JP2017226797A - Processing method of silver ink composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method of a silver ink composition, by which a fine pattern of metal silver having little fluctuations in a resistance value can be formed even when a silver ink composition prepared by compounding a material for forming metal silver is subjected to continuous printing.SOLUTION: The processing method of a silver ink composition includes a step of processing a silver ink composition prepared by compounding a β-ketocarboxylic acid silver, a nitrogen-containing compound, a reducing agent, and acetylene alcohols to satisfy a relation of expression (i) 306.47e≤y≤2403.2e, where x represents a process temperature (°C) of the silver ink composition and y (h) represents a process time, and x ranges from 0 to 42.SELECTED DRAWING: None

Description

  The present invention relates to a method for treating a silver ink composition.

  A laminate in which a conductive fine pattern is formed on a substrate is useful as a member of various electronic devices, for example. As such a member, for example, a wiring board in which a conductive thin wire is formed on a substrate can be cited, and it can be used to configure a transparent electrode, an electromagnetic wave shield, a touch panel, and the like. In particular, the demand for touch panels is rapidly increasing in various display elements including information communication devices such as portable terminals, and members such as the above-described wiring boards occupy important positions.

  As a constituent material of such a conductive fine pattern, metallic silver is considered promising. For example, a fine pattern is formed by a printing method using a conductive ink composition containing metallic silver particles. A method of forming a wiring pattern by heat-treating is disclosed (see Patent Document 1).

JP 2012-253172 A

  On the other hand, when a fine pattern is formed by a printing method, it is important that the fine pattern can be stably formed when the ink composition is continuously printed. In the case of a fine pattern of metallic silver, it is desired that the resistance value fluctuates little even when the ink composition is formed by continuous printing. On the other hand, the ink composition disclosed in Patent Document 1 is not suitable for suppressing such variation in resistance value.

  In recent years, in addition to an ink composition containing metallic silver particles, a silver ink composition containing a metallic silver forming material that forms metallic silver by a reaction has been reported. Such a silver ink composition is highly versatile because it can easily form metallic silver under mild conditions, and even when continuously printed in the same manner as described above, a fine pattern of metallic silver with a small variation in resistance value can be obtained. It is very useful if it can be formed.

  The present invention has been made in view of the above circumstances, and even when a silver ink composition containing a metallic silver forming material is subjected to continuous printing, a fine pattern of metallic silver having a small variation in resistance value. It is an object of the present invention to provide a method for treating a silver ink composition so as to form a film.

In order to solve the above problems, the present invention provides a silver β-ketocarboxylate represented by the following general formula (1), an amine compound having 25 or less carbon atoms, a quaternary ammonium salt having 25 or less carbon atoms, ammonia, and the above-mentioned Selected from the group consisting of one or more nitrogen-containing compounds selected from the group consisting of an ammonium salt formed by reaction of an amine compound or ammonia with an acid, and oxalic acid, hydrazine and a compound represented by the following general formula (5) A silver ink composition comprising one or more reducing agents and an acetylene alcohol represented by the following general formula (2): a treatment temperature x (° C.) of the silver ink composition and a treatment Provided is a method for treating a silver ink composition, which comprises a step of treating so that time y (h) satisfies the relationship of the following formula (i) (where x is 0 to 42).
HC (= O) -R ²¹ (5)
(In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.)
306.47e ^−0.139x ≦ y ≦ 2403.2e ^−0.128x (i)

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

（式中、Ｒ’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 each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)

  In the method for treating a silver ink composition of the present invention, the silver ink composition rotates the stirring blade in a stirring tank, whereby the silver β-ketocarboxylate, the nitrogen-containing compound, and the reducing agent The acetylene alcohols are produced by a production method having a step of stirring the acetylene alcohols in the stirring tank, and as the stirring blade, the drive shaft and the vicinity of the inner peripheral surface of the stirring tank are rotated and moved. It is preferable to use the one provided with a forced flow generating blade portion having an outer side and a connecting portion connecting the drive shaft and the forced flow generating blade portion.

  According to the present invention, a silver ink composition in which a metal silver forming material is blended can be used to form a fine pattern of metal silver with a small resistance variation even when subjected to continuous printing. A method of treating an ink composition is provided.

L ^* a ^* b ^* L ^* value in the color system of the silver ink composition is a schematic view for explaining a method of measuring values and b ^* values of a ^*. It is a figure which shows typically one Embodiment of the fine pattern of the metallic silver formed by applying the processing method of this invention, (a) is a front view, (b) is in the II line | wire of (a). It is sectional drawing. It is a figure which shows typically other embodiment of the fine pattern of the metallic silver formed by applying the processing method of this invention. In the present invention, it is a schematic diagram showing an example of an anchor-shaped stirring blade suitable for use in the production of a silver ink composition. In this invention, it is a schematic diagram which shows the other example of the stirring blade of an anchor shape suitable for using at the time of manufacture of a silver ink composition. It is a graph which shows the relationship between the processing temperature and processing time of the silver ink composition produced in the Example.

◎ Processing Method of Silver Ink Composition The processing method of the silver ink composition of the present invention is abbreviated as “β-ketocarboxylate (hereinafter referred to as“ β-ketocarboxylate (1) ”) represented by the following general formula (1)”. 1) selected from the group consisting of an amine compound having 25 or less carbon atoms, a quaternary ammonium salt having 25 or less carbon atoms, ammonia, and an ammonium salt obtained by reacting the amine compound or ammonia with an acid. One or more selected from the group consisting of at least one nitrogen-containing compound (hereinafter sometimes simply referred to as “nitrogen-containing compound”), oxalic acid, hydrazine, and a compound represented by the following general formula (5) And a acetylene alcohol represented by the following general formula (2) (hereinafter sometimes abbreviated as “acetylene alcohol (2)”). The silver ink composition may be abbreviated as “silver ink composition (A)”, and the processing temperature x (° C.) and processing time y (h) of the silver ink composition satisfy the relationship of the following formula (i) ( However, x is 0 to 42).
HC (= O) -R ²¹ (5)
(In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.)
306.47e ^−0.139x ≦ y ≦ 2403.2e ^−0.128x (i)

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

（式中、Ｒ’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 each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)

  When the silver ink composition (A) is subjected to continuous printing immediately after production, it is not always possible to form a fine pattern of metallic silver having a small resistance variation. On the other hand, according to the treatment method of the present invention, the silver ink composition (A) can form a fine pattern of metallic silver having a small resistance variation even when subjected to continuous printing. More specifically, the silver ink composition (A) was treated by the treatment method of the present invention, and the resulting silver ink composition (hereinafter sometimes abbreviated as “silver ink composition (B)”). When a printing method is applied and a fine print pattern is continuously formed, a print pattern at an initial stage of printing such as the first to tenth printing and a printing such as the 40th to 60th printing are performed a predetermined number of times. When the printed pattern after comparison is compared, changes in shape and the like are suppressed. For example, when the print pattern is a thin line, fluctuations in the line width of the thin line are suppressed. As a result, a fine pattern of metallic silver (for example, a fine line of metallic silver) formed by solidifying the printed pattern as described later is formed from a printed pattern at the beginning of printing of the silver ink composition (B). And the one formed from the print pattern after the silver ink composition (B) is printed a predetermined number of times, changes in shape and the like are suppressed, and fluctuations in resistance value are suppressed.

  As described above, the reason why the silver ink composition (A) is suitable for continuous printing by the treatment method of the present invention is not clear, but as described above, the silver ink composition (A) is a specific component. From the point that it is essential to be blended, with time, these components interact with each other after blending and react in some cases, resulting in stabilization of the state of the silver ink composition (B). It is presumed that this is because

A printing method suitable for applying the silver ink composition (B) has a step of transferring the silver ink composition (B) filled in the recesses or holes, and is preferable in such a printing method. Examples of the method include a gravure offset printing method, a screen printing method, a flexographic printing method, and the like.
When the silver ink composition (B) is subjected to continuous printing, the reason why the above-described effects can be obtained is not clear, but the silver ink composition (B) is in a state where it is filled in the recesses or holes. It is presumed that it is because it has a characteristic that it does not easily remain (not easily clogged) in the recess or hole when it is transferred.

The width of the filled portion of the silver ink composition (B) is preferably 2 to 20 μm, more preferably 3 to 18 μm, and particularly preferably 3.5 to 15 μm. In the present specification, the “filled portion of the silver ink composition (B)” means, for example, a concave portion of an intaglio plate used in a gravure offset printing method, a hole portion of a screen mask used in a screen printing method, or a flexographic printing method. It means a recess (cell) or the like of an anilox roll.
On the other hand, the depth of the filled portion of the silver ink composition (B) is preferably 1 to 20 μm.

  The relationship of the formula (i) when the silver ink composition (A) is processed is derived based on experimental data in examples described later.

  The treatment temperature x (° C.) of the silver ink composition (A) in the treatment (i) step is 0 to 42, for example, preferably 1.5 to 41.5, and preferably 2.5 to 41. Is more preferable, and 3.5 to 40.5 is particularly preferable. When the processing temperature x is in such a range, the effect of forming a fine pattern of metallic silver having a small variation in resistance value is further enhanced.

  In the process (i), the process temperature x (° C.) is basically constant, but even if it fluctuates, the same effect as when it is constant can be obtained if the fluctuation range is small. From such a viewpoint, when the processing temperature x (° C.) fluctuates in the process (i), the fluctuation range (that is, the difference between the maximum value and the minimum value of the processing temperature x (° C.)) is preferably 2 ° C. or lower, more preferably 1 ° C. or lower, particularly preferably 0.5 ° C. or lower.

  The processing time y (h) of the silver ink composition (A) in the processing (i) step is not particularly limited as long as the relationship of the formula (i) is satisfied, but may be adjusted according to the processing temperature x (° C.). Preferably, it is 1.1 to 1000, more preferably 1.2 to 990, and particularly preferably 1.3 to 970.

  In the treatment (i) step, the silver ink composition (A) may be treated in an air atmosphere or in an inert gas atmosphere. Examples of the inert gas include nitrogen gas, argon gas, helium gas, and the like.

  In the treatment (i) step, the silver ink composition (A) may be treated in a stationary state or may be treated in a stirred state. In the case of processing with stirring, the silver ink composition (A) may be stirred by a known method such as a method of rotating a stirring bar or a stirring blade.

  In the treatment (i) step, the silver ink composition (A) may be treated without being shielded from light, but is preferably treated while being shielded from light. By treating the silver ink composition (A) with light shielding, the effect of forming a fine pattern of metallic silver with a small variation in resistance value during continuous printing is further enhanced.

  In the treatment method of the present invention, the treatment (i) step is preferably carried out only once continuously, but may be carried out discontinuously with one or more interruptions. When the processing (i) step is performed discontinuously, the total processing time y (h) may be set so as to satisfy the relationship of the formula (i).

The treatment method of the present invention may have a step other than the step (i) (hereinafter may be abbreviated as “other step”) within a range not impairing the effects of the present invention.
The other steps can be arbitrarily selected according to the purpose, and the conditions may be appropriately adjusted.
However, even if the processing method of the present invention includes only the process (i), the effects of the present invention are sufficiently exhibited.

The other steps may be only one step, may be two or more steps, and when there are two or more steps, the combination and number of these steps can be arbitrarily adjusted.
The other steps may be performed at any stage before the process (i), during the process (i), and after the process (i), or may be performed at all stages.

  In addition, in this specification, the said other process is in the middle of performing the process (i) process to the target object which performs this process, ie, silver ink composition (A), silver ink composition (A). This target is obtained by performing the process on the processed composition obtained by performing any process such as the process (i) or the process (i) other than the process (i) on the intermediate composition or the silver ink composition (A). It means a process that causes a change in physical properties to a level that can be detected.

<< Silver Ink Composition (A) >>
The silver ink composition (A) is obtained by blending silver β-ketocarboxylate (1), the nitrogen-containing compound, a reducing agent, and acetylene alcohol (2). Hereinafter, each component will be described.

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

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

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

Examples of the alkenyl group in R include a vinyl group (ethenyl group, —CH═CH ₂ ), an allyl group (2-propenyl group, —CH ₂ —CH═CH ₂ ), and a 1-propenyl group (—CH═CH -CH _3), isopropenyl _{(-C (CH 3) = CH} 2), 1- butenyl group _{(-CH = CH-CH 2 -CH} 3), 2- butenyl group _(-CH 2 -CH = CH- CH ₃ ), a 3-butenyl group (—CH ₂ —CH ₂ —CH═CH ₂ ), a cyclohexenyl group, a cyclopentenyl group and the like, one single bond (C— And a group in which C) is substituted with a double bond (C═C).
Examples of the alkynyl group in R include one single bond (C) between carbon atoms of the alkyl group in R, such as ethynyl group (—C≡CH) and propargyl group (—CH ₂ —C≡CH). And groups in which -C) is substituted with a triple bond (C≡C).

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

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

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

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

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

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

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

In the general formula (1), two X ^{1 s} may be bonded as one group via a double bond with a carbon atom sandwiched between two carbonyl groups. For example, a group represented by the formula “═CH—C ₆ H ₄ —NO ₂ ” and the like can be mentioned.

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

β-ketocarboxylate silver (1) is silver 2-methylacetoacetate (CH ₃ —C (═O) —CH (CH ₃ ) —C (═O) —OAg), silver acetoacetate (CH ₃ —C (= O) —CH ₂ —C (═O) —OAg), silver 2-ethylacetoacetate (CH ₃ —C (═O) —CH (CH ₂ CH ₃ ) —C (═O) —OAg), silver propionyl acetate _{(CH 3 CH 2 -C (=} O) -CH 2 -C (= O) -OAg), isobutyryl silver acetate _{((CH 3) 2 CH-} C (= O) -CH 2 -C (= O) - OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C—C (═O) —CH ₂ —C (═O) —OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH ₂ —C (═O) _{) -CH 2 -C (= O)} -OAg), 2-n- Buchiruaseto silver acetate _{(CH 3 -C (= O)} -CH (C _{H 2 CH 2 CH 2 CH 3} ) -C (= O) -OAg), 2- benzyl acetoacetate silver _{(CH 3 -C (= O)} -CH (CH 2 C 6 H 5) -C (= O) -OAg), silver benzoylacetate _{(C 6 H 5 -C (=} O) -CH 2 -C (= O) -OAg), Pibaroiruaseto silver acetate _{((CH 3) 3 C-} C (= O) -CH 2 _{-C (= O) -CH 2 -C} (= O) -OAg), isobutyryl acetoacetate silver _{((CH 3) 2 CH-} C (= O) -CH 2 -C (= O) -CH 2 -C (= O) -OAg), 2- acetyl pivaloyl silver acetate _{((CH 3) 3 C-} C (= O) -CH (-C (= O) -CH 3) -C (= O) -OAg), 2- acetyl isobutyryl silver acetate _{((CH 3) 2 CH-} C (= O) -CH (-C (= O) -CH 3) -C (= O) - Ag), or is preferably acetone dicarboxylic silver _{(AgO-C (= O)} -CH 2 -C (= O) -CH 2 -C (= O) -OAg).

  The silver β-ketocarboxylate (1) can further reduce the concentration of remaining raw materials and impurities in metallic silver formed by a solidification process such as a drying process or a heating (baking) process. The smaller the raw materials and impurities, for example, the better the contact between the formed metal silvers, the easier the conduction, and the lower the resistivity.

  The β-ketocarboxylate (1) is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent known in the art, as described later, It is possible to form metallic silver.

  In the present invention, β-ketocarboxylate (1) may be used singly or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof are arbitrary. Can be selected.

β-ketocarboxylate (1) is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionyl acetate, silver isobutyryl acetate, silver pivaloyl acetate, silver caproyl acetate, silver 2-n-butylacetoacetate, It is preferably at least one selected from the group consisting of silver 2-benzylacetoacetate, silver benzoylacetate, silver pivaloylacetoacetate, silver isobutyrylacetoacetate and silver acetonedicarboxylate.
Among these silver carboxylates, silver 2-methylacetoacetate and silver acetoacetate are excellent in compatibility with a nitrogen-containing compound (especially an amine compound) described later, and increase the concentration of the silver ink composition (A). Are particularly suitable.

  In the silver ink composition (A), the blending amount of the β-ketocarboxylate (1) is not particularly limited, but the ratio of the blending amount of the β-ketocarboxylate (1) to the total blending amount of all the components is as follows. It is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, and particularly preferably 20 to 60% by mass. When the ratio is in such a range, the handleability of the silver ink composition (A) is improved and high-purity metallic silver can be easily formed.

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

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

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

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

  As an aryl group which comprises the said monoarylamine, a phenyl group, 1-naphthyl group, 2-naphthyl group etc. are mentioned, for example, It is preferable that carbon number is 6-10.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Ammonium salt derived from ammonia]
In the present invention, the ammonia-derived ammonium salt is an ammonium salt obtained by reacting ammonia with an acid, and examples of the acid include the same ammonium salts derived from the amine compound.
Examples of the ammonium salt derived from ammonia include ammonium chloride, but are not limited thereto.

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

  In the silver ink composition (A), the compounding amount of the nitrogen-containing compound is preferably 0.3 to 15 mol, and 0.3 to 5 mol per mol of the β-ketocarboxylate silver (1). It is more preferable that When the blending amount of the nitrogen-containing compound is within such a range, the silver ink composition (A) is further improved in stability, and the quality of the conductor (metal silver) is further improved. Furthermore, the conductor can be formed more stably without performing heat treatment at a high temperature.

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

The alkyl group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and may be any of linear, branched and cyclic, for example, the alkyl group in R of the general formula (1) The same thing etc. are mentioned.

The alkoxy group having 20 or less carbon atoms in R ²¹ has 1 to 20 carbon atoms, and examples thereof include a monovalent group formed by bonding the alkyl group in R ^{21 to} an oxygen atom.

The N, N-dialkylamino group having 20 or less carbon atoms in R ²¹ has 2 to 20 carbon atoms, and the two alkyl groups bonded to the nitrogen atom may be the same as or different from each other. Each alkyl group has 1 to 19 carbon atoms. However, the total value of the carbon number of these two alkyl groups is 2-20.
The alkyl group bonded to the nitrogen atom may be any of linear, branched and cyclic, for example, in the R of the general formula (1) except that it has 1 to 19 carbon atoms. The same thing as the said alkyl group etc. are mentioned.

As the reducing agent, monohydrate (H ₂ N—NH ₂ .H ₂ O) may be used as hydrazine.

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

  In the silver ink composition (A), the compounding amount of the reducing agent is preferably 0.04 to 1.5 mol, and 0.06 to 1 mol per mol of the β-ketocarboxylate silver (1). More preferably, it is 0.0 mol. When the blending amount of the reducing agent is within such a range, the silver ink composition (A) can form a conductor (metal silver) more easily and more stably.

<Acetylene alcohol (2)>
The acetylene alcohol (2) is represented by the general formula (2).
In the formula, R ′ and R ″ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group having 1 to 20 carbon atoms in R ′ and R ″ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. Examples of the alkyl group in R ′ and R ″ include those similar to 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, for example, a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, A monovalent group formed by bonding an aromatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, etc., and the hydrogen atom of the phenyl group in R is substituted. It is the same as the above-mentioned substituent. And the number and position of a substituent are not specifically limited, When there are two or more substituents, these several substituents may mutually be same or different.

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

  Preferred acetylene alcohols (2) include, for example, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 2 -Propin-1-ol, 4-ethyl-1-octin-3-ol, 3-ethyl-1-heptin-3-ol, etc. are mentioned.

  In this invention, acetylene alcohol (2) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, the combination and ratio can be selected arbitrarily. .

  In the silver ink composition (A), the blending amount of acetylene alcohol (2) is preferably 0.01 to 0.7 mole per mole of blending silver β-ketocarboxylate (1), and 0.02 More preferably, it is -0.3 mol. When the blending amount of acetylene alcohol (2) is within such a range, the stability of the silver ink composition is further improved.

<Other ingredients>
Further, the silver ink composition of the present invention has the essential components (that is, silver β-ketocarboxylate (1), the nitrogen-containing compound, the reducing agent, and acetylene alcohol (2) within the range not impairing the effects of the present invention. In addition to)), other components may be blended.
Examples of the other components include alcohols other than acetylene alcohol (2) (hereinafter sometimes abbreviated as “other alcohols”), solvents other than acetylene alcohol (2) and the other alcohols, and the like. .

  In the present invention, the other components may be used singly or in combination of two or more, and when two or more are used in combination, the combination and ratio can be arbitrarily selected. .

In the silver ink composition (A), the blending amount of the components other than the other alcohols and solvents may be appropriately selected according to the type of the components, and is not particularly limited.
Especially, in the silver ink composition (A), the ratio of the blending amount of the components other than the alcohol and the solvent is preferably 10% by mass or less with respect to the total blending amount of all the components. It is more preferable that Further, in the silver ink composition (A), the lower limit of the ratio of the blending amount of the components other than the alcohol and the solvent to the total blending amount of all the components is not particularly limited, and is, for example, 0% by mass. May be.

[Other alcohol]
The other alcohol is not particularly limited as long as it is an alcohol other than acetylene alcohol (2).
However, the other alcohols are preferably liquid at room temperature. In the present specification, “normal temperature” means a temperature that is not cooled or heated, that is, a normal temperature, and includes a temperature of 15 to 30 ° C., for example.

  More specifically, examples of the other alcohol include acetylene alcohol other than acetylene alcohol (2), acetylene alcohol (2), and other alcohols.

(Acetylene alcohol other than acetylene alcohol (2))
The acetylene alcohol other than acetylene alcohol (2) is not particularly limited as long as it is an alcohol having a triple bond (C≡C) between carbon atoms, which is not represented by the general formula (2).
Acetylene alcohol other than acetylene alcohol (2) may be linear, branched or cyclic, and when cyclic, it may be monocyclic or polycyclic, but is linear or branched. It is preferable.

(Acetylene alcohol (2) and other alcohols)
The acetylene alcohol (2) and other alcohols are not particularly limited as long as they do not have a triple bond (C≡C) between carbon atoms. For example, any of monohydric alcohols and dihydric or higher polyhydric alcohols. It may be either a saturated alcohol or an unsaturated alcohol, and in the case of an unsaturated alcohol, an aliphatic alcohol (an alcohol having no aromatic cyclic group) and an aromatic alcohol (an alcohol having an aromatic cyclic group) ).
Acetylene alcohol (2) and other alcohols may be linear, branched or cyclic, and may be monocyclic or polycyclic when cyclic.

  As acetylene alcohol (2) and other alcohols, more specifically, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2- Examples thereof include monohydric alcohols such as methyl-2-propanol, 1-pentanol, hexanol and heptanol; dihydric alcohols such as ethylene glycol and propylene glycol.

The acetylene alcohol (2) and other alcohols preferably have 1 to 7 carbon atoms.
In addition, the acetylene alcohol (2) and other alcohols are preferably linear or branched.

When the silver ink composition (A) is formed by blending the other alcohol, the blending amount of the other alcohol in the silver ink composition (A) is not particularly limited.
Especially, in the silver ink composition (A), the ratio of the blending amount of the other alcohol to the blending amount of the acetylene alcohol (2) is preferably 1 to 10% by mass, and 1 to 5% by mass. More preferably. When the ratio is equal to or higher than the lower limit value, the effect obtained by using the other alcohol is more remarkably obtained. Moreover, the effect of this invention is acquired more notably because the said ratio is below the said upper limit.

[solvent]
The solvent is not particularly limited as long as it is other than acetylene alcohol (2) and other alcohols (having no hydroxyl group).
However, the solvent is preferably a liquid at room temperature.

  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, Aliphatic hydrocarbons such as tetradecane, pentadecane and decahydronaphthalene; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, monomethyl glutarate and 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; N, N-dimethylformamide (DMF), N, N-dimethyla Amides such as Toamido like.

When the silver ink composition (A) is a mixture of the solvent, the amount of the solvent in the silver ink composition (A) is not particularly limited.
Among them, in the silver ink composition (A), the amount of the solvent is preferably 0.5 to 5 mol per mol of the β-ketocarboxylate (1), and 0.5 to 3 More preferably, it is 0.5 mol, and particularly preferably 0.5-2 mol. The effect by using the said solvent is more notably acquired because the said ratio is more than the said lower limit. Moreover, the effect of this invention is acquired more notably because the said ratio is below the said upper limit.

  In the silver ink composition (A), all of the compounding components may be dissolved, or some or all of the components may be dispersed without dissolving, but all the compounding components are dissolved. Preferably, the undissolved component is preferably dispersed uniformly.

The silver ink composition (A) preferably has a b ^* value in the L ^* a ^* b ^* color system of 0.00 to 0.51. By subjecting such a silver ink composition (A) to the process (i) and performing continuous printing, the effect of forming a fine pattern of metallic silver with a small variation in resistance value is further enhanced.

In the silver ink composition (A), the value of a ^* in the L ^* a ^* b ^* color system is preferably 1.00 to 1.39, more preferably 1.05 to 1.37. 1.10 to 1.35 is particularly preferable. By subjecting such a silver ink composition (A) to the process (i) and performing continuous printing, the effect of forming a fine pattern of metallic silver with a small variation in resistance value is further enhanced.

In the silver ink composition (A), the value of L ^* in the L ^* a ^* b ^* color system is preferably 21.0 to 28.5, and more preferably 23.0 to 27.5. 25.0 to 26.5 is particularly preferable. By subjecting such a silver ink composition (A) to the process (i) and performing continuous printing, the effect of forming a fine pattern of metallic silver with a small variation in resistance value is further enhanced.

The values of L ^* , a ^*, and b ^* in the L ^* a ^* b ^* color system of the silver ink composition (A) are, for example, the types and amounts of the compounding components of the silver ink composition (A), and the compounding components It can be adjusted by adjusting the blending method and blending order.

L ^* value, a ^* value and b ^* value in the L ^* a ^* b ^* color system of the silver ink composition such as the silver ink composition (A) and the silver ink composition (B) described later Can be measured, for example, by the following method. FIG. 1 is a schematic diagram for explaining a method of measuring L ^* , a ^* , and b ^* values in the L ^* a ^* b ^* color system of a silver ink composition.

  That is, first, the silver ink composition 2 is adhered on the surface of one glass plate 9. The silver ink composition 2 can be attached to the glass plate 9 by, for example, dropping it onto the surface of the glass plate 9 using a dropper or the like.

Next, another glass plate 9 is placed on the surface of the glass plate 9 on the side to which the silver ink composition 2 is adhered, and the silver ink composition 2 is sandwiched between the surfaces of the two glass plates 9 and 9. The silver ink composition 2 is spread between the glass plates 9 and 9. At this time, the expanded silver ink composition 2 is preferably circular or substantially circular. The silver ink composition 2 having such a shape is uniformly spread between the glass plates 9 and 9, and the measurement accuracy of L ^* , a ^* and b ^* is improved. FIG. 1 shows a case where the silver ink composition 2 is thus circular or substantially circular.
The two glass plates 9 and 9 may be the same as each other or different from each other.

The size of the silver ink composition 2 that is spread out is not particularly limited, and may be adjusted as appropriate according to the type of the L ^* a ^* b ^* measuring device. However, normally, when the shape of the silver ink composition 2 is circular or substantially circular, the diameter D is preferably 20 to 80 mm.
The size of the expanded silver ink composition 2 can be adjusted by, for example, the amount of the silver ink composition 2 attached to the glass plate 9.

<< Method for Producing Silver Ink Composition (A) >>
The silver ink composition (A) is obtained by blending silver β-ketocarboxylate (1), the nitrogen-containing compound, the reducing agent, acetylene alcohol (2), and, if necessary, the other components. After the blending of the respective components, the obtained product may be used as it is as the silver ink composition (A), or a product obtained by performing a known purification operation as necessary as the silver ink composition (A). Also good. At the time of blending the above components, impurities that inhibit conductivity are not generated, or the amount of such impurities generated can be suppressed to a very small amount. Even if it uses, the conductor (metal silver) which has sufficient electroconductivity is obtained.

At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
The mixing method is not particularly limited, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill or the like; a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.
In the silver ink composition (A), when the undissolved component is uniformly dispersed, it is preferable to apply a method of dispersing using, for example, the above-described three rolls, kneader or bead mill.

The temperature at the time of compounding is not particularly limited as long as each compounding component does not deteriorate. For example, in the silver ink composition (A), the blending temperature is preferably -5 to 60 ° C. And the temperature at the time of mixing | blending is good to adjust suitably so that the mixture obtained by mix | blending may become the viscosity which is easy to stir according to the kind and quantity of a mixing | blending component.
Further, the blending time is not particularly limited as long as each blending component does not deteriorate. In the silver ink composition (A), the blending time is preferably 10 minutes to 36 hours.

  The blending method and blending order of the β-ketocarboxylate silver (1), the nitrogen-containing compound, the reducing agent, the acetylene alcohol (2), and the other components during the production of the silver ink composition (A) are particularly It is not limited. For example, all of these components may be added all at once or in divided portions. And in any case of collective addition and divided addition, the addition order of each compounding component is not particularly limited. Moreover, you may add 2 or more types of compounding components simultaneously at the time of manufacture of a silver ink composition (A).

However, since the effect of forming a fine pattern of metallic silver with small fluctuations in resistance value is enhanced by the aging treatment of the silver ink composition (A), when all of the above-mentioned blending components are added at once, the blending components As a preferable addition method,
A method of adding the nitrogen-containing compound, silver β-ketocarboxylate (1), the reducing agent, and acetylene alcohol (2) in this order;
a method of adding silver β-ketocarboxylate (1), the nitrogen-containing compound, the reducing agent, and acetylene alcohol (2) in this order;
Etc. In addition, these are examples of the preferable addition method of a mixing | blending component.

The order of adding the other components may be appropriately selected according to the type of the other components, and is not particularly limited.
For example, in the method of adding the nitrogen-containing compound, silver β-ketocarboxylate (1), the reducing agent, and acetylene alcohol (2) in this order, the addition order of the other components is the same as that of the nitrogen-containing compound. Between the nitrogen-containing compound and silver β-ketocarboxylate (1), between the silver β-ketocarboxylate (1) and the reducing agent, between the reducing agent and acetylene alcohol (2), and acetylene alcohol. Any one after (2) may be used.
For example, in the method of adding silver β-ketocarboxylate (1), the nitrogen-containing compound, the reducing agent, and acetylene alcohol (2) in this order, the addition order of the other components is β-ketocarboxylic acid. Before the silver (1), between the silver β-ketocarboxylate (1) and the nitrogen-containing compound, between the nitrogen-containing compound and the reducing agent, between the reducing agent and acetylene alcohol (2), and Any one after acetylene alcohol (2) may be used.

When the solvent is used as the other component, as a preferred method of adding the compounding component,
A method of adding the nitrogen-containing compound, the solvent, silver β-ketocarboxylate (1), the reducing agent, and acetylene alcohol (2) in this order;
A method of adding the solvent, the nitrogen-containing compound, silver β-ketocarboxylate (1), the reducing agent, and acetylene alcohol (2) in this order;
a method of adding silver β-ketocarboxylate (1), the solvent, the nitrogen-containing compound, the reducing agent, and acetylene alcohol (2) in this order;
A method in which the solvent, silver β-ketocarboxylate (1), the nitrogen-containing compound, the reducing agent, and acetylene alcohol (2) are added in this order;
Etc.

  In addition, when one or more of the above-mentioned blending components are added in a divided manner (including the case where all the blending components are added in a split manner), as a preferred method for adding the blending components, for example, the above-mentioned blending components are used. In the case of adding all at once, there may be mentioned a method of additionally adding the same blending components as one or more already added at any stage.

  The silver ink composition (A) is prepared by rotating a stirring blade in a stirring tank, so that the silver β-ketocarboxylate (1), the nitrogen-containing compound, the reducing agent, acetylene alcohol (2), and as necessary. What was manufactured with the manufacturing method which has the process of stirring the said other component in the said stirring tank is preferable. By subjecting such a silver ink composition (A) to the process (i) and performing continuous printing, the effect of forming a fine pattern of metallic silver with a small variation in resistance value is further enhanced.

The stirring blade is preferably anchor-shaped. By stirring with an anchor-shaped stirring blade, the stirring efficiency of the compounding components of the silver ink composition (A) is increased, and it is estimated that the reaction of these compounding components can be performed efficiently.
As the anchor-shaped stirring blade, for example, a drive shaft, a forced flow generating blade portion having an outer side rotating in the vicinity of the inner peripheral surface of the stirring tank, the drive shaft and the forced flow generating blade portion The thing provided with the connection part to connect is mentioned.

  That is, as a preferable silver ink composition (A), for example, by rotating a stirring blade in a stirring tank, β-ketocarboxylate silver (1), the nitrogen-containing compound, the reducing agent, acetylene alcohol (2) , And if necessary, the other components are produced by a production method having a step of stirring in the stirring vessel, and the stirring blade includes a drive shaft and an inner peripheral surface of the stirring vessel. Examples include those using a forced flow generating blade portion having an outer side that rotates and moves in the vicinity, and a connecting portion that connects the drive shaft and the forced flow generating blade portion. By subjecting such a silver ink composition (A) to the process (i) and performing continuous printing, the effect of forming a fine pattern of metallic silver having a small resistance variation is further enhanced.

Examples of the anchor-shaped stirring blade include those shown in FIG. FIG. 4 is a schematic diagram showing an example of an anchor-shaped stirring blade suitable for use in the production of the silver ink composition (A).
In addition, in the drawings used in the following description, in order to make the characteristics easy to understand, for the sake of convenience, there is a case where a main part is shown in an enlarged manner, and the dimensional ratio of each component is the same as the actual one. Is not limited.

A stirring blade 800 shown in FIG. 4 includes a drive shaft 810, a forced flow generation blade portion 820 having an outer side 820a that rotates around the inner peripheral surface of a stirring tank (for example, a container such as a beaker), and the drive shaft 810. And a connecting portion 830 that connects the forced flow generating blade portion 820.
The forced flow generating blade 820 preferably extends in the depth direction of the stirring tank (in a direction parallel to the drive shaft 810). In this case, the forced flow generating blade 820 may extend linearly in parallel with the drive shaft 810 as shown in FIG. 4, or extends while twisting in a spiral shape in the depth direction of the agitation tank, for example. (Not shown).
The ratio of the diameter of the stirring blade (the distance from one outer side 820a in FIG. 1 to the other outer periphery 820a) to the inner diameter (diameter) of the stirring tank is preferably 85 to 95%.

  Examples of the anchor-shaped stirring blade include those shown in FIG. FIG. 5 is a schematic view showing another example of an anchor-shaped stirring blade suitable for use in the production of the silver ink composition (A).

A stirring blade 900 shown in FIG. 5 is of a max blend type, and includes a drive shaft 910 and a forced flow generation blade portion having an outer side 920a that rotates around the inner peripheral surface of a stirring tank (for example, a container such as a beaker). 920, a first connecting portion 930 that connects the drive shaft 910 and the forced flow generating blade portion 920 at their lower portions, and a second connection that connects the drive shaft 910 and the forced flow generating blade portion 920 at their upper portions. And a connecting portion 940. Further, the stirring blade 900 includes a third connection portion 950 that connects the first connection portion 930 and the second connection portion 940 at a position between the drive shaft 910 and the forced flow generation blade portion 920.
A stirring blade 900 shown in FIG. 5 includes a first connecting portion 930 and a second connecting portion 940 that connect the drive shaft 910 and the forced flow generating blade portion 920, and further includes a first connecting portion that connects these connecting portions. Except for the point provided with the 3 connection part 950, it is the same as that of the stirring blade 800 shown in FIG.

The widths of the first connecting part 930 and the second connecting part 940 are not particularly limited. For example, as shown in FIG. 5, the first connecting part 930 may be wider than the second connecting part 940. The width of the second connecting portion 940 may be wider than that of the first connecting portion 930, and the width of the first connecting portion 930 and the second connecting portion 940 may be the same.
The same applies to the widths of the forced flow generating blade portion 920 and the third connecting portion 950. For example, the forced flow generating blade portion 920 may be wider than the third connecting portion 950 as shown in FIG. The third connecting portion 950 may be wider than the forced flow generating blade portion 920, or the forced flow generating blade portion 920 and the third connecting portion 950 may have the same width.

  As for the rotation speed when the anchor-shaped stirring blade is rotated to stir the mixture, for example, the total amount of the blended components (components used for mixing) of the silver ink composition (A) is about 30 to 300 g. In that case, it is preferably 100 to 500 rpm.

<< Silver ink composition (B) >>
In the silver ink composition (B), the processing temperature x (° C.) and the processing time y (h) of the silver ink composition (A) satisfy the relationship of the above formula (i) ( However, x is 0-42.) It was obtained by the processing method which has the process of processing.
The compounding component of the silver ink composition (B) includes the compounding component of the silver ink composition (A).

  In the silver ink composition (B), all of the blending components may be dissolved, or some or all of the components may be dispersed without dissolving, but all the blending components are dissolved. Preferably, the undissolved component is preferably dispersed uniformly.

The silver ink composition (B) preferably has a b ^* value of −0.60 to −0.10 in the L ^* a ^* b ^* color system. By using such a silver ink composition (B) for continuous printing, the effect of forming a fine pattern of metallic silver with a small variation in resistance value is further enhanced.

The silver ink composition (B) preferably has a value of a ^{* in} the L ^* a ^* b ^* color system of 1.48 to 1.90. By using such a silver ink composition (B) for continuous printing, the effect of forming a fine pattern of metallic silver with a small variation in resistance value is further enhanced.

In the silver ink composition (B), the value of L ^* in the L ^* a ^* b ^* color system is preferably 21.0 to 28.7, and more preferably 23.0 to 27.7. 25.0 to 26.7 is particularly preferable. By using such a silver ink composition (B) for continuous printing, the effect of forming a fine pattern of metallic silver with a small variation in resistance value is further enhanced.

The values of L ^* , a ^* and b ^* in the L ^* a ^* b ^* color system of the silver ink composition (B) can be adjusted, for example, by adjusting the conditions of the time-dependent treatment of the silver ink composition (A). Can be adjusted.

◎ Metallic silver and its production method For metallic silver, for example, the silver ink composition (B) is adhered to a target location such as a base material, and solidification treatment such as drying treatment or heating (firing) treatment is appropriately selected. It can be formed by doing.
Various laminated bodies can be manufactured by forming the layer (silver layer) which consists of the said metal silver on a base material.

The silver ink composition (B) is preferably deposited on the substrate by the printing method described above.
The amount of metallic silver formed on the substrate is adjusted by adjusting the amount of silver ink composition (B) to be deposited or the amount of silver β-ketocarboxylate (1) in the silver ink composition (B). it can.

  When the silver ink composition (B) is subjected to continuous printing to form a metal silver pattern, even if this pattern is fine (for example, a metal silver fine pattern), as described above, The variation in resistance value is reduced. That is, the silver ink composition (B) is suitable for continuous formation of a fine pattern of metallic silver.

In the present invention, as will be described later in the examples, when the metallic silver fine pattern is continuously formed, the sheet resistance Rst (10) of the metallic silver fine pattern formed by the 10th printing and the 50th printing. The absolute value of the 50th sheet resistance fluctuation rate calculated from the following formula is preferably 9% or less (sheet resistance fluctuation rate is −9%) To 9%), more preferably 8% or less (sheet resistance fluctuation rate of -8% to 8%), and even more preferably 7% or less (sheet resistance fluctuation rate of -7% to 7%).
50th sheet resistance fluctuation rate (%) = (Rst (50) −Rst (10)) / Rst (10) × 100

  When the silver ink composition (B) is dried, it may be performed by a known method, for example, under normal pressure, reduced pressure, or blowing conditions, and in the atmosphere and in an inert gas atmosphere. Any of these may be used. Also, the drying temperature is not particularly limited, and may be either heat drying or room temperature drying. As a preferable drying method when the heat treatment is unnecessary, for example, a method of drying in the atmosphere at 18 to 30 ° C. can be mentioned.

  When the silver ink composition (B) is heated (baked), the conditions may be appropriately adjusted according to the type of the silver ink composition (B) or the compounding component of the silver ink composition (A). Usually, it is preferable that heating temperature is 60-370 degreeC, and it is more preferable that it is 70-280 degreeC. The heating time may be adjusted according to the heating temperature, but is usually preferably 1 minute to 24 hours, and more preferably 1 minute to 12 hours. Unlike other metal silver forming materials such as silver oxide, β-ketocarboxylate silver (1) decomposes at a low temperature without using a reducing agent known in the art. Reflecting such decomposition temperature, the silver ink composition (B) can form metallic silver at an extremely lower temperature than the conventional one as described above.

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

  The method for heat treatment of the silver ink composition (B) is not particularly limited, and for example, heating by an electric furnace, heating by a thermal head, heating by far infrared irradiation, heating by blowing a hot gas, etc. Can do. In addition, the heat treatment of the silver ink composition (B) may be performed in the air, in an inert gas atmosphere, or may be performed under humidified conditions. And you may carry out under any of normal pressure, pressure reduction, and pressurization.

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

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

The heat treatment of the silver ink composition (B) may be performed in two stages. For example, in the first stage heat treatment, there is a method in which the silver ink composition (B) is mainly dried rather than the formation of metal silver, and the formation of metal silver is performed to the end in the second stage heat treatment. .
In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of the silver ink composition (B) or the blending component of the silver ink composition (A), but it is 60 to 120 ° C. Preferably, it is 70-120 degreeC, It is especially preferable that it is 80-110 degreeC. Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 5 second-12 hours, and it is more preferable that it is 30 second-2 hours.
In the second stage heat treatment, the heating temperature may be appropriately adjusted according to the type of the silver ink composition (B) or the compounding component of the silver ink composition (A) so that metallic silver is formed satisfactorily. Although it is good, it is preferable that it is 60-280 degreeC, and it is more preferable that it is 70-260 degreeC. Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 1 minute-12 hours, and it is more preferable that it is 1 minute-10 hours.
When the silver ink composition (B) is attached to a substrate having low heat resistance and is heated (baked), the heating temperature in the first and second stages of heat treatment may be less than 130 ° C. Preferably, it is 125 degrees C or less, and it is especially preferable that it is 120 degrees C or less.

The heat treatment of the silver ink composition (B) described so far is performed in the gas phase. However, when the heat treatment of the silver ink composition (B) is performed in two stages, the second stage is performed. The heat treatment may be performed in the liquid phase, not in the gas phase. The silver ink composition (B) that has been completely or partially dried after the first stage heat treatment can be subjected to the second stage heat treatment without impairing its shape by contacting with the heated liquid. it can. Then, the heat treatment in the second-stage liquid phase after the first-stage heat treatment of the silver ink composition (B) is to immerse the silver ink composition (B) in the heated liquid. It is preferable to carry out with. The heating temperature and heating time in the heat treatment in the liquid phase are the same as the heating temperature and heating time in the second-stage heat treatment described above.
The heated liquid is preferably hot water (heated water), and the second stage heat treatment includes immersing the silver ink composition (B) subjected to the first stage heat treatment in hot water, That is, it is preferably performed by hot water.
When the second stage heat treatment is performed in the liquid phase, the metallic silver formed by this heat treatment may be further dried.

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

  When heat treatment under humidified conditions is adopted, the silver ink composition (B) is heat-treated in the first stage of heat treatment under non-humidified conditions and not with the formation of metallic silver as described above. It is particularly preferable that the composition (B) is mainly dried, and the second stage heat treatment is performed by a two-stage method in which the formation of metallic silver is performed to the end under humidified conditions as described above.

When performing the second stage heat treatment under humidified conditions, the heating temperature during the heat treatment under the first stage non-humidified conditions is preferably 60 to 120 ° C, and preferably 70 to 120 ° C. More preferably, it is 80-110 degreeC. The heating time is preferably 5 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and particularly preferably 30 seconds to 10 minutes.
It is preferable that the heating temperature at the time of the heat treatment under the second-stage humidification condition performed after the heat treatment under the first-stage non-humidification condition is 60 to 140 ° C, and 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 (B) is attached to a substrate having low heat resistance and is heated (baked), the heat treatment under the first stage non-humidifying condition and the second stage humidifying condition are performed. The heating temperature in the heat treatment is preferably less than 130 ° C, more preferably 125 ° C or less, and particularly preferably 120 ° C or less.

  As described above, a preferable method for producing metallic silver includes, for example, one having a step of forming the metallic silver using the silver ink composition (B). For example, in the step of forming the metallic silver, the silver ink composition (B) is heat-treated under non-humidified conditions, and then further heat-treated under humidified conditions or in contact with a heated liquid. And what forms the said metal silver is mentioned.

A processed product (conductor) formed by the solidification treatment of the silver ink composition (B) (in this specification, the processed product (conductor) itself may be referred to as “metallic silver” as described above. ) Is extremely high purity, and the ratio of metallic silver is sufficiently high that it can be regarded as apparently consisting only of metallic silver, for example, preferably 97% by mass or more, more preferably 98% by mass or more, and particularly preferably It can be 99 mass% or more.
On the other hand, the processed product (conductor) formed by the solidification treatment of the silver ink composition (B) has an upper limit of the ratio of metallic silver of 100% by mass, 99.9% by mass, 99.8% by mass, 99.7% by mass, 99.6% by mass, 99.5% by mass, 99.4% by mass, 99.3% by mass, 99.2% by mass and 99.1% by mass, These are examples.

  The metallic silver formed using the silver ink composition (B) is excellent in electrical conductivity, and the sheet resistance required by the method described in the examples described later is preferably 40 to 56 (Ω / □), more preferably 41.5 to 55 (Ω / □), and particularly preferably 43 to 54 (Ω / □).

  In the laminated body provided with the layer made of the metallic silver (silver layer) on the base material, the thickness of the base material may be appropriately selected according to the purpose, but is preferably 10 to 5000 μm. More preferably, it is -3000 micrometers.

The material of the substrate is not particularly limited, but preferred examples include polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polymethylpentene (PMP), poly Acrylic resins such as cycloolefin, polystyrene (PS), polyvinyl acetate (PVAc), polymethyl methacrylate (PMMA), AS resin, ABS resin, polyamide (PA), polyimide, polyamideimide (PAI), polyacetal, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polysulfone (PS) ), Polyethersulfone (PES), polyetherketone (PEK), polyetheretherketone (PEEK), polycarbonate (PC), polyurethane, polyphenylene ether (PPE), modified polyphenylene ether (m-PPE), polyarylate, epoxy Examples thereof include synthetic resins such as resins, melamine resins, phenol resins, and urea resins.
In addition to the above, the material of the base material includes ceramics such as glass and silicon, and paper.
Further, the base material may be a combination of two or more materials such as glass epoxy resin and polymer alloy.

The substrate may be composed of one layer (single layer) or may be composed of two or more layers. When a base material consists of multiple layers, these multiple layers may be mutually the same or different, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.
In the present specification, not limited to the case of a base material, “a plurality of layers may be the same or different from each other” means “all layers may be the same or all layers are different. Means that only some of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.
In addition, when a base material consists of multiple layers, it is good to make it the total thickness of each layer be the thickness of said preferable base material.

  The thickness of the silver layer can be arbitrarily set according to the purpose, for example, 3 nm to 40 μm, 4 nm to 30 μm, etc., but preferably 5 nm to 10 μm, more preferably 7 nm to 5 μm. The thickness is preferably 10 nm to 1 μm.

The silver layer may be composed of one layer (single layer) or may be composed of two or more layers. When a silver layer consists of multiple layers, these multiple layers may be the same or different from each other, and the combination of these multiple layers is not particularly limited as long as the effects of the present invention are not impaired.
In the case where the silver layer is composed of a plurality of layers, the total thickness of each layer may be set to the preferred thickness of the silver layer.

  The said laminated body provided with the silver layer on the base material may be equipped with the 1 or 2 or more other structure in the range which does not impair the effect of this invention other than a base material and a silver layer. The other configurations can be arbitrarily selected according to the purpose.

  The silver layer can also be formed at a low temperature, and a wide variety of materials such as a substrate can be selected in the laminate. Therefore, the degree of freedom in designing the laminate is high.

FIG. 2 is a diagram schematically showing an embodiment of a fine pattern of metallic silver formed using the silver ink composition (B), where (a) is a front view and (b) is a diagram of (a). It is sectional drawing in II line (sectional drawing of a direction perpendicular | vertical with respect to the line length (longitudinal) direction of a silver fine wire).
In FIG. 2 and subsequent figures, the same components as those shown in the already explained figures are given the same reference numerals as those in the already explained figures, and their detailed explanations are omitted.

  The fine pattern of metallic silver shown here includes a plurality of linear silver thin wires 12, and the plurality of silver thin wires 12 are arranged in parallel in two orthogonal directions to form a mesh. The plurality of silver thin wires 12 are formed on the surface (one main surface) 11 a of the base material 11 and constitute the laminate 1 together with the base material 11. Since the silver thin wire 12 has a narrow line width and can reduce sheet resistance and volume resistivity, the laminate 1 is suitable as a member such as an electromagnetic wave shield and a touch panel in various electronic devices, and is useful as, for example, a wiring board. .

In the cross section, the width W of the thin silver wire 12 is, for example, preferably 1 to 20 μm, more preferably 1.3 to 15 μm, and particularly preferably 1.5 to 13 μm.
In addition, the cross-sectional shape of the silver thin wire 12 shown here is a semi-elliptical shape in which a substantially half region in the minor axis direction of the ellipse is cut off. As the cross-sectional shape of the silver thin wire 12, it is preferable that the top width of the silver thin wire 12 be smaller than the width of the contact portion of the silver thin wire 12 with the base material 11 in the cross section.

Other preferable cross-sectional shapes of the silver thin wire 12 are, for example, a trapezoidal shape as shown in FIG. 3A, a triangular shape as shown in FIG. 3B, and FIG. 3C. The composite shape etc. which 2 or more types of shapes shown in FIG. 3 combined were mentioned, and the shape by which the corner | angular part was rounded in FIG.
As shown in FIG. 3B, in the cross section, when the top of the silver thin wire 12 is non-planar, the width of the top of the silver thin wire 12 is naturally the contact of the silver thin wire 12 with the base material 11. Smaller than the width of the part (the width is zero). As shown in FIGS. 3A and 3C, in the cross section, when the top of the silver thin wire 12 is a flat surface, the width of the flat portion is the contact of the silver thin wire 12 with the base material 11. It is smaller than the width of the part.

Moreover, although the said cross-sectional shape of the silver fine wire 12 is left-right symmetric toward the paper surface here, the said cross-sectional shape is not limited to this, A left-right asymmetric may be sufficient.
In addition, here, the cross section of the silver fine wire 12 is schematically shown, and the surface of the silver fine wire 12 is a smooth surface, but the surface of the silver fine wire 12 is not limited to this, and is regular or irregular. A rough surface may be used.
That is, the cross-sectional shape of the silver thin wire 12 shown in FIG. 2 and FIG. 3 is only a part of the example, and the cross-sectional shape of the silver thin wire 12 is not limited thereto.

  In the cross section of the thin silver wire 12, the region whose width becomes narrower as the height from the surface 11a of the substrate 11 becomes higher, for example, occupies 80% or more in the height direction of the thin silver wire 12. Preferably, it occupies 85% or more, more preferably 90% or more, particularly preferably 95% or more, and may occupy 100%.

  The above-described shape of the silver thin wire 12 is typical when the silver thin wire 12 is formed by a gravure printing method, a screen printing method, a flexographic printing method, or the like.

The pitch (distance between adjacent silver thin wires 12) P of the silver thin wires 12 can be arbitrarily set according to the purpose. It is preferable that it is 320 micrometers, and it is more preferable that it is 70-260 micrometers.
The pitch P of the silver thin wires 12 may be all the same, may all be different, or may be partially different. For example, the pitch P of the silver thin wires 12 may be the same as or different from each other in two orthogonal directions.

  The thin silver wire 12 has a variation rate of the width W ({[maximum value of W] − [minimum value of W]} / [average value of W] × 100) of 20% or less in the wire length (longitudinal) direction. It is preferable that it is 10% or less.

Here, an example in which a plurality of fine silver wires are arranged in parallel to two orthogonal directions to form a network is shown as a laminate, but the laminate in the present invention is not limited to this, and silver The fine line may form another pattern.
Other patterns formed by the silver thin wires include, for example, an angle where a plurality of silver thin wires intersect (intersect) is not 90 ° as described above but an angle other than 90 °, or a part of the silver thin wires Or everything is not a straight line but a curve, a plurality of silver thin lines are arranged without intersecting (when a plurality of silver thin lines are arranged in parallel in one direction without intersecting, etc. And those having a striped pattern).

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

<Manufacture of silver ink composition (A)>
[Production Example 1]
In a beaker, 2-ethylhexylamine (1.45 times mole amount based on 2-methylacetoacetate silver described later) and n-hexane (1.63 times mole amount based on silver 2-methylacetoacetate described later). In addition to this order, silver 2-methylacetoacetate was added to the beaker so that the liquid temperature would be 50 ° C. or lower while rotating and stirring the mechanical stirrer corresponding to the stirring blade shown in FIG.
After completion of the addition of silver 2-methylacetoacetate, formic acid (0.5 molar amount relative to silver 2-methylacetoacetate) was dropped over 10 minutes using a syringe pump in a beaker while maintaining the same state. Then, after completion of the dropwise addition of formic acid, the mixture was further stirred for 1.5 hours.
Subsequently, 3,5-dimethyl-1-hexyn-3-ol (hereinafter, sometimes abbreviated as “DMHO”) (0.032-fold molar amount with respect to silver 2-methylacetoacetate) and 4-ethyl-1 -A mixture of octin-3-ol (hereinafter sometimes abbreviated as "EOO") (0.004 times mole amount relative to silver 2-methylacetoacetate) was added to a beaker, and after completion of addition, further The silver ink composition (A) was obtained by stirring for 5 minutes in this state.
As DMHO, “Surfinol 61” manufactured by Air Products Japan was used, and as EOO, manufactured by Tokyo Chemical Industry Co., Ltd. was used.

  Table 1 shows the types and blending ratios of each blending component. In Table 1, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of nitrogen-containing compound per mole of silver β-ketocarboxylate (1) ([number of moles of nitrogen-containing compound]. / [Number of moles of silver β-ketocarboxylate (1)]). Similarly, the “reducing agent (molar ratio)” is the blending amount of the reducing agent per mole of the β-ketocarboxylic acid silver (1) (number of moles) ([number of moles of reducing agent] / [β-ketocarboxylic acid]. Means the number of moles of silver (1)]). Similarly, the "acetylene alcohol (2) (molar ratio)" is the blending amount (number of moles) of acetylene alcohol (2) per mole of blending silver β-ketocarboxylate (1) ([acetylene alcohol (2) Number of moles] / [number of moles of silver β-ketocarboxylate (1)]). Similarly, the “solvent (molar ratio)” is the blending amount (number of moles) of the solvent per mole of the β-ketocarboxylate (1) ([number of moles of solvent] / [silver β-ketocarboxylate (1 ) Number of moles]).

<Processing of silver ink composition (A) (production of silver ink composition (B))>
[Example 1]
After encapsulating the silver ink composition (A) obtained above in a polypropylene container in an air atmosphere, the container is allowed to stand at 5 ° C. for 170 hours to treat the silver ink composition (A). A silver ink composition (B) was obtained. Table 2 shows the processing conditions at this time.

<Evaluation of silver ink composition>
(Measurement of L ^* a ^* b ^* of silver ink composition)
L ^* a ^* b ^* of the silver ink composition (B) obtained above was measured by the method described with reference to FIG.
In other words, the silver ink composition (B) (0.1 g) was sandwiched between two glass plates having a size of 50 mm × 50 mm and a thickness of 120 μm (“MATUNAMI MICRO COVER GLASS” manufactured by Matsunami Glass Industry Co., Ltd.) The silver ink composition (B) was spread out so as to form a substantially circular shape having a diameter of about 50 mm between these two glass plates.
Next, these glass plates and the like are placed on a smooth surface, and using an integrating sphere spectrocolorimeter “X-Rite model SP60”, a silver ink composition under conditions of a visual field of 10 deg, a light source D65 / 2, and an SCI mode. For (B), the reflectance of light having a wavelength of 400 to 700 nm was measured. Then, L ^* a ^* b ^* of the silver ink composition (B) was calculated using the measured value. The results are shown in Table 2.

(Evaluation of continuous printing stability of silver ink composition)
Using the gravure offset printing method, printing is performed on one main surface (surface) of a polycarbonate substrate (thickness 1 mm) using the silver ink composition (B) obtained above, as shown in FIG. A reticulated print pattern was formed. More specifically, it is as follows.
The following was used as a printing apparatus. That is, as the intaglio, one made of metal and having a groove with a width of 4 μm and a depth of 10 μm which is a silver thin wire mold on the surface thereof was used. As the offset roll, a metal cylinder whose surface was covered with a silicone resin blanket material was used.

Using such a printing apparatus, the above silver ink composition (B) is supplied to the intaglio, and the excess silver ink composition (B) is removed by a doctor blade, and the groove is filled with the silver ink composition. After transferring (B) to the surface of the blanket material of the offset roll, printing was performed with this silver ink composition (B) on the surface of the substrate conveyed by the belt conveyor unit. Such printing was continuously performed 50 times on the substrate.
Next, the printed pattern obtained by the 10th printing and the printed pattern obtained by the 50th printing are each dried at 100 ° C. for 10 minutes, and the substrate provided with the dried printing pattern is heated to a temperature. By placing the printed pattern after drying in a steam atmosphere at 100 ° C. and 100% relative humidity for 10 minutes, the printed pattern is heated (baked) to form a fine silver mesh wire shown in FIG. It was.

About the silver fine wire of the obtained wiring board, sheet resistance (surface resistance value) was measured using the digital multimeter ("ADCMT 7461A" made from ADC. And the sheet | seat of the silver fine wire formed by the 10th printing From the resistance Rst (10) and the sheet resistance Rst (50) of the silver thin wire formed by the 50th printing, the 50-time sheet resistance fluctuation rate (%) was calculated by the following formula. Is 10% or less (50 times sheet resistance fluctuation rate is −10% to 10%), the continuous printing stability is determined as ○ (pass), and the 50 times sheet resistance fluctuation rate is 10 When the content exceeds 50% (the 50th sheet resistance fluctuation rate is -10%> or 10% <), the continuous printing stability was determined as x (failed), and the results are shown in Table 2.
50th sheet resistance fluctuation rate (%) = (Rst (50) −Rst (10)) / Rst (10) × 100

<Processing of Silver Ink Composition (A) (Production of Silver Ink Composition (B)) and Evaluation of Silver Ink Composition>
[Examples 2-7, Comparative Examples 2-4]
The silver ink composition (A) was processed in the same manner as in Example 1 except that the processing conditions were as shown in Table 2 (in Examples 2 to 7, the silver ink composition (B) was produced), The silver ink composition was evaluated. The results are shown in Table 2.

<Evaluation of silver ink composition (A)>
[Comparative Example 1]
The silver ink composition (A) was evaluated by the same method as in the case of the silver ink composition (B) described above. The results are shown in Table 2.

  As is clear from the above results, the silver ink composition after treatment in Examples 1 to 7 (silver ink composition (B)) was excellent in continuous printing stability, but after treatment in Comparative Examples 2 to 4 The silver ink composition was inferior in continuous printing stability. The silver ink composition (silver ink composition (A)) before the treatment of Comparative Example 1 (Production Example 1) was also inferior in continuous printing stability.

<Derivation of relationship of formula (i)>
For Examples 1 to 4, by plotting the processing temperature of the silver ink composition (A) on the x-axis and the processing time of the silver ink composition (A) on the logarithmic scale on the y-axis, the silver ink composition ( A graph showing the relationship between the processing temperature and the processing time of A) (hereinafter sometimes referred to as “graph (G1)”) was prepared. As a result, in the graph (G1), the relationship of x and y by regression calculation, approximated to a function of ^{y = 388.55e -0.14x.}
For Examples 5 to 7, plotting is performed with the processing temperature of the silver ink composition (A) on the horizontal axis and the processing time of the silver ink composition (A) on the logarithmic scale on the vertical axis in the same manner as described above. Thus, a graph showing the relationship between the processing temperature and processing time of the silver ink composition (A) (hereinafter sometimes referred to as “graph (G2)”) was prepared. As a result, in the graph (G2), the relationship of x and y by regression ^calculation, approximated to a function of ^{y = 1912.7e -0.128x.}
The graph (G1) and the graph (G2) are collectively shown in FIG.

From these results, the processing temperature x (° C.) and the processing time y (h) of the silver ink composition (A) are at least 388.55e− ^0.14x ≦ y, for example, when x is in the range of 0 to 42. When the relationship of ≦ 1912.7e− ^0.128x is satisfied, it can be said that the effect of the present invention is exhibited. Furthermore, since all the silver ink compositions (silver ink composition (B)) after the treatment in Examples 1 to 7 have the effects of the present invention, x is in the range of 0 to 42, and y is y. = 388.55e ^−0.14x is slightly smaller than the value specified, and y is slightly larger than the value specified by y = 1912.7e− ^0.128x. It can be said that there is an effect of the present invention. That is, the region surrounded by 0 ≦ x ≦ 42, 388.55e− ^0.14x ≦ y ≦ 1912.7e− ^0.128x on the xy plane is a direction in which y in the y-axis direction decreases and increases. If the processing conditions include x and y in a region slightly enlarged in both directions, the effect of the present invention can be said to be achieved. It can be said that it plays. 6, graph (G1) and together with the graph (G2), the graph of the function ^{y = 306.47e -0.139x} involved in the formula (i) (G3), and the function ^{y = 2403.2e -0.128x} A graph (G4) is also shown. The processing conditions of Examples 1 to 7 satisfy the relationship of the formula (i), but the processing conditions of Comparative Examples 2 to 4 do not satisfy the relationship of the formula (i).

<Manufacture of silver ink composition (A)>
[Production Examples 2 to 8]
A silver ink composition was produced in the same manner as in Production Example 1 except that the types and blending ratios of the blending components were as shown in Table 3.

<Processing of Silver Ink Composition (A) (Production of Silver Ink Composition (B)) and Evaluation of Silver Ink Composition>
[Examples 8 to 13, Comparative Examples 5 to 6]
The silver ink compositions (A) of Production Examples 1 to 8 were treated in the same manner as in Example 1 except that the treatment conditions were as shown in Table 4 (in Examples 8 to 13, the silver ink composition (B And the silver ink composition was evaluated. The results are shown in Tables 4 and 5.

  As is clear from the above results, the silver ink compositions after treatment in Examples 8 to 13 (silver ink composition (B)) were excellent in continuous printing stability, but after treatment in Comparative Examples 5 to 6 The silver ink composition was inferior in continuous printing stability. The processing conditions of Examples 8 to 13 satisfy the relationship of the formula (i), but the processing conditions of Comparative Examples 5 to 6 do not satisfy the relationship of the formula (i).

  INDUSTRIAL APPLICABILITY The present invention can be used for the production of a laminate in which a metallic silver fine pattern is formed on a substrate, and is suitable for application to the production of members in various electronic devices such as transparent electrodes, electromagnetic wave shields, and touch panels. It is.

DESCRIPTION OF SYMBOLS 1 ... Laminated body, 11 ... Base material, 11a ... Surface of base material, 12 ... Silver fine wire 800, 900 ... Stirrer blade, 810, 910 ... Drive shaft, 820, 920 ... Forced flow generating blades, 820a, 920a ... Outside edge of forced flow generating blades, 830 ... Connecting portion, 930 ... First connecting portion, 940 ... Second connecting portion, 950 ... Third connecting part

Claims (2)

Β-ketocarboxylate silver represented by the following general formula (1):
One or more nitrogen-containing compounds selected from the group consisting of amine compounds having 25 or less carbon atoms, quaternary ammonium salts having 25 or less carbon atoms, ammonia, and ammonium salts obtained by reacting the amine compounds or ammonia with acids. When,
One or more reducing agents selected from the group consisting of oxalic acid, hydrazine and a compound represented by the following general formula (5);
A silver ink composition comprising an acetylene alcohol represented by the following general formula (2) is blended, and the processing temperature x (° C.) and processing time y (h) of the silver ink composition are expressed by the following formula ( A method for treating a silver ink composition, comprising a step of treating so as to satisfy the relationship i) (where x is 0 to 42).
HC (= O) -R ²¹ (5)
(In the formula, R ²¹ represents an alkyl group having 20 or less carbon atoms, an alkoxy group, an N, N-dialkylamino group, a hydroxyl group, or an amino group.)
306.47e ^−0.139x ≦ y ≦ 2403.2e ^−0.128x (i)

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

(In the formula, R ′ and R ″ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.) By rotating the stirring blade in the stirring tank, the silver ink composition causes the silver β-ketocarboxylate, the nitrogen-containing compound, the reducing agent, and the acetylene alcohols in the stirring tank. Produced by a production method having a step of stirring,
As the stirring blade, a driving shaft, a forced flow generating blade portion having an outer side that rotates in the vicinity of the inner peripheral surface of the stirring tank, and a connecting portion that connects the driving shaft and the forced flow generating blade portion. The processing method of the silver ink composition of Claim 1 using what was equipped with these.

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