the average value thereof was calculated. The results are shown in Table 2.

[Comparative Example 1]
<Manufacturing of silver ink composition>
A silver ink composition was obtained in the same manner as in Example 1 except that neodecanoic acid was not added dropwise. That is, the silver ink composition obtained by adding silver 2-methylacetate acetate and continuing stirring at room temperature for one day was used as it was.

<Evaluation of silver ink composition>
The silver ink composition obtained above was applied onto one surface of a polyethylene terephthalate base material (Toray Industries, Inc. "Lumirror (registered trademark) S10", thickness 100 μm, size 50 mm × 50 mm) using a spin coater. After coating, the coated substrate was immediately placed on a hot plate and heated at 60 ° C. for 5 minutes. The rotation conditions during coating by the spin coater were 1000 rpm for 5 seconds and then 2000 rpm for 10 seconds.
Next, immediately using a dryer (“HAS-42” manufactured by Taketsuna Seisakusho), the coated material (coating film) on the substrate after heating is heated (baked) at 100 ° C. for 15 minutes. , Metallic silver layer (metal silver film) (R1) -1 was formed.
Further, the metallic silver layer (R1) -1R is formed in the same manner as in the case of the metallic silver layer (R1) -1, except that the base material is not heated separately after the silver ink composition is applied. bottom.
Furthermore, except that the heating conditions of the base material after coating the silver ink composition were changed to 5 minutes at 40 ° C. for 5 minutes and 5 minutes at 30 ° C. for metal. The metallic silver layers (R1) -2 and (R1) -3 were formed by the same method as in the case of the silver layer (R1) -1.
Further, separately, the heating (baking) treatment condition of the coated material is changed to 15 minutes at 120 ° C. instead of 15 minutes at 100 ° C., except that the method is the same as that for the metallic silver layer (R1) -1. , Metallic silver layer (R1) -4 was formed.
Further, the metallic silver layer (R1) -2R is formed in the same manner as in the case of the metallic silver layer (R1) -4, except that the base material is not heated separately after the silver ink composition is applied. bottom.
Table 2 shows the heating conditions for the base material after coating and the heating (firing) treatment conditions for the coated product.
Then, the metallic silver layers (R1) -1 to (R1) to 4 and (R1) -1R to (R1) to 2R obtained above are reflected by light having a wavelength of 550 nm in the same manner as in Example 1. The rate was measured and the average value was calculated. The results are shown in Table 2.

[Comparative Example 2]
<Manufacturing and evaluation of silver ink composition>
A silver ink composition was obtained in the same manner as in Example 2 except that neodecanoic acid was not added dropwise. That is, the silver ink composition obtained by adding silver pivaloyl acetate and continuing stirring at room temperature for one day was used as it was.
Then, using the obtained silver ink composition, the metallic silver layer (R2) -1 was formed by the same method as in Example 2, and the evaluation was performed by the same method as in Example 2. The results are shown in Table 2.

From the comparison between the results of the metallic silver layers (1) -1 and (1) -1R of Example 1 and the results of the metallic silver layers (R1) -1 to (R1) -4 of Comparative Example 1, Examples It was confirmed that by using the silver ink composition of No. 1, a metallic silver layer having high gloss can be formed even when printing is performed while heating the base material.
Also, from the comparison between the results of the metallic silver layers (1) -2 and (1) -2R of Example 1 and the results of the metallic silver layers (R1) -4 and (R1) -2R of Comparative Example 1. It was confirmed that by using the silver ink composition of Example 1, a metallic silver layer having high glossiness can be formed even when printing is performed while heating the base material.

From the comparison between the result of the metallic silver layer (2) -1 of Example 2 and the result of the metallic silver layer (R2) -1R of Comparative Example 2, the silver ink composition of Example 2 was used as a basis. It was confirmed that a highly glossy metallic silver layer can be formed even when printing is performed while heating the material.

From the results of Examples 1 and 2, it was confirmed that when the base material is heated after the silver ink composition is applied, a highly glossy metallic silver layer can be formed even if different types of organic silver compounds are used. In Examples 1 and 2, the light reflectance of the metallic silver layer when the base material was heated after the silver ink composition was applied was 62% or more.

In both Examples 1 and 2 and Comparative Examples 1 and 2, the thickness of the formed metallic silver layer was about 0.1 μm.

[Example 3]
<Manufacturing of silver ink composition>
2-Ethylhexylamine (78.18 parts by mass, 6.53 times the molar amount of silver 2-methylacetate acetate described later) and DMHO (1.17 parts by mass, 0 with respect to silver 2-methylacetate acetate) in a beaker. .10 times the molar amount) and mix, and while rotating the mechanical stirrer and stirring, further here, silver 2-methylacetate acetate (20.65 parts by mass) so that the liquid temperature becomes 40 ° C. or less. Was added to dissolve each compounding component, and stirring was continued for 1 day as it was at room temperature.
Next, 2-propylvaleric acid (1.00 parts by mass, 0.07 times the molar amount with respect to silver 2-methylacetate acetate) is added dropwise to the stirring liquid so that the liquid temperature becomes 30 ° C. or lower, and the mixture is stirred. As a result, the silver ink composition (I) was obtained as the silver ink composition.
As 2-propyl valeric acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Table 3 shows the types and ratios of each compounding ingredient. In Table 3, in the column of "carboxylic acid", 2-propylvaleric acid, which is a branched-chain saturated aliphatic carboxylic acid, and its molar ratio are listed. This also applies to the subsequent examples.

<Evaluation of silver ink composition>
The silver ink composition obtained above was applied onto one surface of a polyethylene terephthalate base material (Toray Industries, Inc. "Lumirror (registered trademark) S10", thickness 100 μm, size 50 mm × 50 mm) using a spin coater. After coating, the coated substrate was immediately placed on a hot plate and heated at 60 ° C. for 5 minutes. The rotation conditions during coating by the spin coater were 1000 rpm for 5 seconds and then 2000 rpm for 10 seconds.
Next, immediately using a dryer (“HAS-42” manufactured by Taketsuna Seisakusho), the coated material (coating film) on the substrate after heating is heated (baked) at 120 ° C. for 15 minutes. , Metallic silver layer (metal silver film) (3) -1 was formed.
Further, the metallic silver layer (3) -1R is formed by the same method as in the case of the metallic silver layer (3) -1, except that the base material is not heated separately after the silver ink composition is applied. bottom.
Table 4 shows the heating conditions for the base material after coating and the heating (firing) treatment conditions for the coated product.
Then, with respect to the metallic silver layers (3) -1 and (3) -1R obtained above, the reflectance of light having a wavelength of 550 nm was measured by the same method as in Example 1, and the average value thereof was calculated. The results are shown in Table 4.

[Example 4]
<Manufacturing and evaluation of silver ink composition>
Instead of setting the amount of 2-propylvaleric acid to be 1.00 parts by mass (0.07 times the molar amount with respect to silver 2-methylacetate acetate) at the time of producing the silver ink composition, 2.00. A silver ink composition (I) was obtained as a silver ink composition by the same method as in Example 3 except that the amount was set to parts by mass (0.15 times the molar amount with respect to silver 2-methylacetate acetate).
Then, using the obtained silver ink composition, the metallic silver layers (4) -1 and (4) -1R were formed by the same method as in Example 3, and the evaluation was performed by the same method as in Example 3. .. The results are shown in Table 4.

[Example 5]
<Manufacturing and evaluation of silver ink composition>
In the production of the silver ink composition, the amount of 2-propylvaleric acid blended is 3.00 instead of 1.00 parts by mass (0.07 times the molar amount of silver 2-methylacetate acetate). A silver ink composition (I) was obtained as a silver ink composition by the same method as in Example 3 except that the amount was set to parts by mass (0.22 times the molar amount with respect to silver 2-methylacetate acetate).
Then, using the obtained silver ink composition, the metallic silver layers (5) -1 and (5) -1R were formed by the same method as in Example 3, and the evaluation was performed by the same method as in Example 3. .. The results are shown in Table 4.

[Example 6]
<Manufacturing and evaluation of silver ink composition>
In the production of the silver ink composition, the amount of 2-propylvaleric acid blended is 4.00 instead of 1.00 parts by mass (0.07 times the molar amount of silver 2-methylacetate acetate). A silver ink composition (I) was obtained as a silver ink composition by the same method as in Example 3 except that the amount was set to parts by mass (0.30 times the molar amount with respect to silver 2-methylacetate acetate).
Then, using the obtained silver ink composition, the metallic silver layers (6) -1 and (6) -1R were formed by the same method as in Example 3, and the evaluation was performed by the same method as in Example 3. .. The results are shown in Table 4.

[Example 7]
<Manufacturing and evaluation of silver ink composition>
2-Ethylhexylamine (78.18 parts by mass, 6.53 times the molar amount of silver 2-methylacetate acetate described later) and DMHO (1.17 parts by mass, 0 with respect to silver 2-methylacetate acetate) in a beaker. .10 times the molar amount) and mix, and while rotating the mechanical stirrer and stirring, further here, silver 2-methylacetate acetate (20.65 parts by mass) so that the liquid temperature becomes 40 ° C. or less. Was added to dissolve each compounding component, and stirring was continued for 1 day as it was at room temperature.
Next, 3,5,5-trimethylhexane acid (1.00 parts by mass, 0.07 times the molar amount with respect to silver 2-methylacetate acetate) was added dropwise to this stirred solution so that the solution temperature was 30 ° C. or lower. The silver ink composition (I) was obtained as the silver ink composition.
As the 3,5,5-trimethylcaproic acid, those manufactured by Tokyo Chemical Industry Co., Ltd. were used.
Table 3 shows the types and ratios of each compounding ingredient.
Then, using the obtained silver ink composition, the metallic silver layers (7) -1 and (7) -1R were formed by the same method as in Example 3, and the evaluation was performed by the same method as in Example 3. .. The results are shown in Table 4.

[Example 8]
<Manufacturing and evaluation of silver ink composition>
Instead of setting the blending amount of 3,5,5-trimethylhexaneic acid at the time of producing the silver ink composition to 1.00 parts by mass (0.07 times the molar amount with respect to silver 2-methylacetate acetate). , 2.00 parts by mass (0.14 times the molar amount with respect to silver 2-methylacetate acetate) was obtained in the same manner as in Example 7 to obtain a silver ink composition (I) as a silver ink composition. rice field.
Then, using the obtained silver ink composition, the metallic silver layers (8) -1 and (8) -1R were formed by the same method as in Example 7, and the evaluation was performed by the same method as in Example 7. .. The results are shown in Table 4.

[Reference example 1]
<Manufacturing and evaluation of silver ink composition>
2-Ethylhexylamine (78.18 parts by mass, 6.53 times the molar amount of silver 2-methylacetate acetate described later) and DMHO (1.17 parts by mass, 0 with respect to silver 2-methylacetate acetate) in a beaker. .10 times the molar amount) and mix, and while rotating the mechanical stirrer and stirring, further here, silver 2-methylacetate acetate (20.65 parts by mass) so that the liquid temperature becomes 40 ° C. or less. Was added to dissolve each compounding component, and stirring was continued for 1 day as it was at room temperature.
Next, n-hexane acid (1.00 parts by mass, 0.09 times the molar amount with respect to silver 2-methylacetate acetate) is added dropwise to the stirred solution so that the liquid temperature becomes 30 ° C. or lower, and the mixture is stirred. To obtain a silver ink composition.
As the n-hexane acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Table 3 shows the types and ratios of each compounding ingredient. In Table 3, in the column of "carboxylic acid", n-hexane acid which is not a branched-chain saturated aliphatic carboxylic acid and its molar ratio are listed. This also applies to the following reference examples.
Then, using the obtained silver ink composition, the metallic silver layers (1') -1 and (1') -1R are formed by the same method as in Example 3, and the evaluation is performed by the same method as in Example 3. went. The results are shown in Table 4.

[Reference example 2]
<Manufacturing and evaluation of silver ink composition>
Instead of setting the blending amount of n-hexaneic acid to 1.00 parts by mass (0.09 times the molar amount with respect to silver 2-methylacetate acetate) at the time of producing the silver ink composition, it is 2.00 mass by mass. A silver ink composition was obtained in the same manner as in Reference Example 1 except that the portion (0.19 times the molar amount of 2-methylacetate silver) was used.
Then, using the obtained silver ink composition, the metallic silver layers (1') -2 and (1') -2R are formed by the same method as in Reference Example 1, and evaluated by the same method as in Reference Example 1. went. The results are shown in Table 4.

[Reference example 3]
<Manufacturing of silver ink composition>
2-Ethylhexylamine (78.18 parts by mass, 6.53 times the molar amount of silver 2-methylacetate acetate described later) and DMHO (1.17 parts by mass, 0 with respect to silver 2-methylacetate acetate) in a beaker. .10 times the molar amount) and mix, and while rotating the mechanical stirrer and stirring, further here, silver 2-methylacetate acetate (20.65 parts by mass) so that the liquid temperature becomes 40 ° C. or less. Was added to dissolve each compounding component, and stirring was continued for 1 day as it was at room temperature.
Next, cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount with respect to silver 2-methylacetate acetate) is added dropwise to the stirred solution so that the liquid temperature becomes 30 ° C. or lower, and the mixture is stirred. To obtain a silver ink composition.
As the cyclopropanecarboxylic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Table 3 shows the types and ratios of each compounding ingredient.

<Evaluation of silver ink composition>
The silver ink composition obtained above was applied onto one surface of a polyethylene terephthalate base material (Toray Industries, Inc. "Lumirror (registered trademark) S10", thickness 100 μm, size 50 mm × 50 mm) using a spin coater. Painted. The rotation conditions during coating by the spin coater were 1000 rpm for 5 seconds and then 2000 rpm for 10 seconds.
Next, immediately, using a dryer (“HAS-42” manufactured by Taketsuna Seisakusho), the coated material (coating film) on the base material after coating this silver ink composition is heated at 120 ° C. for 15 minutes ( By the treatment (calcination), a metallic silver layer (metal silver film) (1')-3R was formed.
Then, with respect to the metallic silver layer (1')-3R obtained above, the reflectance of light having a wavelength of 550 nm was measured by the same method as in Example 1, and the average value thereof was calculated. The results are shown in Table 4.

[Reference example 4]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount of silver 2-methylacetate), 3-methylcrotonic acid (1.00 parts by mass, 2-methylacetacetate) A silver ink composition was obtained by the same method as in Reference Example 3 except that 0.11 times the molar amount of silver was blended.
As the 3-methyl crotonic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Then, using the obtained silver ink composition, a metallic silver layer (1')-4R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference example 5]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by weight, 0.13 times the molar amount of silver 2-methylacetate acetate), 2,2-bis (hydroxymethyl) butyric acid (1.00 parts by mass) , 2-Mole amount of 0.07 times as much as silver 2-methylacetate acetate) was added, and a silver ink composition was obtained by the same method as in Reference Example 3.
As 2,2-bis (hydroxymethyl) butyric acid, those manufactured by Tokyo Chemical Industry Co., Ltd. were used.
Then, using the obtained silver ink composition, a metallic silver layer (1') -5R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference example 6]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount of silver 2-methylacetate), hydroxypivalic acid (1.00 parts by mass, silver 2-methylacetate acetate) A silver ink composition was obtained in the same manner as in Reference Example 3 except that 0.09 times the molar amount was blended.
As the hydroxypival acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Then, using the obtained silver ink composition, a metallic silver layer (1') -6R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference Example 7]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount with respect to silver 2-methylacetate), dehydroacetic acid (1.00 parts by mass, with respect to silver 2-methylacetate acetate) A silver ink composition was obtained in the same manner as in Reference Example 3 except that 0.06 times the molar amount was blended.
As the dehydroacetic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Then, using the obtained silver ink composition, a metallic silver layer (1') -7R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference Example 8]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by weight, 0.13 times the molar amount of silver 2-methylacetate acetate), 2,2-bis (hydroxymethyl) propionic acid (1.00 parts by mass) A silver ink composition was obtained in the same manner as in Reference Example 3 except that the amount was 0.08 times the molar amount of silver 2-methylacetate acetate.
As the 2,2-bis (hydroxymethyl) propionic acid, those manufactured by Tokyo Chemical Industry Co., Ltd. were used.
Then, using the obtained silver ink composition, a metallic silver layer (1')-8R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference example 9]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount of silver 2-methylacetate), DL-lactic acid (1.00 parts by mass, silver 2-methylacetate acetate) A silver ink composition was obtained by the same method as in Reference Example 3 except that 0.12 times the molar amount was blended.
As DL-lactic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Then, using the obtained silver ink composition, a metallic silver layer (1') -9R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference Example 10]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount of silver 2-methylacetate), n-decanoic acid (1.00 parts by mass, silver 2-methylacetate acetate) A silver ink composition was obtained in the same manner as in Reference Example 3 except that 0.06 times the molar amount was blended.
As the n-decanoic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Then, using the obtained silver ink composition, a metallic silver layer (1')-10R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference Example 11]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount with respect to silver 2-methylacetate), palmitic acid (1.00 parts by mass, with respect to silver 2-methylacetate acetate) A silver ink composition was obtained in the same manner as in Reference Example 3 except that 0.04 times the molar amount was blended.
As the palmitic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Then, using the obtained silver ink composition, a metallic silver layer (1') -11R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

[Reference Example 12]
<Manufacturing and evaluation of silver ink composition>
Instead of blending cyclopropanecarboxylic acid (1.00 parts by mass, 0.13 times the molar amount of silver 2-methylacetate), n-octanoic acid (1.00 parts by mass, silver 2-methylacetate acetate) A silver ink composition was obtained in the same manner as in Reference Example 3 except that 0.07 times the molar amount was blended.
As the n-octanoic acid, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Then, using the obtained silver ink composition, a metallic silver layer (1')-12R was formed by the same method as in Reference Example 3, and evaluation was performed by the same method as in Reference Example 3. The results are shown in Table 4.

As is clear from the results of Examples 3 to 8, when the base material is heated after coating the silver ink composition, metallic silver having high gloss even when different types of branched-chain saturated aliphatic carboxylic acids are used. It was confirmed that a layer could be formed. In Examples 3 to 8, the light reflectance of the metallic silver layer when the base material was heated after the silver ink composition was applied was 56% or more.

In Examples 3 to 6, when the base material was not heated after the silver ink composition was applied, the blending amount of the branched chain saturated aliphatic carboxylic acid (2-propyl valeric acid) in the silver ink composition was increased. As the number increased (in the order of metallic silver layer (3) -1R, (4) -1R, (5) -1R and (6) -1R), the glossiness of the metallic silver layer tended to decrease. However, when the base material is heated after the silver ink composition is applied (in the case of the metallic silver layer (3) -1, (4) -1, (5) -1, and (6) -1), the branched chain The glossiness of the metallic silver layer was stable regardless of the blending amount of the state saturated aliphatic carboxylic acid (2-propylvaleric acid).
On the other hand, in Examples 7 to 8, when the base material was not heated after the silver ink composition was applied (in the case of the metallic silver layer (7) -1R and (7) -2R) and when it was heated. (In the case of metallic silver layers (7) -1 and (7) -2), depending on the blending amount of the branched chain saturated aliphatic carboxylic acid (3,5,5-trimethylcaproic acid). However, the glossiness of the metallic silver layer was stable. Further, in Examples 7 to 8, the dullness of the metallic silver layer was suppressed to the highest degree.

On the other hand, in Reference Examples 1 to 12 in which other compounds (carboxylic acids) were used instead of the branched-chain saturated aliphatic carboxylic acid, a highly glossy metallic silver layer could not be formed.
In Reference Examples 1 and 2 and 10 to 12, linear saturated aliphatic carboxylic acid is used instead of branched chain saturated aliphatic carboxylic acid, and in Reference Examples 1 and 2, n-hexanoic acid is used and Reference Example. In No. 10, n-decanoic acid was used, in Reference Example 11, palmitic acid was used, and in Reference Example 12, n-octanoic acid was used.
In Reference Example 3, cyclopropanecarboxylic acid, which is a cyclic saturated aliphatic carboxylic acid, was used instead of the branched saturated aliphatic carboxylic acid.
In Reference Example 4, 3-methylcrotonic acid, which is a branched unsaturated aliphatic carboxylic acid, was used instead of the branched saturated aliphatic carboxylic acid.
In Reference Examples 5, 6 and 8, a branched saturated aliphatic hydroxycarboxylic acid is used instead of a branched saturated aliphatic carboxylic acid, and in Reference Example 5, 2,2-bis (hydroxymethyl) butyric acid is used. In Reference Example 6, hydroxypivalic acid was used, and in Reference Example 8, 2,2-bis (hydroxymethyl) propionic acid was used.
In Reference Example 7, dehydroacetic acid, which is a ketocarboxylic acid, was used instead of the branched-chain saturated aliphatic carboxylic acid.
In Reference Example 9, DL-lactic acid, which is a linear saturated aliphatic hydroxycarboxylic acid, was used instead of the branched chain saturated aliphatic carboxylic acid.

In Reference Example 1, a metallic silver layer having high gloss could not be formed by heating the base material at 60 ° C. for 5 minutes after coating the silver ink composition.
In Reference Examples 2 to 12, even if the metallic silver layer is formed without heating the base material after the silver ink composition is applied, the metallic silver layer having high gloss cannot be formed, and the branched chain saturation occurs. Other compounds used in place of the aliphatic carboxylic acid were not suitable for the formation of the metallic silver layer.
In Reference Examples 1 and 2, the light reflectance of the metallic silver layer when the base material was heated after the silver ink composition was applied was 36% or less.

As described above, the effect of the present invention can be obtained only when the silver ink composition in which the organic silver compound and the branched-chain saturated aliphatic carboxylic acid are blended is used. In particular, when the results of Reference Example 10 are compared with the results of Examples 1 and 2 described above, it is particularly clear that the branched-chain saturated aliphatic carboxylic acid is an essential compounding component.

In each of Examples 3 to 8 and Reference Examples 1 to 12, the thickness of the formed metallic silver layer was about 0.1 μm.

[Example 9]
<Manufacturing of silver ink composition>
A silver ink composition was produced by the procedure shown below with reference to Example 4 described in Japanese Patent No. 5243409.
That is, at room temperature, 2-ethylhexyl ammonium 2-ethylhexyl carbamate (45.5 g, 150.41 mmol) was dissolved in 2-propanol (105 g), and silver oxide (14 g, 60.41 mmol) was added thereto. , Reacted at room temperature. The reaction solution at this time was initially a black suspension, and the color gradually faded as the target organic silver complex was formed. At the stage of reacting for 4 hours, a small amount of silver oxide precipitate remained in the reaction solution. Therefore, by centrifuging this reaction solution, the precipitate was removed to obtain a transparent reaction solution (reaction solution). rice field.

Using an electric furnace, the transparent reaction solution obtained above was heat-treated at 400 ° C. for 3.5 hours, and the mass change before and after this heat treatment (mass of the reaction solution before heat treatment and the reaction solution described above). The silver content of the reaction solution was measured from the difference between the mass and the mass of the treated product obtained by heat treatment, and was found to be 5.8% by mass.

Next, neodecanoic acid (0.3 g, 1.74 mmol) was added to the transparent reaction solution (30 g) obtained above at room temperature and stirred to prepare a silver ink composition as a silver ink composition. The thing (II) was obtained.

<Evaluation of silver ink composition>
(Formation of metallic silver layer)
The silver ink composition obtained above was applied onto one surface of a polyethylene terephthalate base material (Toray Industries, Inc. "Lumirror (registered trademark) S10", thickness 100 μm, size 50 mm × 50 mm) using a spin coater. After coating, the coated substrate was immediately placed on a hot plate and heated at 60 ° C. for 5 minutes. The rotation conditions during coating by the spin coater were 1000 rpm for 5 seconds and then 2000 rpm for 10 seconds.
Next, immediately using a dryer (“HAS-42” manufactured by Taketsuna Seisakusho), the coated material (coating film) on the substrate after heating is heated (baked) at 150 ° C. for 15 minutes. , Metallic silver layer (metal silver film) (9) -1 was formed.
Further, the metallic silver layer (9) -1R is formed by the same method as in the case of the metallic silver layer (9) -1, except that the base material is not heated separately after the silver ink composition is applied. bottom.
Table 5 shows the heating conditions for the base material after coating and the heating (firing) treatment conditions for the coated product.

(Measurement of reflectance of metallic silver layer)
With respect to the metallic silver layers (9) -1 and (9) -1R obtained above, the reflectance of light having a wavelength of 550 nm was measured by the same method as in Example 1, and the average value thereof was calculated. The results are shown in Table 5.

[Example 10]
<Manufacturing and evaluation of silver ink composition>
At the time of producing the silver ink composition, the blending amount of neodecanoic acid with respect to the transparent reaction solution (30 g) was set to 0.48 g (2.79 mmol) instead of 0.3 g (1.74 mmol). A silver ink composition (II) was obtained as a silver ink composition in the same manner as in Example 9 except for the points.
Then, using the obtained silver ink composition, the metallic silver layers (10) -1 and (10) -1R were formed by the same method as in Example 9, and the evaluation was performed by the same method as in Example 9. .. The results are shown in Table 5.

[Example 11]
<Manufacturing and evaluation of silver ink composition>
At the time of producing the silver ink composition, the blending amount of neodecanoic acid with respect to the transparent reaction solution (30 g) was 0.9 g (5.22 mmol) instead of 0.3 g (1.74 mmol). A silver ink composition (II) was obtained as a silver ink composition in the same manner as in Example 9 except for the points.
Then, using the obtained silver ink composition, the metallic silver layers (11) -1 and (11) -1R were formed by the same method as in Example 9, and the evaluation was performed by the same method as in Example 9. .. The results are shown in Table 5.

[Comparative Example 3]
<Manufacturing and evaluation of silver ink composition>
A silver ink composition was obtained in the same manner as in Example 9 except that neodecanoic acid was not added. That is, the transparent reaction solution (reaction solution) obtained by adding silver oxide and centrifuging was used as it was as a silver ink composition.
Then, using the obtained silver ink composition, the metallic silver layers (R3) -1 and (R3) -1R were formed by the same method as in Example 9, and the evaluation was performed by the same method as in Example 9. .. The results are shown in Table 5.

As is clear from the results of Examples 9 to 11, it was confirmed that a highly glossy metallic silver layer can be formed even when the base material is heated after the silver ink composition is applied. In Examples 9 to 11, the light reflectance of the metallic silver layer when the base material was heated after the silver ink composition was applied was 51% or more.

In Examples 9 to 11, the branched chain saturated aliphatic carboxylic acid in the silver ink composition is used regardless of whether the base material is heated after the silver ink composition is applied or not. As the blending amount of the acid (neodecanic acid) increases (metal silver layer (9) -1R, (10) -1R and (11) -1R, in that order, the metal silver layer (9) -1, (10) -1 and (11) -1), the glossiness of the metallic silver layer tended to improve.

On the other hand, in Comparative Example 3, even when the base material was heated after the silver ink composition was applied, the decrease in glossiness of the metallic silver layer could be suppressed to some extent, but the metallic silver in this case. The light reflectance of the layer was only 47%.

In each of Examples 9 to 11 and Comparative Example 3, the thickness of the formed metallic silver layer was about 0.1 μm.

The present invention can be used for various products and the like in which a metallic silver pattern is used for decoration or decoration. Further, the present invention can be used for various products and the like having a metallic silver layer on a base material and using the surface of the metallic silver layer as a mirror surface.

1 ... Laminated body, 11 ... Base material, 11a ... First surface of base material, 11b ... Second surface of base material, 12 ... Metallic silver layer

Claims (2)

A silver ink composition comprising an organic silver compound and a branched-chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms .
The organic silver compound is silver β-ketocarboxylate represented by the following general formula (1), a compound represented by the following general formula (95) -1, or a compound represented by the following general formula (95) -2. can be,
When the organic silver compound is a compound represented by the following general formula (95) -1 or a compound represented by the following general formula (95) -2, the silver ink composition further contains nitrogen. The compound is mixed,
In the silver ink composition, the amount of the branched saturated aliphatic carboxylic acid compounded is 0.01 to 1 mol per 1 mol of the amount of silver atoms in the organic silver compound .

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

(In the formula, R ^{101 to} R ¹¹¹ are independently hydrogen atoms, aliphatic or alicyclic alkyl or aryl groups having 1 to 30 carbon atoms, alkyl or aryl groups substituted with functional groups, and hetero. A group selected from the group consisting of cyclic groups, however, ^{not all R 101 to} R ¹¹¹ are hydrogen atoms; m ₁₀₁ and m ₁₀₂ are independently at 0.5 to 1.5, respectively. be.) A laminate comprising a base material and a metallic silver layer formed on the base material.
The metallic silver layer is formed by using the silver ink composition according to claim 1.
A laminate of the metallic silver layer having a reflectance of light having a wavelength of 550 nm of 50% or more.

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