JP2018200174A - Sulfuration detection sensor, sulfuration detection method - Google Patents

Abstract

To provide a sulfuration detection sensor and sulfuration detection method capable of detecting easily in a short time the degree of sulfuration of an electrode made of silver.SOLUTION: A sulfuration detection sensor 10 of the present invention includes a mesh electrode 20 and electrodes 30 connected to both end portions 20a, 20b of the mesh electrode 20, respectively, and extending along both end portions 20a, 20b. The mesh electrode 20 includes a first wiring group 22 composed of a plurality of first fine wires 21 formed with regular intervals, and a second wiring group 24 intersecting perpendicular to the first wiring group 22 and composed of a plurality of second fine wires 23 formed with regular intervals. The longitudinal direction of the first fine wires 21, the longitudinal direction of the second fine wires 23 and the longitudinal direction of the electrode 30 obliquely intersect each other. The first fine wires 21 and the second fine wires 23 are made of silver.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a sulfide detection sensor and a sulfide detection method.

  Electronic devices have many electronic components including silver electrodes such as resistors and capacitors. It is known that silver (metal silver) tends to react with a sulfur-containing compound such as sulfur or a compound containing a sulfur atom to produce silver sulfide. In addition, the sulfur-containing compound is not only contained in a minute amount in the atmosphere, but may be contained in daily products such as cardboard and rubber. Such a sulfur-containing compound may cause the silver electrode to sulfidize and cause the electronic component to fail.

Therefore, various apparatuses for detecting sulfur-containing compounds have been studied.
As a sulfur-containing compound detection device, for example, a sulfide detection sensor having an insulating substrate, a sulfide detector, a bottom electrode, a side electrode, and a protective film is known (see, for example, Patent Document 1). In this sulfidation detection sensor, the sulfidation detector is a conductor mainly composed of silver which is easily sulfided. Further, the protective film has a sulfide gas permeability and is formed to be transparent. This sulfuration detection sensor detects the change in the color of the sulfide detector, detects the change in resistance value of the sulfide detector, or detects the reflected light from the sulfide detector. Detect the degree of sulfidation.

  In addition, as a sulfur-containing compound detection device, for example, a plurality of combinations of a sulfur-containing compound detection unit that causes a color change upon contact with a sulfur-containing compound and a comparison unit for comparing the detection unit and color. An equipped sulfur-containing compound detection device is known (for example, see Patent Document 2). In this sulfur-containing compound detection device, the detection unit has an exposed surface containing metallic silver, and the surface roughness of the exposed surface is different between some or all combinations. This sulfur-containing compound detection device uses a phenomenon in which metallic silver contained in an exposed surface (detection unit) undergoes a color change due to contact with a sulfur-containing compound, and exposed surfaces having different surface roughnesses have surface roughness. Depending on the degree, the degree of sulfuration on the exposed surface is detected by utilizing the fact that a difference in the degree of color change occurs even when the exposure amount of the sulfur-containing compound is the same.

JP 2009-250611 A JP 2014-89063 A

However, the sulfide detection sensor described in Patent Document 1 requires an electronic circuit, and thus has a complicated structure, and also requires a measuring device corresponding to each detection method. Therefore, this sulfuration detection sensor cannot detect a sulfur-containing compound easily and inexpensively.
Moreover, since the sulfur-containing compound detection apparatus described in Patent Document 2 requires a detection unit and a comparison unit, it cannot be installed in a narrow place. In addition, since this sulfur-containing compound detection device cannot objectively evaluate the degree of color change between the detection unit and the comparison unit by numerical values, the variation in detection results is large.
Further, these apparatuses require a long time to detect the degree of sulfidation, and cannot detect the degree of sulfidation in a short time of several minutes to several tens of minutes.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a sulfide detection sensor and a sulfide detection method capable of detecting the degree of sulfuration of an electrode made of silver easily and in a short time. And

  The sulfide detection sensor of the present invention is a sulfide detection sensor comprising a mesh electrode and electrodes connected to both ends of the mesh electrode and extending along the both ends, and the mesh The electrode includes a first wiring group composed of a plurality of first fine wirings formed at equal intervals, and a second wiring composed of a plurality of second fine wirings formed perpendicularly to the first wiring group and formed at equal intervals. A length direction of the first fine wiring, a length direction of the second fine wiring, and a length direction of the electrode are obliquely intersected, and the first fine wiring and the second fine wiring are It is made of silver.

  The sulfide detection method of the present invention is a sulfide detection method using the sulfide detection sensor of the present invention, wherein the mesh electrode is measured from a change in the resistance value of the mesh electrode by measuring the resistance value of the mesh electrode. It is characterized by detecting the degree of sulfidation of the electrode.

  According to the present invention, it is possible to provide a sulfide detection sensor and a sulfide detection method that can detect the degree of sulfuration of an electrode made of silver simply and in a short time.

It is the schematic which shows the sulfide detection sensor of embodiment, (a) is a top view, (b) is an enlarged view of the area | region (alpha) in (a). In an Example, it is a figure which shows the change of the resistance value of the mesh electrode which comprises the sulfide detection sensor exposed to air | atmosphere.

Embodiments of the sulfide detection sensor and the sulfide detection method of the present invention will be described.
Note that this embodiment is specifically described in order to better understand the gist of the invention, and does not limit the present invention unless otherwise specified.

[Sulfurization detection sensor]
Hereinafter, with reference to the drawings, the sulfide detection sensor of the present embodiment will be specifically described.
FIG. 1 is a schematic view showing a sulfuration detection sensor of the present embodiment, where (a) is a plan view and (b) is an enlarged view of a region α in (a).
As shown in FIG. 1, the sulfide detection sensor 10 of the present embodiment is connected to a mesh electrode 20 and both ends of the mesh electrode 20 (ends in the left-right direction in FIG. 1) 20a and 20b. The electrode 30 (30A, 30B) extending along the both end portions 20a, 20b.

The mesh electrode 20 has a square shape in plan view. The length of the mesh electrode 20 in the vertical direction (L ₁ in FIG. 1A) and the length of the mesh electrode 20 in the horizontal direction (L ₂ in FIG. 1A) are not particularly limited. The level is appropriately adjusted according to the degree of sulfuration detected by the sensor 10 (sensitivity for detecting the degree of sulfuration) and the like.

  The mesh electrode 20 perpendicularly intersects the first wiring group 22 composed of a plurality of first fine wirings 21 formed at equal intervals and the first wiring group 22 (first fine wiring 21), and is formed at equal intervals. And a second wiring group 24 including a plurality of second fine wirings 23. Accordingly, the mesh electrode 20 has a large number of lattices 26 formed by the first fine wiring 21 and the second fine wiring 23 and has a mesh shape. In the sulfide detection sensor 10 of the present embodiment, as shown in FIG. 1, the lattice 26 has a square shape in plan view.

The interval between the first fine wires 21 (W ₁ in FIG. 1B) and the interval between the second fine wires 23 (W ₂ in FIG. 1B) are not particularly limited, and are detected by the sulfide detection sensor 10. It is appropriately adjusted according to the degree of sulfuration (sensitivity for detecting the degree of sulfuration). The interval between the first fine wires 21 and the interval between the second fine wires 23 may be the same or different. If the distance between the first fine wirings 21 and the distance between the second fine wirings 23 are the same, the lattice 26 has a square shape in plan view. If the interval between the first fine wires 21 and the interval between the second fine wires 23 are different, the lattice 26 has a rectangular shape in plan view.

  The width of the first fine wiring 21, that is, the length perpendicular to the extending direction (length direction) in the first fine wiring 21 is not particularly limited, and depends on the degree of sulfuration detected by the sulfuration detection sensor 10. It is adjusted accordingly. Similarly, the width of the second fine wiring 23, that is, the length perpendicular to the extending direction (length direction) in the second fine wiring 23 is not particularly limited, and the sulfuration detected by the sulfuration detection sensor 10 is not particularly limited. It is appropriately adjusted depending on the degree and the like. The width of the first fine wiring 21 and the width of the second fine wiring 23 may be the same or different.

  In addition, as shown in FIG. 1B, the length direction of the first fine wiring 21 and the length direction of the second fine wiring 23 and the length direction of the electrode 30 intersect diagonally. In this way, since the lattice 26 formed by the first fine wiring 21 and the second fine wiring 23 obliquely intersects with the electrode 30, the first fine wiring 21 and the second fine wiring 23 are arranged in the vicinity of the electrode 30. Can be used effectively. When the length direction of the first fine wiring 21 or the length direction of the second fine wiring 23 and the length direction of the electrode 30 intersect perpendicularly, one side of the lattice 26 is parallel to the length direction of the electrode 30. Therefore, one side of the lattice 26 and the electrode 30 overlap, and the first fine wiring 21 or the second fine wiring 23 may not be effectively used in the vicinity of the electrode 30.

  The first fine wiring 21 and the second fine wiring 23 are made of silver which is easily sulfided.

  The electrode 30 (30A, 30B) has a rectangular shape (strip shape) in plan view, and a square-shaped electrode tab 31 (31A, 31B) is provided in the center in the length direction.

The length of the electrode 30 (L ₃ in FIG. 1A) is not particularly limited, and is appropriately adjusted according to the size of the mesh electrode 20. The width of the electrode 30 (W ₃ in FIG. 1A) is not particularly limited, and is appropriately adjusted according to the size of the mesh electrode 20.

The vertical width (W ₄ in FIG. 1A) of the electrode tab 31 is not particularly limited, and is appropriately adjusted according to the size of the mesh electrode 20. The width in the horizontal direction of the electrode tab 31 (W ₅ in FIG. 1A) is not particularly limited, and is appropriately adjusted according to the size of the mesh electrode 20.

  Moreover, the mesh electrode 20 and the electrode 30 may be provided on a film-like or sheet-like base material (not shown).

For example, a metal ink composition is used to form the first fine wiring 21 and the second fine wiring 23.
Examples of the metal ink composition include a composition in which a metal forming material is blended.
The metal forming material may be any material that has a corresponding metal atom (element) and generates a metal by structural change such as decomposition. Examples of such metal forming materials include metal salts, metal complexes, organometallic compounds (compounds having a metal-carbon bond), and the like. The metal salt and metal complex may be either a metal compound having an organic group or a metal compound having no organic group. Among these, the metal forming material is preferably a metal salt, and more preferably a silver salt.

The metal forming material is preferably an organic silver compound.
The organic silver compound is a compound that has an organic group and a silver atom in one molecule, and generates metallic silver by a structural change such as decomposition. Examples of such organic silver compounds include silver salts of organic acids and organic silver complexes. Among these, a silver salt of an organic acid is preferable, and silver carboxylate (a silver salt of carboxylic acid) is more preferable.

  The silver carboxylate is not particularly limited as long as it has a group represented by the formula “—COOAg”. For example, the number of groups represented by the formula “—COOAg” may be only one, or two or more. Further, the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.

  The metal forming material in the metal ink composition may be used alone or in combination of two or more, and when there are two or more, the combination and ratio thereof can be arbitrarily adjusted.

  The metal ink composition may be a composition in which a metal (single metal or alloy) is blended in addition to the metal forming material. The metal to be blended is preferably silver or copper, and more preferably silver.

The metal (single metal or alloy) to be blended is preferably in the form of particles or fibers (tube shape, wire shape, etc.), more preferably nanoparticles or nanowires, silver nanoparticles, silver nanoparticles It is more preferable that they are a wire, a copper nanoparticle, or a copper nanowire, and it is especially preferable that they are a silver nanoparticle or a silver nanowire.
In the present specification, “nanoparticle” means a particle having a particle size of 1 nm or more and less than 1000 nm, preferably 1 nm to 100 nm, and “nanowire” means a width of 1 nm or more and less than 1000 nm, preferably It means a wire that is 1 nm to 100 nm.

The metal ink composition can be attached to the substrate by a known method such as a printing method.
Examples of the printing method include screen printing method, flexographic printing method, offset printing method, dip printing method, ink jet printing method, dispenser printing method, jet dispenser printing method, gravure printing method, gravure offset printing method, The pad printing method etc. are mentioned. Among these, the gravure offset printing method, the screen printing method, and the flexographic printing method are preferable.

  The metal ink composition contains, for example, a silver β-ketocarboxylate represented by the following general formula (1) (hereinafter sometimes abbreviated as “β-ketocarboxylate (1)”) as a metal forming material. What is made is preferable. Examples of such a metal ink composition include a silver ink composition (A1) obtained by blending silver β-ketocarboxylate (1), a nitrogen-containing compound, a reducing agent, and acetylene alcohol (2). Hereinafter, each component will be described.

<Silver β-ketocarboxylate (1)>
The β-ketocarboxylate (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 (1), R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a general formula “R” in which one or more hydrogen atoms may be substituted with a substituent. ^1- CY ¹ _2- "," CY ¹ _3- "," R ¹ -CHY ^1- "," R ² O- "," R ⁵ R ⁴ N- "," (R ³ O) ₂ CY ^1-" Or a group represented by “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 Good. 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 group, 1-ethyl-1-methylpropyl group, n-heptyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group Sil 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 Group, 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, Examples include 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. Etc. Further, the number and position of substituents are not particularly limited. When the number of substituents is plural, the plural substituents may be the same as or different from each other. That is, all the substituents may be the same, all the substituents may be different, or only some of the substituents may be different.

In the phenyl group in R, one or more hydrogen atoms may be substituted with a substituent. Preferred examples of the substituent include a saturated or unsaturated monovalent aliphatic having 1 to 16 carbon atoms. A hydrocarbon 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 as 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, 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 are the same as the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 16. It is done.
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 for R except that the number of carbon atoms is 1 to 18.
R ⁶ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO—”. 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 whose number 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), X ¹ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. 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 “ It is a group represented by “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 X ¹ include those similar to the aliphatic hydrocarbon group in 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—), or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. or diphenyl group (biphenyl _{group, C 6 H 5 -C 6 H} 4 -) is. Examples of the aliphatic hydrocarbon group for R ⁷ include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 10. In addition, examples of the substituent of the phenyl group and diphenyl group in R ⁷ include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and the number and position of the 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.
When R ⁷ is a thienyl group or a diphenyl group, the bonding position of these with an adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X ¹ is not particularly limited. For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.

In the general formula (1), two X ^{1 s} may be bonded as one group through 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 preferably decomposed at a low temperature of 60 ° C. to 210 ° C., more preferably 60 ° C. to 200 ° C., without using a reducing agent known in the art, as will be described later. In addition, metallic silver can be formed.

  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) to be described later, and increase the concentration of the silver ink composition (A1). Are particularly suitable.

  In the silver ink composition (A1), the blending amount of β-ketocarboxylate (1) is not particularly limited, but the ratio of the blending amount of β-ketocarboxylate (1) to the total blending amount of all components is It is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 70% by mass, and particularly preferably 20% by mass to 60% by mass. When the ratio is in such a range, the handleability of the silver ink composition (A1) is improved, and high-purity metallic silver can be easily formed.

<Nitrogen-containing compounds>
The nitrogen-containing compound includes 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 “quaternary ammonium salt”). Ammonia, an ammonium salt formed by a reaction of 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 as an acid. And 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 straight-chain having 1 to 19 carbon atoms or It is preferably a branched 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 a carbon atom 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 benzoxdiazolyl 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 preferable 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 constituting the dialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms, or 3 to 3 carbon atoms. 7 is a cyclic alkyl group. Two alkyl groups in one molecule of dialkylamine may be the same 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 as 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 carbon atoms. It is preferably a cyclic alkyl group of ˜7. 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 has a carbon atom number. It is preferably a 3-7 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 halogenated tetraalkylammonium may be the same 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 has 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 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 substituents. 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 substituted group. As the group, a cyclic alkyl group having 3 to 7 carbon atoms having an alkyl group having 1 to 5 carbon atoms is preferable, and specific examples of the monoalkylamine having such a substituent include, for example, , 2-phenylethylamine, benzylamine, 2,3-dimethylcyclohexylamine and the like.
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. Specific examples of the arylamine 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 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 each 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 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 (A1), the compounding amount of the nitrogen-containing compound is preferably from 0.3 mol to 15 mol per mol of the β-ketocarboxylate silver (1), and from 0.3 mol to More preferably, it is 5 moles. When the blending amount of the nitrogen-containing compound is within such a range, the silver ink composition (A1) 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 in R of the general formula (1) Examples are the same as those described above.

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 or different from each other. The alkyl groups each have 1 to 19 carbon atoms. However, the total number of carbon atoms 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, R in the general formula (1) except that the number of carbon atoms is 1 to 19. Examples thereof include the same as the above alkyl group.

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 (A1), the compounding amount of the reducing agent is preferably 0.04 mol to 1.5 mol per mol of the β-ketocarboxylate (1) compounding amount, and 0.06 mol. More preferably, it is -1.0 mol. When the blending amount of the reducing agent is within such a range, the silver ink composition (A1) can form a conductor (metal silver) more easily and more stably.

<Acetylene alcohol (2)>
Acetylene alcohol (2) is represented by general formula (2).

In formula (2), R ′ and R ″ each independently represent 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. is there.
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 aliphatic 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. are mentioned, and the hydrogen atom of the phenyl group in R is substituted. It is the same as the above-described 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 are a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. It is more preferable.

  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 (A1), the blending amount of acetylene alcohol (2) is preferably 0.01 to 0.7 mole per mole of silver β-ketocarboxylate (1). It is more preferable that it is 02 mol-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 (A1) may be used in addition to the β-ketocarboxylate (1), the nitrogen-containing compound, the reducing agent, and the acetylene alcohol (2) as long as the effects of the present invention are not impaired. These ingredients may be blended.
Examples of the other components include alcohols other than acetylene alcohol (2) (hereinafter sometimes abbreviated as “other alcohols”), acetylene alcohol (2), and solvents other than the other alcohols. .

  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 (A1), the blending amount of the components other than the alcohol and the solvent may be appropriately selected according to the type of the component, and is not particularly limited.
Especially, in the silver ink composition (A1), 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 (A1), 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 examples thereof include a temperature of 15 ° C. to 30 ° C.

  More specific 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 a monohydric alcohol and a dihydric or higher polyhydric alcohol 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.

  More specifically, examples of the acetylene alcohol (2) and other alcohols include 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.
The acetylene alcohol (2) and other alcohols are preferably linear or branched.

When the silver ink composition (A1) is formed by blending the other alcohol, the blending amount of the other alcohol in the silver ink composition (A1) is not particularly limited.
Among these, in the silver ink composition (A1), the ratio of the blending amount of the other alcohol to the blending amount of the acetylene alcohol (2) is preferably 1% by mass to 10% by mass, and preferably 1% by mass to 1% by mass. More preferably, it is 5 mass%. 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 (A1) is formed by blending the solvent, the blending amount of the solvent in the silver ink composition (A1) is not particularly limited.
In particular, in the silver ink composition (A1), the amount of the solvent is preferably 0.5 mol to 5 mol per mol of the β-ketocarboxylate (1), and preferably 0.5 mol. It is more preferably ˜3.5 mol, particularly preferably 0.5 mol to 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 (A1), 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 (A1) 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 each component, the obtained product may be used as it is as the silver ink composition (A1), or the product obtained by performing a known purification operation as necessary as the silver ink composition (A1). Also good. At the time of blending each of the above components, the silver ink composition (A1) that has not been subjected to a refining operation because 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 of the components may be added and then mixed, or some components may be mixed while being sequentially added, or all components may be mixed while being sequentially added. 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 applying ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.
In the silver ink composition (A1), when the undissolved components are 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 (A1), the temperature at the time of blending is preferably −5 ° C. 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 (A1), the blending time is preferably 10 minutes to 36 hours.

  In the production of the silver ink composition (A1), 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 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. Further, at the time of producing the silver ink composition (A1), two or more kinds of blending components may be added simultaneously.

  For example, a metal ink composition is used to form the electrode 30 as in the formation of the first fine wiring 21 and the second fine wiring 23.

When the mesh electrode 20 and the electrode 30 are provided on a base material, examples of the material of the base material include polyethylene terephthalate (PET), polycarbonate (PC), polymethyl methacrylate (PMMA), and polyethylene naphthalate (PEN). , Polyethersulfone (PES), cyclic olefin copolymer (COC), triacetylcellulose (TAC), polyvinyl alcohol (PVA), polyimide (Polyimide; PI), polystyrene (Polystyrene; PS), biaxial stretching Examples include polystyrene (K resin-containing biaxially oriented PS; BOPS), paper, glass, tempered glass, and the like.
Further, in order to improve the adhesion of the first fine wiring 21 and the second fine wiring 23 to the base material, a high-frequency treatment or a primer (Primer) is formed on the surface of the base material on which the first fine wiring 21 and the second fine wiring 23 are formed. ) Processing may be performed.

  According to the sulfide detection sensor 10 of the present embodiment, the mesh electrode 20 is provided from the first wiring group 22 and the second wiring group 24 intersecting perpendicularly to the first wiring group 22, and the first fine wiring 21 and the second wiring 20 are provided. The fine wiring 23 is made of silver, and the surface area of the mesh electrode 20 is large. For example, since the fine wiring 23 is easily contacted with a sulfur-containing compound contained in the atmosphere, the sulfide electrode of the mesh electrode 20 made of silver can be easily and quickly. The degree can be detected. Thereby, the degree of sulfidation of an electronic component or the like can be predicted in the environment where the sulfidation detection sensor 10 is installed.

[Sulfurization detection method]
The sulfide detection method of the present embodiment is a sulfide detection method using the above-described sulfide detection sensor 10 of the present embodiment. The resistance value of the mesh electrode 20 is measured and the resistance value of the mesh electrode 20 is changed. From this, the degree of sulfidation of the mesh electrode 20 is detected.

In the sulfide detection method of the present embodiment, a resistance meter terminal is connected to the electrode tabs 31A and 31B of the sulfide detection sensor 10, and the resistance value between the electrodes 30A and 30B, that is, the resistance value of the mesh electrode 20 is measured. To do.
For example, in order to detect the degree of sulfidation of the mesh electrode 20 due to a sulfur-containing compound contained in the atmosphere by exposing the sulfide detection sensor 10 to a specific atmosphere, the resistance value of the mesh electrode 20 immediately before the exposure is measured. To do. The degree of sulfidation of the mesh electrode 20 can be detected by measuring the resistance value of the mesh electrode 20 every predetermined time or continuously after the exposure of the sulfide detection sensor 10 is started.

Among the sulfur-containing compounds that sulfidize the mesh electrode 20, examples of those contained in the atmosphere include sulfur dioxide (SO ₂ ), sulfur trioxide (SO ₃ ), and hydrogen sulfide (HS).

  According to the sulfide detection method of the present embodiment, the degree of sulfurization of the mesh electrode 20 made of silver can be detected easily and in a short time using the sulfide detection sensor 10 of the present embodiment. Thereby, the degree of sulfidation of an electronic component or the like can be predicted in the environment where the sulfidation detection sensor 10 is installed. Since silver sulfidation is faster than oxidation, it is possible to confirm whether or not the container has been opened by installing the sulfidation detection sensor 10 in a container in which contents such as food are enclosed. it can. That is, if the resistance value of the mesh electrode 20 is the same as when the contents are enclosed in the container, it can be determined that the container is not opened, and the resistance value of the mesh electrode 20 is determined so that the contents are contained in the container. If it is different from when it was sealed, it can be determined that the container was opened.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

[Example]
(Manufacture of silver ink composition)
In a beaker, 2-ethylhexylamine (1.45-fold mol amount relative to 2-methylacetoacetate silver described later), n-hexane (1.63-fold mol amount based on 2-methylacetoacetate silver described later), Were added in this order, and silver 2-methylacetoacetate was added to the beaker while rotating and stirring the mechanical stirrer so that the liquid temperature was 50 ° C. or lower.
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 In this state, the mixture was stirred for 5 minutes to obtain a silver ink composition.
As DMHO, “Surfinol 61” manufactured by Air Products Japan was used, and as EOO, manufactured by Tokyo Chemical Industry Co., Ltd. was used.

(Manufacture of transparent conductive substrate)
The main surface of the polycarbonate substrate is coated with the silver ink composition obtained above by a gravure offset printing method, and as shown in FIG. 1, the first wiring group 22 and the second wiring group A print pattern of 24 electrodes 20 and electrodes 30 extending along both end portions 20a and 20b of the mesh electrode 20 was formed to obtain the sulfide detection sensor 10 of the example.
The obtained mesh electrode 20 had a longitudinal length (L ₁ in FIG. 1A) and a lateral length (L ₂ in FIG. 1A) of 25 mm. The pitch of the mesh electrodes 20 (distance between adjacent first fine wires 21 and second fine wires 23) was 195 μm, and the widths of the first fine wires 21 and the second fine wires 23 were 5 μm. The length of the electrode 30 (L ₃ in FIG. 1A) was 25 mm, and the width of the electrode 30 (W ₃ in FIG. 1A) was 3 mm. The electrode tab 31 had a vertical width (W ₄ in FIG. 1A) and a horizontal width (W ₅ in FIG. 1A) of 3 mm.

Details of the printing method are as follows.
The intaglio used for printing is made of metal and has a groove serving as a conductive thin film mold on its surface. The pitch of the grooves (distance between adjacent grooves) is 195 μm. As the offset roll, a metal cylinder whose surface was covered with a silicone resin blanket material was used.
The silver ink composition was supplied to the plate, and doctoring was performed using a doctor blade to fill the groove of the plate with the silver ink composition. Excess metal ink composition was removed.
The silver ink composition was transferred from the plate to a transfer material (blanket), and the transfer material was dried to form a conductive film.
The transferred silver ink composition was dried in two steps. In the first stage heat treatment, the silver ink composition is mainly dried rather than the formation of metallic silver, and in the second stage heat treatment, the formation of metallic silver is performed to the end. In the first stage heat treatment, hot air was used, the heating temperature was 120 ° C., and the heating time was 5 minutes. In the second stage heat treatment, humidification was performed with heated steam. The heating temperature was 120 ° C. and the heating time was 10 minutes. The relative humidity in the heat treatment under humidified conditions was 30% to 90%.
The “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.

  In this way, two sulfuration detection sensors 10 having the same structure were produced.

(Evaluation)
A resistance meter terminal was connected to the electrode tabs 31A and 31B of the obtained sulfuration detection sensor 10, the sulfuration detection sensor 10 was exposed to the atmosphere, and the resistance value of the mesh electrode 20 was measured every predetermined time. The results are shown in Table 1, Table 2 and FIG.

  In Tables 1 and 2, and n1 and n2, n1 and n2 indicate one of the two produced sulfuration detection sensors 10, respectively. The resistance value change rate in Table 2 is based on the resistance value of the mesh electrode 20 at the start of exposure (resistance value 1.000), and the ratio of the resistance value of the mesh electrode 20 at each exposure time to the reference value. It is.

  From the results of Tables 1 and 2 and FIG. 2, it was confirmed that the resistance value of the mesh electrode 20 increases with the passage of the exposure time to the atmosphere. That is, it was confirmed that the degree of sulfidation of the mesh electrode 20 can be detected from the change in the resistance value of the mesh electrode 20.

DESCRIPTION OF SYMBOLS 10 ... Sulfide detection sensor, 20 ... Mesh electrode, 21 ... 1st fine wiring, 22 ... 1st wiring group, 23 ... 2nd fine wiring, 24 ... 2nd wiring Group, 26 ... lattice, 30, 30A, 30B ... electrode, 31, 31A, 31B ... electrode tab.

Claims (2)

A sulfide detection sensor comprising a mesh electrode and electrodes connected to both ends of the mesh electrode and extending along the both ends,
The mesh electrode is composed of a first wiring group composed of a plurality of first fine wirings formed at equal intervals and a plurality of second fine wirings formed perpendicularly to the first wiring group and formed at equal intervals. A second wiring group,
The length direction of the first fine wiring and the length direction of the second fine wiring, and the length direction of the electrode cross each other diagonally;
The sulfide detection sensor, wherein the first fine wiring and the second fine wiring are made of silver. A sulfuration detection method using the sulfide detection sensor according to claim 1,
A sulfurization detection method comprising: measuring a resistance value of the mesh electrode and detecting a degree of sulfidation of the mesh electrode from a change in the resistance value of the mesh electrode.

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