JP2011063813A - Ink and method for forming wiring - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink containing β-ketocarboxylate having excellent stability in printing. <P>SOLUTION: The ink comprises a silver β-ketocarboxylate presented by formula (I): R-CO-CX<SB>2</SB>-COOAg, wherein R and X are defined in the specification, and a compound having a lone electron pair, wherein the compound containing the lone electron pair is one or more selected from the group consisting of an amine compound, a thiol compound and a phosphorous compound. Preferably, the ink further contains a solvent. In addition, the method for forming wiring by firing a board on which the ink is arranged is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an ink containing silver β-ketocarboxylate, a wiring manufactured using the ink, and a method of forming a wiring using the ink.

  Metallic silver is widely used as a recording material, a printing plate material, and a highly conductive material because of its excellent conductivity. As a general method for producing metallic silver, for example, a method of heating silver oxide which is an inorganic substance in the presence of a reducing agent can be mentioned. Specifically, for example, particulate silver oxide is dispersed in a binder, a reducing agent is added thereto to prepare a paste, and the paste is applied to a substrate or the like and heated. Thus, by heating in the presence of a reducing agent, the silver oxide is reduced, the metallic silver produced by the reduction is fused together, and a film containing metallic silver is formed.

  However, when silver oxide is used as a material for forming metallic silver, there is a problem that a reducing agent is necessary and the processing temperature is as high as about 300 ° C. Further, when metallic silver is used as the conductive material, it is necessary to use finer silver oxide particles in order to reduce the resistance of the formed film.

  On the other hand, in recent years, a method for forming metallic silver using organic acid silver instead of the inorganic material as described above has also been reported. Examples of the organic acid silver include silver behenate (see, for example, Patent Document 1), silver stearate, silver α-ketocarboxylate (see, for example, Patent Documents 2 and 3), and silver β-ketocarboxylate (for example, Patents). Reference 4) has been reported as a new metal silver forming material.

JP 2003-191646 A Japanese Patent Laid-Open No. 10-183207 JP 2004-315374 A International Publication No. 2007/4437 Pamphlet

  The silver β-ketocarboxylate has an excellent characteristic that it can form metallic silver quickly even when heated at a low temperature of about 210 ° C. or lower. In order to form a coating film containing metallic silver using this β-ketocarboxylate, for example, first, β-ketocarboxylate is dissolved in a solvent to form an ink, and the ink is printed on a substrate. The obtained substrate is baked at a temperature of about 210 ° C. or lower to obtain a film containing metallic silver. At this time, the present inventors have found that the ink has low storage stability, and the decomposition of the metal salt starts and the precipitation occurs in about several minutes at room temperature. The ink that has undergone such decomposition contains insoluble matter, and when the insoluble matter collects and precipitates, the active ingredient becomes non-uniform. Using such an ink may cause problems in the printing process. For example, when printing using ink in ink jet printing, the ink is stored in an ink jet printer head having nozzles, and the ink is ejected from the printer head through the nozzles. Since the size of the nozzle is very small in order to form fine wiring, precipitation of the insoluble matter generated by decomposition tends to be clogged, and clogging may occur. Furthermore, since the active ingredient is non-uniform, there is a risk that uniform printing cannot be performed. Further, when printing is performed using ink in gravure printing, there is a risk of scratching. Furthermore, since the active ingredient is non-uniform, there is a risk that uniform printing cannot be performed.

  Therefore, an object of the present invention is to provide an ink containing silver β-ketocarboxylate and having excellent stability during printing.

To solve the above problem,
The present invention is an ink comprising silver β-ketocarboxylate represented by the formula (I) and a compound having a lone electron pair, wherein the compound having a lone electron pair comprises an amine compound, a thiol compound and a phosphorus compound. An ink is provided that is one or more selected from the group consisting of:

［前記式（Ｉ）において、Ｒは、直鎖、分枝もしくは環状の飽和もしくは不飽和Ｃ₁〜Ｃ₂₀脂肪族炭化水素基、Ｒ¹−ＣＹ₂−、ＣＹ₃−、Ｒ¹−ＣＨＹ−、Ｒ²Ｏ−、フェニル基、１個もしくは複数の置換基で置換されたフェニル基、Ｒ⁵Ｒ⁴Ｎ−、水酸基、アミノ基、または、（Ｒ³Ｏ）₂ＣＹ−である。
ただし、Ｙは、同一であるかまたは異なり、それぞれフッ素原子、塩素原子、臭素原子または水素原子であり、Ｒ¹は直鎖、分枝または環状の飽和または不飽和Ｃ₁〜Ｃ₁₉脂肪族炭化水素基、または、フェニル基であり、Ｒ²は直鎖、分枝または環状の飽和または不飽和Ｃ₁〜Ｃ₂₀脂肪族炭化水素基であり、Ｒ³は直鎖、分枝または環状の飽和または不飽和Ｃ₁〜Ｃ₁₆脂肪族炭化水素基であり、Ｒ⁴およびＲ⁵は、同一であるかまたは異なり、それぞれ直鎖、分枝または環状の飽和または不飽和Ｃ₁〜Ｃ₁₈脂肪族炭化水素基である。
前記式（Ｉ）において、Ｘは、同一であるかまたは異なり、それぞれ水素原子、直鎖、分枝または環状の飽和または不飽和Ｃ₁〜Ｃ₂₀脂肪族炭化水素基、Ｒ⁶Ｏ−、Ｒ⁶Ｓ−、Ｒ⁶−ＣＯ−、Ｒ⁶−ＣＯ−Ｏ−、ハロゲン、ベンジル基、フェニル基、１個もしくは複数の置換基で置換されたフェニル基もしくはベンジル基、シアノ基、Ｎ−フタロイル−３−アミノプロピル基、２−エトキシビニル基である。
ただし、Ｒ⁶は直鎖、分枝もしくは環状の飽和もしくは不飽和Ｃ₁〜Ｃ₁₀脂肪族炭化水素基、チオフェニル基、フェニル基、ジフェニル基、または、１個もしくは複数の置換基で置換されたフェニル基もしくはジフェニル基である。］
本発明のインクにおいては、前記孤立電子対を有する化合物の炭素数が２〜２４であるであることが好ましい。
本発明のインクにおいては、前記孤立電子対を有する化合物が、２−フェニルエチルアミン、２−エチルヘキシルアミン、ヘキシルアミン、プロピルアミン、ｔｅｒｔ−ブチルアミン、エチレンジアミン、Ｎ−メチルヘキシルアミン、トリオクチルホスフィン、トリブチルホスフィン、亜リン酸トリブチル、１−ステアリルアミン、ジメチルオクタデシルアミン、メチルベンジルアミン、ジメチルシクロヘキシルアミン、ドデカンチオール、ジエチルホスホノ酢酸エチル、ドデシルトリメチルアンモニウムブロミドおよびテトラデシルアンモニウムブロミドからなる群から選択される１以上であることが好ましい。
また、本発明は、上記本発明のインクを基板上に配置し、前記インクが配置された基板を焼成することにより配線を形成する方法を提供する。

[In the formula (I), R represents a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, R ¹ -CY ₂ —, CY ₃ —, R ¹ —CHY— R ² O—, a phenyl group, a phenyl group substituted with one or more substituents, R ⁵ R ⁴ N—, a hydroxyl group, an amino group, or (R ³ O) ₂ CY—.
Where Y is the same or different and each is a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom, and R ¹ is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₁₉ aliphatic carbonization. A hydrogen group or a phenyl group, R ² is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, and R ³ is a linear, branched or cyclic saturated group. or unsaturated C ₁ -C ₁₆ aliphatic hydrocarbon radical, R ⁴ and R ^5, which are identical or different, each a straight-chain, branched or cyclic saturated or unsaturated C ₁ -C ₁₈ aliphatic It is a hydrocarbon group.
In the formula (I), X's are the same or different and are each a hydrogen atom, a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, R ⁶ O—, R ⁶ S-, R ⁶ -CO-, R ⁶ -CO-O-, halogen, benzyl group, phenyl group, phenyl or benzyl group substituted with one or more substituents, cyano group, N-phthaloyl- 3-aminopropyl group and 2-ethoxyvinyl group.
Where R ⁶ is substituted with a linear, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ aliphatic hydrocarbon group, thiophenyl group, phenyl group, diphenyl group, or one or more substituents It is a phenyl group or a diphenyl group. ]
In the ink of the present invention, the compound having a lone electron pair preferably has 2 to 24 carbon atoms.
In the ink of the present invention, the compound having a lone electron pair is 2-phenylethylamine, 2-ethylhexylamine, hexylamine, propylamine, tert-butylamine, ethylenediamine, N-methylhexylamine, trioctylphosphine, tributylphosphine. 1 or more selected from the group consisting of tributyl phosphite, 1-stearylamine, dimethyloctadecylamine, methylbenzylamine, dimethylcyclohexylamine, dodecanethiol, ethyl diethylphosphonoacetate, dodecyltrimethylammonium bromide and tetradecylammonium bromide It is preferable that
The present invention also provides a method of forming a wiring by disposing the ink of the present invention on a substrate and baking the substrate on which the ink is disposed.

  The ink of the present invention has an advantage of excellent stability during printing. Therefore, there is an advantage that stable printing can be performed for a relatively long time at room temperature. In addition, since the ink of the present invention contains β-ketocarboxylate that is heated to a low temperature and converted to metallic silver, wiring can be formed at a low temperature.

FIG. 1 is an SEM photograph after heating ink on paper. FIG. 1A is a SEM photograph of the surface of the formed film, and FIG. 1B is an SEM photograph of a cross section after the formed film and paper are subjected to FIB processing. FIG. 2 is an optical micrograph showing the state of ink on paper. FIG. 3 is a graph showing the resistance value of the metallic silver film on the paper. FIG. 4 is an optical micrograph of the surface of a metallic silver coating on paper. FIG. 5A is a graph of TGA measurement showing the firing process of the inks of Examples 11-13. FIG. 5B is a graph of TGA measurement showing the firing process of Example 12 and silver nitrate ink. FIG. 6 is a graph showing the surface tension of the inks of Examples 11 to 13. FIG. 7 is an IR spectrum of silver 2-benzylacetoacetate produced in Reference Example 1.

  As described above, the present invention is an ink containing silver β-ketocarboxylate represented by the formula (I) and a compound having a lone electron pair.

In the ink, R is a linear saturated C _{1 to} C ₂₀ aliphatic hydrocarbon group or R ¹ -CY ₂ — (Y is a hydrogen atom), X is different from each other, each of which is a hydrogen atom and a linear chain It is preferably a saturated C _{1 to} C ₂₀ aliphatic hydrocarbon group or a benzyl group.

  In the ink, the compound having a lone electron pair is preferably one or more selected from the group consisting of an amine compound, a thiol compound, and a phosphorus compound.

  The ink of the present invention preferably further contains a solvent. The solvent is at least one selected from the group consisting of alcohol, ketone, ether, ester, aromatic hydrocarbon, aliphatic hydrocarbon, cyano group or aliphatic hydrocarbon substituted with a halogen atom, and water. preferable.

  In addition, the present invention is a method of forming a wiring, and includes a step of forming the wiring by disposing the ink of the present invention on a substrate and baking the substrate on which the ink is disposed.

  The present invention also provides an ink preparation kit comprising silver β-ketocarboxylate represented by the formula (I) and a compound having a lone electron pair.

In the formula (I), R is a linear, branched or cyclic saturated or unsaturated C ₁ -C ₂₀ aliphatic hydrocarbon _{^{group, R 1 -CY 2 -, CY}} 3 -, R 1 -CHY-, R ² O—, a phenyl group, a phenyl group substituted with one or more substituents, R ⁵ R ⁴ N—, a hydroxyl group, an amino group, or (R ³ O) ₂ CY—.

Where Y is the same or different and each is a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom, and R ¹ is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₁₉ aliphatic carbonization. A hydrogen group or a phenyl group, R ² is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, and R ³ is a linear, branched or cyclic saturated group. or unsaturated C ₁ -C ₁₆ aliphatic hydrocarbon radical, R ⁴ and R ^5, which are identical or different, each a straight-chain, branched or cyclic saturated or unsaturated C ₁ -C ₁₈ aliphatic It is a hydrocarbon group.

In the formula (I), X's are the same or different and are each a hydrogen atom, a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, R ⁶ O—, R ⁶ S-, R ⁶ -CO-, R ⁶ -CO-O-, halogen, benzyl group, phenyl group, phenyl or benzyl group substituted with one or more substituents, cyano group, N-phthaloyl- 3-aminopropyl group and 2-ethoxyvinyl group.

Where R ⁶ is substituted with a linear, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ aliphatic hydrocarbon group, thiophenyl group, phenyl group, diphenyl group, or one or more substituents It is a phenyl group or a diphenyl group.

  The β-ketocarboxylate silver represented by the formula (I) contained in the ink and ink preparation kit of the present invention is:

In the formula (I), R is a linear, branched or cyclic saturated or unsaturated C ₁ -C ₂₀ aliphatic hydrocarbon _{^{group, R 1 -CY 2 -, CY}} 3 -, R 1 -CHY-, R ² O—, a phenyl group, a phenyl group substituted with one or more substituents, R ⁵ R ⁴ N—, a hydroxyl group, an amino group, or (R ³ O) ₂ CY—.

When R is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, examples of R include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group. etc. can be mentioned, for _{example, -C n H 2n + 1,} -C n H 2n-1 or _{-C n H 2n-3, (} n is an integer of 1 to 20) may be a group represented by . In the linear, branched or cyclic saturated or unsaturated C ₁ -C ₂₀ aliphatic hydrocarbon group, one or more hydrogen groups may be substituted with a fluorine atom, a chlorine atom or a bromine atom.

When R is a substituted phenyl group, examples of the substituent include R ³ —, R ³ O—, fluorine atom, chlorine atom, bromine atom, hydroxyl group, cyano group, phenoxy group, and the like. Any of o, m, and p may be substituted.

  Y in R may be the same or different and each is a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom.

R ¹ in R is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₁₉ aliphatic hydrocarbon group or a phenyl group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and the like. For example, —C _n H _{2n + 1} , —C _n H _2n−1 , or — C _n H _{2n-3 (n} is 1 to 19 integer) may be a group represented by.

R ² is a linear, branched or cyclic saturated or unsaturated C ₁ -C ₂₀ aliphatic hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, cycloalkenyl group and the like, for _{example, -C n H2 n + 1,} -C n H 2n-1 or, - C _n H _{2n-3 (n} is an integer of 1 to 20) may be a group represented by.

R ³ is a linear, branched or cyclic saturated or unsaturated C ₁ -C ₁₆ aliphatic hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and the like. For example, —C _n H _{2n + 1} , —C _n H _2n−1 , or — C _n H _{2n-3 (n} is 1 to 16 integer) may be a group represented by.

R ⁴ and R ⁵ may be the same or different and are each a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₁₈ aliphatic hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and the like. For example, —C _n H _{2n + 1} , —C _n H _2n−1 , or — C _n H _{2n-3 (n} is 1 to 18 integer) may be a group represented by.

In the formula (I), Xs may be the same or different, and are a hydrogen atom, a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, R ⁶ O—, R ^6. S-, R ⁶ -CO-, R ⁶ -CO-O-, halogen (fluorine, chlorine, bromine, iodine), benzyl group, phenyl group, phenyl group or benzyl group substituted with one or more substituents , A cyano group, an N-phthaloyl-3-aminopropyl group, and a 2-ethoxyvinyl group (C ₂ H ₅ —O—CH═CH—). Where R ⁶ is substituted with a linear, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ aliphatic hydrocarbon group, thiophenyl group, phenyl group, diphenyl group, or one or more substituents It is a phenyl group or a diphenyl group.

  When X is a substituted phenyl group, benzyl group or diphenyl group, examples of the substituent include halogen (fluorine, chlorine, bromine, iodine), nitro group, and any of o, m, and p is substituted. May be.

When X is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, examples of X include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cyclo alkenyl groups and the like, for example, -C _n H _2n + 1, a -C _n H _2n-1 or -C _n H _2n-3 group (n is an integer of from 1 to 20) represented by, Also good.

In R ⁶ O—, R ⁶ S—, R ⁶ —CO—, R ⁶ —CO—O— of X, examples of R ⁶ include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group. etc. can be mentioned, for _{example, -C n H 2n + 1,} -C n H 2n-1 or _{-C n H 2n-3, (} n is an integer of from 1 to 10) may be a group represented by . R ⁶ may be a thiophenyl group, a phenyl group, a diphenyl group, or a phenyl group or a diphenyl group substituted with one or more substituents, as described above. Examples of the substituent include halogen (fluorine, chlorine, bromine, iodine) and the like, and any of o, m, and p may be substituted.

In the formula (I), a group in which one group X is not bonded to X and ═CH—C ₆ H ₄ —NO ₂ is bonded only to the other X may be used.

  In formula (I), the “alkyl group” is not particularly limited, and examples thereof 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. -Butyl group etc. are mentioned, Although it does not specifically limit with "alkenyl group", For example, a vinyl group, an allyl group, 1-propenyl group, an isopropenyl group, 1-butenyl group, 2-butenyl group etc. are mentioned. . The “alkynyl group” is not particularly limited, and examples thereof include an ethynyl group and a propargyl group. The “cycloalkyl group” is not particularly limited, and examples thereof include a cyclopentyl group and a cyclohexyl group. Examples of the “cycloalkenyl group” include, but are not limited to, a 1,3-cyclohexadienyl group, a 1,4-cyclohexadienyl group, a cyclopentadienyl group, and the like. In the formula (I), one or more hydrogen groups in various hydrocarbon groups may be substituted with a fluorine atom, a chlorine atom or a bromine atom.

In the ink, as described above, in the formula (I), R is a linear saturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, X is different from each other, each of which is a hydrogen atom and a linear saturated C _{1 to} C ₂₀ aliphatic hydrocarbon group or benzyl group, R is a linear saturated C _{1 to} C ₆ aliphatic hydrocarbon group, X is different from each other, saturated C ₁ -C ₆ aliphatic hydrocarbon group or a benzyl group at the chain is more preferable.

  In the ink, silver β-ketocarboxylate represented by the formula (I) is silver 2-methylacetoacetate, silver 2-benzylacetoacetate, silver 2-ethylacetoacetate, silver isobutyrylacetate, silver benzoylacetate, silver acetoacetate, propionyl. Silver acetate, silver α-ethylacetoacetate and silver α-n-butylacetoacetate are preferred. Among the compounds represented by the formula (I), these silver β-ketocarboxylates are raw materials and impurities remaining in the metal silver obtained when decomposition into metal silver by sintering as described later. It is particularly preferable because the concentration of can be sufficiently reduced. As the metallic silver has relatively few impurities, for example, the contact between the relatively precipitated silvers becomes better, the conduction becomes easier, and the resistivity is lowered.

  As described above, the compound having a lone electron pair contained in the ink of the present invention is preferably at least one selected from the group consisting of an amine compound, a thiol compound, and a phosphorus compound.

  Among the compounds having a lone electron pair, the amine compound includes a primary amine compound, a secondary amine compound, a tertiary amine compound, a quaternary amine salt compound, and a cyclic amine compound.

  Examples of the primary amine include monoalkylamine, monoarylamine, mono (cycloalkyl) amine, mono (heteroaryl) amine, substituted monoalkylamine, substituted monoarylamine, and substituted monocycloalkylamine. Substituted mono (heteroaryl) amines, diamines, and the like.

Examples of the monoalkylamine include mono C _1-19 alkylamine. As the monoalkylamine, propylamine, hexylamine, 2-ethylhexylamine, t-butylamine, and octadecylamine (stearylamine) are preferable, and propylamine, hexylamine, 2-ethylhexylamine, and t-butylamine are more preferable.

Examples of the monoarylamine include mono C _6-10 arylamine.

Examples of the mono (cycloalkyl) amine include mono C _3-7 cycloalkylamine. As the mono (cycloalkyl) amine, cyclohexylamine is preferable.

  Examples of the mono (heteroaryl) amine include mono (hetero) containing 6 to 12 membered heteroaryl groups containing one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom. Aryl) amine.

  Examples of the substituent of the substituted monoalkylamine include an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxy group, and a trifluoromethyl group. Examples of the substituent of the substituted monoarylamine include an alkyl group, a halogen atom, a cyano group, a nitro group, a hydroxy group, and a trifluoromethyl group. Examples of the substituent such as substituted monocycloalkylamine and substituted mono (heteroaryl) amine include an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxy group, and a trifluoromethyl group. It is done.

Examples of the substituted monoalkylamine include mono C _1-9 alkylamine substituted with an aryl group. As the substituted monoalkylamine, 2-phenylethylamine and benzylamine are preferable, and 2-phenylethylamine is more preferable.

Examples of the substituted monoarylamine include mono-C _6-10 arylamine substituted with a bromine atom. As the substituted monoarylamine, 2-bromobenzylamine is preferable.

Examples of the substituted mono (cycloalkyl) amine include mono C _3-7 cycloalkylamine substituted with C _1-5 alkyl. As the substituted mono (cycloalkyl) amine, 2,3-dimethylcyclohexylamine is preferable.

  Examples of the substituted mono (heteroaryl) amine include a 6-12 membered heteroaryl group containing one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom. Substituted mono (heteroaryl) amines.

Examples of the diamine include C _1-10 alkylene diamine. As said diamine, ethylenediamine is preferable.

  Examples of the secondary amine include dialkylamine, diarylamine, di (cycloalkyl) amine, di (heteroaryl) amine, substituted dialkylamine, substituted diarylamine, substituted dicycloalkylamine, and substituted And di (heteroaryl) amine.

Examples of the dialkylamine include diC _1-9 alkylamines including C _1-9 alkyls which may be the same as or different from each other. As the dialkylamine, methylhexylamine is preferable.

Examples of the diarylamine include diC _6-10 arylamines including C _6-10 aryls which may be the same as or different from each other.

Examples of the di (cycloalkyl) amine include diC _3-7 cycloalkylamine including C _3-7 cycloalkyl, which may be the same as or different from each other.

  The di (heteroaryl) amine may be, for example, 6 to 12-membered one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom, and may be the same or different from each other. Di (heteroaryl) amines containing good heteroaryl groups are mentioned.

  Examples of the substituent of the substituted dialkylamine include an aryl group, a halogen atom, a cyano group, a nitro group, and a trifluoromethyl group. Examples of the substituent of the substituted diarylamine include an alkyl group, a halogen atom, a cyano group, a nitro group, and a trifluoromethyl group. Examples of the substituent such as substituted dicycloalkylamine and substituted di (heteroaryl) amine include an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, and a trifluoromethyl group.

Examples of the substituted dialkylamine include diC _1-9 alkylamines containing C _1-9 alkyl substituted with a hydroxyl group, which may be the same as or different from each other. As the substituted dialkylamine, diethanolamine, methylbenzylamine and the like are preferable.

  Examples of the substituted di (heteroaryl) amine include a 6-12 membered heteroaryl group containing one or more atoms selected from the group consisting of a nitrogen atom, a sulfur atom and an oxygen atom. Substituted mono (heteroaryl) amines.

  Examples of the tertiary amine include trialkylamine, monoaryldialkylamine, and mono (cycloalkyl) dialkylamine.

Examples of the trialkylamine include tri (C _1-19 alkyl) amine. As the trialkylamine, dimethyloctadecylamine and the like are preferable.

Examples of the monoaryl dialkylamine include mono C _6-10 aryl di (C _1-6 alkyl) amine.

Examples of the mono (cycloalkyl) dialkylamine include mono (C _3-7 cycloalkyl) di (C _1-6 alkyl) amine. As the mono (cycloalkyl) dialkylamine, dimethylcyclohexylamine and the like are preferable.

  Examples of the quaternary amine salt include tetraalkylammonium halides.

Examples of the tetraalkylammonium halide include tetra (C _1-19 alkyl) ammonium halide. As the tetraalkylammonium halide, dodecyltrimethylammonium bromide, tetradodecylammonium bromide and the like are preferable.

  As the cyclic amine compound, pyridine is preferable.

  Among the compounds having a lone pair, examples of the thiol compound include monoalkyl thiol and monoaryl thiol.

Examples of the monoalkylthiol include mono (C _1-19 alkyl) thiol. As the monoalkylthiol, todecylthiol and the like are preferable.

Among the compounds having a lone electron pair, examples of the phosphorus compound include (alkyl) ₃ P, (aryl) ₃ P, (substituted alkyl) ₃ P, (substituted aryl) ₃ P, and phosphonic acid esters.

Examples of the (alkyl) ₃ P include (C _1-9 alkyl) ₃ P including C _1-9 alkyl which may be the same as or different from each other. The (C _1-9 alkyl) ₃ P is preferably tributylphosphine or trioctylphosphine.

Examples of the (aryl) ₃ P include (C _6-10 aryl) ₃ P including C _6-10 aryl which may be the same as or different from each other.

Examples of the substituent of the “substituted alkyl” of (substituted alkyl) ₃ P include an aryl group, a halogen atom, a cyano group, a nitro group, and a trifluoromethyl group. In addition, examples of the substituent of the “substituted aryl” of the (substituted aryl) ₃ P include an alkyl group, a halogen atom, a cyano group, a nitro group, and a trifluoromethyl group.

Examples of the (substituted alkyl) ₃ P include (substituted C _1-9 alkyl) ₃ P including substituted C _1-9 alkyl which may be the same as or different from each other. The (substituted C _1-9 alkyl) ₃ P is preferably tributyl phosphite.

Examples of the (substituted aryl) ₃ P include (substituted C _6-10 aryl) ₃ P including substituted C _6-10 aryl which may be the same as or different from each other.

Examples of the phosphonic acid ester include alkylphosphonic acid dialkyl esters and substituted alkylphosphonic acid dialkyl esters. Examples of the alkylphosphonic acid dialkyl ester include C _1-6 alkylphosphonic acid di (C _1-6 alkyl) ester. Examples of the substituted alkylphosphonic acid dialkyl ester include substituted C _1-6 alkylphosphonic acid di (C _1-6 alkyl) esters, and ethyl diethylphosphonoacetate is preferred.

  In the ink of the present invention, the β-ketocarboxylate represented by the formula (I) is preferably a primary amine compound, a phosphorus compound, a secondary amine compound or a thiol compound as the compound having a lone electron pair. More preferred are phosphorus compounds, and even more preferred are primary amine compounds.

  In the ink of the present invention, the content of the silver β-carboxylate represented by the formula (I) and the compound having a lone electron pair is as follows: the silver β-carboxylate (A) and the compound having the lone electron pair (B ) Molar ratio (A) :( B) is, for example, from 1: 1.5 to 200, preferably from 1: 2 to 200, more preferably from 1: 3 to 200.

  As described above, the ink of the present invention may further contain a solvent. The solvent is selected from the group consisting of an alcohol, a ketone, an ester, an ether, an aromatic hydrocarbon, an aliphatic hydrocarbon, a cyano group or an aliphatic hydrocarbon substituted with a halogen atom and water as described above. The above is preferable. As said alcohol, the C1-C9 aliphatic hydrocarbon which has 1-5 hydroxyl groups is mentioned, for example. Examples of the aliphatic hydrocarbon having 1 to 5 hydroxyl groups and having 1 to 5 carbon atoms include methanol, ethanol, propanol, 2-propanol, butanol, pentanol, hexanol, octanol, nonanol, ethylene glycol, glycerol and the like. It is done. As said alcohol, the C1-C5 aliphatic hydrocarbon which has 1-3 said hydroxyl groups is preferable, for example. Examples of the C1-C5 aliphatic hydrocarbon having 1 to 3 hydroxyl groups include methanol, ethanol, propanol, 2-propanol, butanol, pentanol, ethylene glycol, and glycerol.

Examples of the ketone include (alkyl) ₂ C═O, (alkyl) (aryl) C═O, (aryl) ₂ C═O, (substituted alkyl) ₂ C═O, (substituted alkyl) (aryl) C═O. , (Alkyl) (substituted aryl) C═O, (substituted aryl) ₂ C═O, cyclic ketone, and the like.

Examples of the (alkyl) ₂ C═O include (C _1-9 alkyl) ₂ C═O including C _1-9 alkyl which may be the same as or different from each other. The (alkyl) ₂ C═O is preferably 2,2-dimethyl-3-hexanone.

Examples of the (alkyl) (aryl) C═O include (C _1-9 alkyl) (C _6-10 aryl) C═O.

Examples of the (aryl) ₂ C═O include (C _6-10 aryl) ₂ C═O including C _6-10 aryl which may be the same as or different from each other.

As the substituent of the “substituted alkyl” in the above (substituted alkyl) ₂ C═O and (substituted alkyl) (aryl) C═O, aryl group, halogen atom, cyano group, nitro group, hydroxy group, trifluoromethyl group Etc. In addition, examples of the substituent of (alkyl) (substituted aryl) C═O and (substituted aryl) ₂ C═O include an alkyl group, a halogen atom, a cyano group, a nitro group, a hydroxy group, and a trifluoromethyl group. .

Examples of the (substituted alkyl) ₂ C═O include (substituted C _1-9 alkyl) ₂ C═O including substituted C _1-9 alkyl which may be the same as or different from each other.

Examples of the (substituted alkyl) (aryl) C═O include (substituted C _1-9 alkyl) (C _6-10 aryl) C═O.

Examples of the (alkyl) (substituted aryl) C═O include (C _1-9 alkyl) (substituted C _6-10 aryl) C═O.

Examples of the (substituted aryl) ₂ C═O include (substituted C _6-10 aryl) ₂ C═O including substituted C _6-10 aryl which may be the same as or different from each other.

Examples of the cyclic ketone include C _4-10 cycloalkanone. As the cyclic ketone, cyclohexanone is preferable.

  Examples of the ester include an ester of a carboxylic acid having 2 to 20 carbon atoms and an aliphatic alcohol having 1 to 6 carbon atoms. As said ester, ethyl acetate, pentyl acetate, acetic acid 3-methylbutyl ester, and ethyl hexanoate are preferable.

Examples of the ether include (alkyl) ₂ O. Examples of the (alkyl) ₂ O include (C _1-9 alkyl) ₂ O containing C _1-9 alkyl which may be the same as or different from each other. As the (alkyl) ₂ O, diethyl ether is preferable.

  Examples of the aromatic hydrocarbon include aromatic hydrocarbons having 6 to 24 carbon atoms and substituted aromatic hydrocarbons having 6 to 24 carbon atoms. Examples of the directional group hydrocarbon include benzene and toluene, and toluene is preferable.

  As said aliphatic hydrocarbon, a C1-C9 aliphatic hydrocarbon is mentioned. Examples of the aliphatic hydrocarbon having 1 to 9 carbon atoms include pentane, hexane, heptane, octane, and nonane. Examples of the aliphatic hydrocarbon include hexane and isooctane, and isooctane is preferable.

  Examples of the aliphatic hydrocarbon substituted with a cyano group or a halogen atom include C1-C9 aliphatic hydrocarbons substituted with a cyano group or a halogen atom. Examples of the aliphatic hydrocarbon substituted with the cyano group or the halogen atom include acetonitrile, dichloromethane, chloroform and the like, and acetonitrile and chloroform are preferable.

Mono C _1-9 alkylamine, diC _1-9 alkylamine, (C _1-9 alkyl) ₃ P, (substituted C _1-9 alkyl) ₃ P, (C _1-9 alkyl) substituted with the aryl group ) ₂ C═O, (C _1-9 alkyl) (C _6-10 aryl) C═O, (substituted C _1-9 alkyl) ₂ C═O, (substituted C _1-9 alkyl) (C _6-10 aryl) C = O, (C _1-9 alkyl) (C _6-10 aryl) C = O, (C _1-9 alkyl) of 1 to 9 carbon atoms in the ₂ O and alkyl (C _1-9 alkyl ) Is methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, n-pentyl, i-pentyl, sec-pentyl, t-pentyl, 2-methylbutyl N-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethyl Rubutyl, 2-ethylbutyl, 3-ethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1-ethyl-1-methylpropyl, n-heptyl, 1-methylhexyl, 2 -Methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 4-ethylpentyl, 1,1-dimethylpentyl, 2,2- Dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1-propylbutyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4- Ethylhexyl, 5-ethylhexyl, 1,1-dimethylhexyl, 2,2-dimethylhexyl, 3,3-dimethylhexyl, 4,4-dimethylhexyl, 5,5-dimethylhexyl, 1-propylpentyl, and 2-propyl It is linear or branched alkyl such as pentyl, and preferably has 3 to 6 carbon atoms.

The mono C _6-10 aryl amine, C _6-10 aryl amines, mono C _6-10 aryldi (C _1-6 alkyl) amines, (C _6-10 aryl) ₃ P, (C _6-10 aryl) ₃ P, (C _1-9 alkyl) (C _6-10 aryl) C═O, (C _6-10 aryl) ₂ C═O, (substituted C _1-9 alkyl) (C _6-10 aryl) C═O , (C _1-9 alkyl) (substituted C _6-10 aryl) C═O, (substituted C _6-10 aryl) ₂ C═O and the like as aryl having 6 to 10 carbon atoms (ie, C _6-10 aryl) Examples include phenyl and naphthyl.

A cycloalkyl having 3 to 7 carbon atoms in the mono C _3-7 cycloalkylamine, diC _3-7 cycloalkylamine, mono (C _3-7 cycloalkyl) di (C _1-6 alkyl) amine, etc. (ie, C Examples of ( _3-7 cycloalkyl) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like, more preferably those having 1 to 4 carbon atoms, cyclopropyl, and cyclobutyl.

The 3- to 12-membered heteroaryl containing one or more atoms selected from the group consisting of the nitrogen atom, sulfur atom and oxygen atom,
3- to 8-membered, preferably 5- or 6-membered heterocyclic monocyclic group having 1 to 4 nitrogen atoms, such as pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazolyl, tetrazolyl, pyrrolidinyl, imidazolidinyl, Piperidinyl, pyrazolidinyl, piperazinyl and the like;
A 3- to 8-membered, preferably 5- or 6-membered heteromonocyclic group having one oxygen atom, such as furanyl;
A 3-8 membered, preferably 5 or 6 membered heterocyclic monocyclic group having one sulfur atom, such as thienyl;
A 3- to 8-membered, preferably 5- or 6-membered heteromonocyclic group having 1-2 oxygen atoms and 1-3 nitrogen atoms, such as oxazolyl, isoxazolyl, oxadiazolyl, morpholinyl and the like;
A 3- to 8-membered, preferably 5- or 6-membered heteromonocyclic group having 1 or 2 sulfur atoms and 1 to 3 nitrogen atoms, such as thiazolyl, thiadiazolyl, thiazolidinyl and the like;
7-12 membered, preferably 9 or 10 membered heterocyclic group having 1-5 nitrogen atoms such as indolyl, isoindolyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl, tetrazolopyridyl, Tetrazolopyridazinyl, dihydrotriazolopyridazinyl and the like;
A 7-12 membered, preferably 9 or 10 membered, heterocyclic group having 1 to 3 sulfur atoms, such as dithiaphthalenyl, benzothiophenyl and the like;
A 7-12 membered, preferably 9 or 10 membered, heterocyclic group having 1-2 oxygen atoms and 1-3 nitrogen atoms, such as benzoxazolyl, benzooxadiazolyl and the like;
Examples thereof include 7 to 12 member, preferably 9 or 10 membered heterocyclic groups having 1 or 2 sulfur atoms and 1 to 3 nitrogen atoms, such as benzothiazolyl and benzothiadiazolyl.

  As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A fluorine atom, a chlorine atom, and a bromine atom are preferable.

  The ink of the present invention has a viscosity of, for example, 0.5 mPa · s to 50000 mPa · s, preferably 0.5 mPa · s to 100 mPa · s, and more preferably 0.5 mPa · s to 20 mPa · s. If the viscosity is in the range of 0.5 mPa · s to 16 mPa · s as described above, the ink can be suitably used, for example, in an inkjet method. Moreover, if the viscosity is in the range of 10 mPa · s to 50000 mPa · s as described above, the ink can be suitably used in, for example, a gravure printing method. The viscosity was measured at room temperature by a vibration type viscosity measurement method.

  The ink of the present invention has a surface tension of, for example, 5 mN / m or more and 100 mN / m or less, preferably 10 mN / m or more and 80 mN / m or less, more preferably 20 mN / m or more and 60 mN / m or less. If the surface tension is in the range from 5 mN / m to 100 mN / m as described above, the ink can be suitably used, for example, in an ink jet method. The surface tension was measured under the conditions of a bubble frequency of 0.1 Hz to 10 Hz at room temperature by a pressure change measurement method when bubbles were generated.

  Further, in the ink of the present invention, the silver β-ketocarboxylate represented by the formula (I) is, when the compound having the lone pair is a primary amine compound or a secondary amine compound, water, alcohol, Preferred are lower hydrocarbons such as ethers, esters, ketones and isooctanes, aliphatic hydrocarbons substituted with cyano groups or halogen atoms, and alcohols, ethers, esters and ketones are more preferred. Further, the silver β-ketocarboxylate represented by the formula (I) is a solvent containing an oxygen atom such as water, alcohol, ether, ester or ketone as a solvent when the compound having the lone electron pair is a phosphorus compound. Are preferred, and alcohol is more preferred.

  As described above, the ink of the present invention is sufficiently stable during printing, that is, the time required for printing. As a result, stable printing is possible using the ink of the present invention. In addition, the ink of the present invention can be stably stored at a low temperature to a room temperature. For example, it can be stably printed at a room temperature using an ink that has been stored at a low temperature (such as a refrigerator) for a relatively long period of time. it can.

  As described above, the method for forming the wiring of the present invention includes the step of forming the wiring by disposing the ink of the present invention on the substrate and baking the substrate on which the ink is disposed.

  In the above method, the substrate is not particularly limited as long as the ink of the present invention can be disposed on the surface thereof, and examples thereof include those formed from ceramic, glass, resin, paper, metal, silicon and the like. . Since the heating temperature is low in the method, a method that is vulnerable to heating, such as a thermoplastic resin, can be used.

  In the above method, the step of applying the ink on the substrate is not particularly limited as long as the ink of the present invention can be disposed on the substrate surface, but may be performed by, for example, a printing method or a coating method. Examples of the printing method include a screen printing method, an offset printing method, an ink jet printing method, a flexographic printing method, a dispenser printing method, and a gravure printing method, and an ink jet printing method is preferable.

  In the method, the step of baking the substrate on which the ink is disposed can be performed, for example, at 80 ° C. or higher and 200 ° C. or lower, preferably 80 ° C. or higher and 150 ° C. or lower, more preferably 140 ° C.

[Reference Example 1]
(Production of silver 2-benzylacetoacetate)
Sodium hydroxide (1.92 g) was dissolved in water (8 ml). While stirring this at room temperature, ethyl 2-benzylacetoacetate (8.89 g: manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was further stirred for 30 minutes. did. Thereafter, ethanol was removed by a rotary evaporator, and the remaining aqueous layer was washed with ether. Ether (20 ml) was added thereto, and a solution obtained by dissolving concentrated sulfuric acid (2.35 g) in water (8 ml) was added dropwise with stirring under ice cooling. The ether layer was separated, and the aqueous layer was salted out and extracted with ether. The ether layer was collected to obtain an ether solution of 2-benzylacetoacetic acid.

Diethanolamine (4.41 g) was dissolved in water (15 ml), and this solution was added to an ether solution of 2-benzylacetoacetic acid under ice cooling. Subsequently, a solution of silver nitrate (6.36 g) dissolved in water (15 ml) was added dropwise. Then, the precipitated white precipitate was collected by filtration, washed with ice water, followed by isopropanol, and dried to obtain silver 2-benzylacetoacetate as a [white] precipitate (yield 7 g).
FIG. 7 shows FT-IR. IR (KBr): 1700.45, 1538.94 cm- ¹ .
Elemental analysis: C: 43.83%, H: 3.39%, Ag: 35.85%. Theoretical value: C: 44.18%, H: 3.71%, Ag: 36.07%.
¹ H-NMR: δ 1.055 (2H t), 2.119 (3H s), 3.010 (1H t), 7.186 (5H m).

[Example 1]
Silver 2-methylacetoacetate (2.5 g) and phenethylamine (5 g) were mixed while cooling with ice water to produce an ink. The manufactured ink was allowed to stand at room temperature for 24 hours, and then the stability of the ink at room temperature was evaluated. This stability indicates that the ink after standing at room temperature for 24 hours, “◯” means a transparent and precipitate-free solution, “Δ” means a white or yellow solution or gel that is not transparent, “X” means a solution having a black, gray, or silver precipitate. Silver 2-methylacetoacetate was produced according to the method described in International Publication No. 2007/4437. Table 1 shows the compounding ratio (% by weight) of components and the evaluation of stability.

[Examples 2 to 10]
An ink was produced by mixing silver 2-methylacetoacetate (2.5 g), phenethylamine (5 g), and optionally a solvent while cooling with ice water. The stability of the manufactured ink at room temperature was evaluated in the same manner as in Example 1. Table 1 shows the compounding ratio (% by weight) of components and the evaluation of stability.

[Comparative Examples 1 and 2]
In addition, ink was produced by mixing silver 2-methylacetoacetate and a solvent at room temperature (Comparative Examples 1 and 2). The stability of the produced ink was evaluated in the same manner as in Example 1. Table 1 shows the compounding ratio (% by weight) of components and the evaluation of stability.

  As shown in Table 1, from the results of Examples 1 to 10, it was confirmed that the ink containing 2-methylacetoacetic acid and phenethylamine had high stability for 24 hours at room temperature. Further, from the results of Examples 2 to 10, it was confirmed that the ink containing 2-methylacetoacetic acid, phenethylamine, and a solvent was highly stable at room temperature for 24 hours. Therefore, it was confirmed that these inks were stable during printing. In addition, when the ink manufactured in Example 5 was preserve | saved in the freezer, it has also confirmed that it was stable for 1 month or more.

[Example 11]
Silver 2-methylacetoacetate (2.5 g, 25% by weight), phenethylamine (5 g, 50% by weight) and ethanol (2.5 g, 25% by weight) were mixed with cooling with ice water to produce an ink. .

[Example 12]
An ink was produced in the same manner as in Example 11 except that 2-ethylhexylamine was used instead of phenethylamine.

[Example 13]
An ink was produced in the same manner as in Example 11 except that hexylamine was used instead of phenethylamine.

[Example 14]
Silver 2-methylacetoacetate (2.5 g, 25 wt%), 2-ethylhexylamine (5 g, 50 wt%) and n-butanol (2.5 g, 25 wt%) were mixed while cooling with ice water. Ink was produced.

[Example 15]
An ink was produced in the same manner as in Example 14 except that 2-propanol was used instead of n-butanol.

[Example 16]
An ink was produced in the same manner as in Example 11 except that propylamine was used instead of phenethylamine.

(Experiment 1 regarding firing)
The ink produced in Example 11 was used to print on one side of paper (laser printer paper, manufactured by KOKUYO, product name: LBP-FG1310) by an inkjet method. The paper on which the printed ink was placed was heated at 150 ° C. for 5 minutes. The metallic silver film on the obtained paper was observed with SEM. The result is shown in FIG. 1A shows the surface of the coating film by SEM observation, and FIG. 1B shows the cross section of the coating film after FIB (Focused Ion beam) processing. As shown in FIGS. 1 (a) and 1 (b), it was confirmed that when the ink of the present invention was used for heating, a metallic silver film was formed without any gaps. The thickness of the metallic silver film was about 0.3 μm.

  During heating, the state of the ink printed on the laser printer paper at regular intervals was observed with an optical microscope. The result is shown in FIG. As shown in FIG. 2, formation of silver particles was observed from heating at around 75 ° C., formation of a film of silver particles was observed from heating at around 90 ° C., and firing of silver particles from heating at around 120 ° C. Was confirmed to be complete.

(Experiment 2 regarding firing)
Also, using the ink produced in Example 11, a piezo-type ink jet device (product name: KM512LN, manufactured by Konica Minolta IJ Co., Ltd.), glossy paper for laser printers (product name: glossy paper for laser printers, manufactured by KOKUYO). 50 mm on thick (LBP-FG1310), thickness: 193 μm, paper coated with a white or smooth inorganic oxide layer such as calcium carbonate, and a resin adsorption layer such as polyvinyl alcohol on the paper) It was printed in the shape of a band with a size of × 1.5 mm. The paper on which the printed ink was placed was heated at 80 ° C, 100 ° C, 120 ° C, or 150 ° C. The electrical properties of the metallic silver coating on the paper obtained at each heating temperature were measured.

The electrical characteristics were evaluated by volume resistance, and the measurement was performed using a two-terminal tester. The result is shown in FIG. Moreover, the optical micrograph of the surface of the metal silver film obtained by heating at 150 degreeC for 10 minute (s) is shown in FIG. As shown in FIG. 3, it was confirmed that a volume resistance value of 10 ⁻⁴ Ωcm or less was obtained by heating at 120 ° C. for 15 minutes.

(Experiment 3 on firing)
Using the inks produced in Examples 11, 12 and 13, paper (manufactured by KOKUYO, product name: thick glossy paper for laser printers (LBP-FG1310), thickness: 193 μm, whitening or smoothing on the paper, using the ink produced in Examples 11, 12 and 13 Printed on one surface of an inorganic oxide layer such as calcium carbonate and a resin coated layer made of a resin such as polyvinyl alcohol. The paper on which the printed ink was placed was heated over temperature. TGA measurement was performed on the firing of the ink on the obtained paper. The temperature was measured from room temperature to 300 ° C. at a heating rate of 10 ° C./min. The result is shown in FIG. Also, silver nitrate (2.5 g, 25% by weight), 2-ethylhexylamine (5 g, 50% by weight), and ethanol (2.5 g, 25% by weight) were mixed while being cooled with ice water to obtain ink. Manufactured. This silver nitrate ink was printed on one side of the paper in the same manner as described above. FIG. 5 (b) shows the results relating to Example 12 and the firing of this silver nitrate ink. As shown in FIG. 5A, it was confirmed that a metallic silver film was formed at 140 ° C. when heated using the inks of Examples 12 and 13. Further, as shown in FIG. 5B, when heated using the ink of Example 12, a metal film is formed at 140 ° C. On the other hand, when heated using silver nitrate ink, it was confirmed that a metal film was formed at 210 ° C.

(Experiment on viscosity)
The viscosity of the ink produced in Examples 11-16 was measured. Viscosity measurement was performed using a vibration type viscosity measuring apparatus (manufactured by CBC, VM-10A). The obtained results are shown in Table 2.

  As shown in Table 2, it was confirmed that the inks of Examples 11 to 16 had a viscosity of 16 mPa · s or less. An ink having such a viscosity can be printed using an ink jet type cartridge.

(Experiment on surface tension)
The surface tensions of the inks produced in Examples 11 to 13 and 16 were measured. The surface tension was measured using a dynamic surface tension meter (manufactured by SITA). The obtained result is shown in FIG.

  As shown in FIG. 6, it was confirmed that the inks of Examples 11 to 13 and 16 had a surface tension of 20 to 60 mN / m. Ink having such a surface tension can be printed using an ink jet type cartridge.

(Experiment on silver β-ketocarboxylate)
[Example 17]
Silver 2-methylacetoacetate (2.5 g, 25% by weight), 2-ethylhexylamine (5 g, 50% by weight) and ethanol (2.5 g, 25% by weight) were mixed with cooling with ice water to prepare an ink. Manufactured.

[Example 18]
An ink was produced in the same manner as in Example 17 except that 1-butanol was used instead of ethanol.

[Example 19]
An ink was produced in the same manner as in Example 17 except that 2-phenylethylamine was used instead of 2-ethylhexylamine.

[Example 20]
An ink was produced in the same manner as in Example 17 except that 2-phenylethylamine was used instead of 2-ethylhexylamine and 1-butanol was used instead of ethanol.

[Example 21]
Silver 2-benzylacetoacetate (2.5 g, 25 wt%), 2-phenylethylamine (5 g, 50 wt%) and 1-butanol (2.5 g, 25 wt%) were mixed while cooling with ice water. Thus, an ink was manufactured.

[Example 22]
Silver 2-ethylacetoacetate (2.5 g, 25% by weight), 2-ethylhexylamine (5 g, 50% by weight) and ethanol (2.5 g, 25% by weight) were mixed with cooling with ice water to prepare an ink. Manufactured.

  The stability of the inks produced in each of Examples 17 to 22 was evaluated in the same manner as in Example 1. The results are shown in Table 3.

  In the table, “◯” means a clear solution without precipitation, “Δ” means a white or yellow solution or gel that is not transparent, and “×” means a black, gray, or silver-colored solution. Means.

  As shown in Table 3, from the results of Examples 17 to 22, it was confirmed that the ink containing silver β-ketocarboxylate, a compound having a lone electron pair, and a solvent was highly stable at room temperature for 24 hours. . Therefore, it was confirmed that these inks were stable during printing. In addition, when the ink manufactured in Examples 17, 18 and 19 was stored in a freezer, it was confirmed that the ink was stable for one month or more.

(Experiment on types of compounds with lone pairs)
An ink was produced by mixing silver 2-methylacetoacetate, a compound having a lone electron pair, and a solvent while cooling with ice water. The types of these components are shown in Table 4. The stability of the produced ink was evaluated in the same manner as in Example 1. The compounding ratio (% by weight) of the components is 25% by weight of silver 2-methylacetoacetate, 50% by weight of the compound having a lone electron pair, and 25% by weight of the solvent. Table 4 shows the types of compounds and solvents having lone electron pairs, and the evaluation of stability. Silver 2-methylacetoacetate was produced according to the method described in International Publication No. 2007/4437.

  In the table, “◯” means a clear solution without precipitation, “Δ” means a white or yellow solution or gel that is not transparent, and “×” means a black, gray, or silver-colored solution. Means.

  As shown in Table 4, it was confirmed that the ink containing 2-methylacetoacetate silver and compounds having various lone pairs has excellent stability for 24 hours at room temperature. Therefore, it was confirmed that these inks were stable during printing. In particular, an ink using a primary amine or phosphorus compound as a compound having a lone electron pair was stable after 24 hours at room temperature. An ink using a secondary amine, tertiary amine, diamine or thiol as a compound having a lone electron pair was stable after 5 hours at room temperature. In addition, when the ink manufactured in Examples 25, 28, 29, 31, 32, and 34 was stored in a freezer, it was confirmed that the ink was stable for one month or more.

(Solvent experiment)
An ink was produced by mixing silver 2-methylacetoacetate, a compound having a lone electron pair, and a solvent while cooling with ice water. The types of these components are shown in Table 5. The stability of the produced ink was evaluated in the same manner as in Example 1. The compounding ratio (% by weight) of the components is 25% by weight of silver 2-methylacetoacetate, 50% by weight of the compound having a lone electron pair, and 25% by weight of the solvent. Table 5 shows the types of the compound having a lone electron pair and the solvent, and the evaluation of the stability. Silver 2-methylacetoacetate was produced according to the method described in International Publication No. 2007/4437.

  In the table, “◯” means a clear solution without precipitation, “Δ” means a white or yellow solution or gel that is not transparent, and “×” means a black, gray, or silver-colored solution. Means.

  As shown in Table 5, it was confirmed that the ink containing silver 2-methylacetoacetate, compounds having various lone pairs and a solvent had excellent stability at room temperature for 24 hours. Therefore, it was confirmed that these inks were stable during printing. In particular, inks using water or alcohol as a solvent were stable after 24 hours at room temperature. In addition, when the ink manufactured in Example 45, 46, 47 was preserve | saved in the freezer, it has also confirmed that it was stable for one month or more.

(Experiment regarding the ratio of β-ketocarboxylate, compound having lone pair and solvent)
An ink was produced by mixing silver 2-methylacetoacetate, a compound having a lone pair and a solvent while cooling with ice water. Table 6 shows the types and weight ratios of these components. The stability of the produced ink was evaluated in the same manner as in Example 1. Table 5 shows the types of compounds and solvents having lone electron pairs and the evaluation of stability. Silver 2-methylacetoacetate was produced according to the method described in International Publication No. 2007/4437.

  In the table, “◯” means a clear solution without precipitation, “Δ” means a white or yellow solution or gel that is not transparent, and “×” means a black, gray, or silver-colored solution. Means.

  As shown in Table 6, it was confirmed that the ink containing silver 2-methylacetoacetate, a compound having various lone pairs and a solvent had excellent stability for 24 hours at room temperature. Therefore, it was confirmed that these inks were stable during printing. Further, it was confirmed that an ink containing 3 moles or more of a compound having a lone pair with respect to 1 mole of silver β-ketocarboxylate is stable at room temperature.

  The ink of the present invention can also be applied to high-density circuit formation.

Claims (4)

An ink comprising silver β-ketocarboxylate represented by the formula (I) and a compound having a lone pair of electrons,
An ink in which the compound having a lone electron pair is one or more selected from the group consisting of an amine compound, a thiol compound, and a phosphorus compound.

[In the formula (I), R is a straight-chain, saturated or unsaturated C ₁ branched or cyclic -C ₂₀ aliphatic hydrocarbon _{^{group, R 1 -CY 2 -, CY}} 3 -, R 1 -CHY- R ² O—, a phenyl group, a phenyl group substituted with one or more substituents, R ⁵ R ⁴ N—, a hydroxyl group, an amino group, or (R ³ O) ₂ CY—.
Where Y is the same or different and each is a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom, and R ¹ is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₁₉ aliphatic carbonization. A hydrogen group or a phenyl group, R ² is a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, and R ³ is a linear, branched or cyclic saturated group. or unsaturated C ₁ -C ₁₆ aliphatic hydrocarbon radical, R ⁴ and R ^5, which are identical or different, each a straight-chain, branched or cyclic saturated or unsaturated C ₁ -C ₁₈ aliphatic It is a hydrocarbon group.
In the formula (I), X's are the same or different and are each a hydrogen atom, a linear, branched or cyclic saturated or unsaturated C _{1 to} C ₂₀ aliphatic hydrocarbon group, R ⁶ O—, R ⁶ S-, R ⁶ -CO-, R ⁶ -CO-O-, halogen, benzyl group, phenyl group, phenyl or benzyl group substituted with one or more substituents, cyano group, N-phthaloyl- 3-aminopropyl group and 2-ethoxyvinyl group.
Where R ⁶ is substituted with a linear, branched or cyclic saturated or unsaturated C ₁ -C ₁₀ aliphatic hydrocarbon group, thiophenyl group, phenyl group, diphenyl group, or one or more substituents It is a phenyl group or a diphenyl group. ]   The ink according to claim 1, wherein the compound having a lone electron pair has 2 to 24 carbon atoms.   The compound having the lone electron pair is 2-phenylethylamine, 2-ethylhexylamine, hexylamine, propylamine, tert-butylamine, ethylenediamine, N-methylhexylamine, trioctylphosphine, tributylphosphine, tributylphosphite, 1 or more selected from the group consisting of stearylamine, dimethyloctadecylamine, methylbenzylamine, dimethylcyclohexylamine, dodecanethiol, ethyl diethylphosphonoacetate, dodecyltrimethylammonium bromide and tetradecylammonium bromide The ink described in 1. The ink according to any one of claims 1 to 3 is arranged on a substrate,
A method of forming a wiring by baking a substrate on which the ink is disposed.

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