Conductive composition, method for producing the same, method for recording conductive image, and conductive image

Abstract

To provide: a conductive composition which is capable of easily recording a conductive image having excellent electrical conductivity even with a simple aftertreatment; and a method for producing the same.SOLUTION: The conductive composition contains metal particles and a treatment agent for coating the metal particles. The treatment agent is at least one selected from the group consisting of compounds represented by general formulas (1) to (7).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a conductive composition and a method for producing the same, a method for recording a conductive image, and a conductive image. [Background technology]

[0002] Liquid conductive compositions containing metal particles are used as materials for recording and forming conductive images, such as conductive patterns and circuits. To stably disperse metal particles in such conductive compositions, it is necessary to use modifiers that can adsorb to the metal particles. However, since such modifiers do not contribute to conductivity, they had to be removed from the recorded conductive images by high-temperature firing or solvent-based cleaning. However, with the increasing diversification of substrates used to record conductive images, there is a growing demand for conductive compositions that do not require high-temperature firing.

[0003] For example, Patent Document 1 proposes a conductive ink for forming a conductive pattern, containing conductive particles and an ionic liquid (Patent Document 1). Also, Patent Document 2 proposes a conductive ink for forming a conductive film, containing metal particles, an organic component that can adsorb to the surface of these metal particles to form a micelle structure, and an amine compound that acts as a stabilizer. Furthermore, Patent Document 3 proposes a nano-ink composition for forming a conductive film, containing metal particles and an organic π-conjugated ligand such as phthalocyanine that π-bonds to these metal particles. Also, Patent Document 4 proposes a conductive paste for heated steam treatment containing metal particles, a resin binder, and a hydrazone compound. Patent Document 4 discloses that after screen printing the paste, a reducing hydrazine compound is generated from the hydrazone compound by heated steam treatment, thereby reducing the metal oxide back to the metal. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2006-335995 [Patent Document 2] Japanese Patent Publication No. 2014-240491 [Patent Document 3] Japanese Patent Publication No. 2016-026237 [Patent Document 4] Japanese Patent Publication No. 2015-076233 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, with conductive inks proposed in Patent Documents 1 to 4, simply drying them without firing them at high temperatures after application to the substrate is insufficient to remove components that do not contribute to conductivity, making it difficult to record images with excellent conductivity.

[0006] Therefore, an object of the present invention is to provide a conductive composition that allows for the easy recording of conductive images with excellent conductivity even with simple post-processing. Another object of the present invention is to provide a method for producing this conductive composition, a method for recording conductive images using this conductive composition, and conductive images. [Means for solving the problem]

[0007] In other words, the present invention provides a conductive composition comprising metal particles and a treatment agent for coating the metal particles, wherein the treatment agent is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following general formula (5), a compound represented by the following general formula (6), and a compound represented by the following general formula (7).

[0008] TIFF2023010589000001.tif28170 (In the above general formula (1), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is the hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0009] TIFF2023010589000002.tif28170 (In the above general formula (2), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is the hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0010] TIFF2023010589000003.tif22170 (In the above general formula (3), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0011] TIFF2023010589000004.tif23170 (In the above general formula (4), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0012] TIFF2023010589000005.tif16170 (In the above general formula (5), R1 represents a hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0013] TIFF2023010589000006.tif37170 (In the above general formula (6), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond.)

[0014] TIFF2023010589000007.tif43170 (In the above general formula (7), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond.) [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a conductive composition that allows for the easy recording of conductive images with excellent conductivity even with simple post-processing. Furthermore, according to the present invention, it is possible to provide a method for manufacturing this conductive composition, a method for recording conductive images using this conductive composition, and conductive images. [Modes for carrying out the invention]

[0016] The present invention will be described in more detail below with reference to preferred embodiments. In the present invention, when a compound is a salt, the salt exists in the composition dissociated into ions, but for convenience, it will be expressed as "contains a salt." In the present invention, a conductive composition may be simply referred to as "composition" or "ink." Also, in the present invention, "image" includes characters, photographs, line drawings, wiring, patterns, etc., and the expression of a desired "image" on a substrate will be described as "recording" or "forming." Unless otherwise specified, physical property values ​​are values ​​at room temperature (25°C).

[0017] As a result of various studies, the present inventors have found that it is effective to use a low molecular weight compound having a hydrazine structure that functions as an adsorption site for metal particles and a hydrophilic group for dispersing the metal particles as a modifier for the metal particles. That is, by using together a metal particle and a specific low molecular weight compound having a hydrazine structure and a hydrophilic group, it has been found that a conductive image excellent in conductivity can be recorded only by performing a simple post-treatment such as drying, and the present invention has been achieved.

[0018] <Conductive composition> The conductive composition of the present invention contains metal particles and a treatment agent for coating the metal particles. Hereinafter, each component constituting the conductive composition will be described separately.

[0019] (Metal particles) The conductive composition contains metal particles. The metal particles are preferably formed of at least one metal selected from the group consisting of nickel, palladium, platinum, copper, silver, and gold. Among them, as the material for forming the metal particles, platinum, copper, silver, and gold are preferable, and silver and gold are particularly preferable.

[0020] At least a part of the particle surface of the metal particles is coated with a treatment agent described later. When the treatment agent interacts with the metal particles, the treatment agent adheres to and is immobilized on the surface of the metal particles. The interaction between the metal particles and the treatment agent includes physical adsorption and chemical adsorption. In the case of physical adsorption, it is a mixture of van der Waals interaction and ion adsorption and is considered to be in an equilibrium state. On the other hand, in the case of chemical adsorption, it is considered that a chemical bond (covalent bond) is formed between the metal atoms contained in the metal particles and the nitrogen atoms contained in the treatment agent. The coating of the metal particles with the treatment agent may be either physical adsorption or chemical adsorption.

[0021] The compounds described later, used as processing agents for metal particles, are all thought to have nitrogen atoms that interact with the metal particles to coat them, while hydrophilic groups function as dispersing groups to disperse the metal particles. By using such specific low-molecular-weight compounds, metal particles that are difficult to disperse in liquid media such as aqueous media can be stably dispersed. In addition, conductive compositions that can easily form conductive images with excellent conductivity can be obtained by simply performing post-treatment such as drying.

[0022] Whether or not at least a portion of the surface of a metal particle is coated with a treatment agent can be confirmed by the zeta potential of the metal particle. The zeta (ζ) potential of a metal particle not coated with a treatment agent is usually 0mV or higher, that is, the zeta potential is zero or a positive value with a small absolute value (a value of about 0 to +3mV). In contrast, the zeta potential of a metal particle whose surface at least a portion is coated with a treatment agent changes depending on the hydrophilic group of the treatment agent. If the hydrophilic group of the treatment agent is anionic, the zeta potential of the metal particle coated with the treatment agent is lower than that of the uncoated metal particle (mainly a negative value, specifically a value of -1mV or less). On the other hand, if the hydrophilic group of the treatment agent is a heteroaromatic group or a tertiary alkylamino group, the zeta potential of the metal particle coated with the treatment agent is higher than that of the uncoated metal particle (mainly a positive value with a large absolute value, specifically a value of +5mV or higher).

[0023] The zeta potential can be measured using a zeta potential measuring device. When measuring the zeta potential, it is preferable to use a sample prepared by first centrifuging the conductive composition to remove the supernatant in order to exclude treatment agents that do not coat metal particles, thereby obtaining a wet cake, and then diluting it with a liquid medium (such as water).

[0024] In the manufacturing process of conductive compositions, whether or not at least a portion of the surface of metal particles is coated with the treatment agent can be confirmed by tracking the amounts of these compounds before and after contact with the metal particles. For example, after contacting the metal particles with the treatment agent, the metal particles are separated into solid and liquid by centrifugation, and the amount of treatment agent in the resulting supernatant is quantitatively analyzed to verify whether or not a portion or all of the surface of the metal particles is coated with the treatment agent. Methods for tracking the amount of treatment agent before and after contact with metal particles (analytical methods) include using high-performance liquid chromatography (HPLC) or gas chromatography (GC).

[0025] Metal particles exist in a dispersed state within the conductive composition. From the viewpoint of storage stability, the volume-based cumulative 50% particle diameter of the metal particles in the conductive composition is preferably between 5 nm and 100 nm. Hereinafter, "volume-based cumulative 50% particle diameter" will also be simply referred to as "average particle diameter." If the average particle diameter of the metal particles is less than 5 nm, aggregation may occur easily within the conductive composition. On the other hand, if the average particle diameter of the metal particles exceeds 100 nm, sedimentation may occur easily within the conductive composition. The volume-based cumulative 50% particle diameter (average particle diameter) of the metal particles can be measured by dynamic light scattering. When the metal particles are formed of gold or silver, differences in particle diameter can be easily determined by measuring the ultraviolet-visible absorption spectrum.

[0026] (Treatment agent) The conductive composition contains at least one compound selected from the group consisting of compounds represented by the following general formulas (1) to (7) as a treatment agent for coating metal particles. The treatment agent is preferably a colorless compound (a compound that does not have an absorption maximum in the wavelength region of 360 to 830 nm). In other words, the treatment agent is not a so-called "colorant". The molecular weight of the treatment agent is preferably 1,000 or less, more preferably 600 or less, particularly preferably 500 or less, and also preferably 100 or more. The molecular weight of the treatment agent is for a structure in which the anionic group is in the acid form and the cationic group is in the basic form.

[0027] TIFF2023010589000008.tif28170

[0028] In general formula (1), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is a hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. A hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which a hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. Compounds represented by general formula (1) can also be called hydrazine compounds.

[0029] TIFF2023010589000009.tif28170

[0030] In general formula (2), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is a hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. A hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which a hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. Compounds represented by general formula (2) can also be called hydrazone compounds.

[0031] In general formula (3), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. A hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which a hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.

[0032] In general formula (4), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. A hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which a hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.

[0033] In general formula (5), R1 represents a hydrophilic group. A hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which a hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.

[0034] In general formula (6), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is a hydrophilic group. A hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which a hydrophilic functional group is attached, which may contain a heteroatom, an amide bond, or an ester bond.

[0035] In general formula (7), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is a hydrophilic group. A hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which a hydrophilic functional group is attached, which may contain a heteroatom, an amide bond, or an ester bond.

[0036] Aliphatic groups represented by R1-R4 in general formula (1), R1-R4 in general formula (2), R1-R8 in general formula (6), and R1-R8 in general formula (7) include alkyl groups and alkenyl groups. Alkyl groups and alkenyl groups may be linear, branched, or cyclic, and preferably have 1 to 12 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, neopentyl, hexyl, cyclopentyl, and cyclohexyl groups. Examples of alkenyl groups include ethenyl, propenyl, and butenyl groups. At least some of the hydrogen atoms constituting the aliphatic group may be substituted with halogen atoms such as fluorine, chlorine, and bromine, or heteroatoms such as nitrogen, oxygen, and sulfur.

[0037] Aromatic groups represented by R1-R4 in general formula (1), R1-R4 in general formula (2), R1 and R2 in general formula (3), R1 and R2 in general formula (4), R1-R8 in general formula (6), and R1-R8 in general formula (7) include aryl groups and heteroaryl groups. The aryl group and heteroaryl group may be monocyclic or compound ring, and the number of atoms constituting the ring is preferably 3 to 10. Examples of heteroatoms constituting the heteroaryl group include nitrogen, oxygen, and sulfur atoms. Examples of aryl groups include phenyl, naphthyl, anthracenyl, phenantrenyl, and biphenyl groups. Examples of heteroaryl groups include pyridyl, imidazolyl, pyrazolyl, pyridinyl, thienyl, and thiazolyl groups. Among these, phenyl, naphthyl, anthracenyl, phenantrenyl, biphenyl, and pyridinyl groups are preferred, with phenyl being even more preferred.

[0038] The acid ester groups represented by R1-R4 in general formula (1), R1-R4 in general formula (2), R1-R8 in general formula (6), and R1-R8 in general formula (7) are groups in which the above-mentioned aliphatic group or aromatic group is bonded to the ester bond -C(=O)-O- of a carboxylic acid. Examples of acid ester groups include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, and phenoxycarbonyl group.

[0039] In general formula (1), at least one of R1 to R4 is a hydrophilic group, and not all of the remaining groups are hydrogen atoms at the same time. In general formula (2), at least one of R1 to R4 is a hydrophilic group, and not all of the remaining groups are hydrogen atoms at the same time. By not making all of the non-hydrophilic groups among R1 to R4 in general formula (1) and R1 to R4 in general formula (2) hydrogen atoms, and instead creating a structure with substituents other than hydrophilic groups, the reactivity of the hydrazine structure, which is the reaction active site, can be reduced. This can suppress the aggregation of metal particles due to reduction. Also, at least one of R1 and R2 in general formula (3) is a hydrophilic group. At least one of R1 and R2 in general formula (4) is a hydrophilic group. R1 in general formula (5) is a hydrophilic group.

[0040] The hydrophilic groups represented by R1 to R4 in general formula (1), R1 to R4 in general formula (2), R1 and R2 in general formula (3), R1 and R2 in general formula (4), and R1 in general formula (5) are any of the following (i) to (iii). (i) Heteroaromatic groups (ii) Aromatic groups to which at least one hydrophilic functional group selected from the group consisting of hydroxyl groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, phosphonic acid groups, tertiary alkylamino groups, and heteroaromatic groups is attached. (iii) an aromatic group in which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphate group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.

[0041] (i) Examples of heteroatoms constituting the heteroaromatic group include nitrogen, oxygen, and sulfur atoms. Examples of heteroaromatic groups include pyridyl, pyridazyl, pyrazyl, pyrimidyl, triazyl, imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, and furanyl groups. Among these, pyridazyl, pyrazyl, pyrimidyl, and triazyl groups are preferred. That is, the hydrophilic group in general formula (1) and the hydrophilic group in general formula (2) are preferably independently one of the heteroaromatic groups selected from the group consisting of (i) pyridazyl, pyrazyl, pyrimidyl, and triazyl groups.

[0042] (ii) Examples of aromatic groups to which hydrophilic functional groups such as hydroxyl groups are attached include aryl groups and heteroaryl groups. The aryl group and heteroaryl group may be monocyclic or complex, and the number of atoms constituting the ring is preferably 3 to 10. Examples of heteroatoms constituting the heteroaryl group include nitrogen, oxygen, and sulfur atoms. Examples of aryl groups include phenyl, naphthyl, anthracenyl, phenantrenyl, and biphenyl groups. Examples of heteroaryl groups include pyridyl, imidazolyl, pyrazolyl, pyridinyl, thienyl, and thiazolyl groups. Among these, phenyl, naphthyl, anthracenyl, phenantrenyl, biphenyl, and pyridinyl groups are preferred, and phenyl is more preferred.

[0043] (iii) Aromatic groups in which a hydrophilic functional group such as a hydroxyl group is bonded via an aliphatic group which may contain a heteroatom, amide bond, or ester bond include aryl groups and heteroaryl groups. The aryl group and heteroaryl group may be monocyclic or complex ring, and the number of atoms constituting the ring is preferably 3 to 10. Examples of heteroatoms constituting the heteroaryl group include nitrogen, oxygen, and sulfur atoms. Examples of aryl groups include phenyl, naphthyl, anthracenyl, phenantrenyl, and biphenyl groups. Examples of heteroaryl groups include pyridyl, imidazolyl, pyrazolyl, pyridinyl, thienyl, and thiazolyl groups. Among these, phenyl, naphthyl, anthracenyl, phenantrenyl, biphenyl, and pyridinyl groups are preferred, and phenyl is more preferred. Examples of aliphatic groups include alkylene groups having 1 to 6 carbon atoms, such as methylene, ethylene, n-propylene, i-propylene, butylene, propylene, and hexylene. Examples of heteroatoms include nitrogen, oxygen, and sulfur atoms.

[0044] In general formulas (1) to (5), the hydrophilic group is preferably independently either (ii) or (iii) below: (ii) a phenyl group to which a hydrophilic functional group is attached; or (iii) a phenyl group to which a hydrophilic functional group is attached via an aliphatic group which may contain a heteroatom, amide bond, or ester bond. Furthermore, it is even more preferable that the hydrophilic group is a phenyl group to which at least one of a carboxylic acid group and a sulfonic acid group is attached. The total number of carboxylic acid groups and sulfonic acid groups attached to the phenyl group is preferably 2 or 3 from the viewpoint of hydrophilicity and availability.

[0045] At least one of R1 to R8 in general formula (6) is a hydrophilic group. At least one of R1 to R8 in general formula (7) is a hydrophilic group. The hydrophilic groups represented by R1 to R8 in general formula (6) and R1 to R8 in general formula (7) are (i) or (ii) shown below. (i) Any hydrophilic functional group selected from the group consisting of hydroxyl groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, phosphonic acid groups, tertiary alkylamino groups, and heteroaromatic groups (ii) an aliphatic group which may contain a heteroatom, amide bond, or ester bond, to which any hydrophilic functional group selected from the group consisting of a hydroxyl group, carboxylic acid group, sulfonic acid group, phosphate group, phosphonic acid group, tertiary alkylamino group, and heteroaromatic group is attached.

[0046] Examples of heteroatoms constituting a heteroaromatic group include nitrogen, oxygen, and sulfur atoms. Examples of heteroaromatic groups include pyridyl, pyridazyl, pyrazyl, pyrimidyl, triazyl, imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, and furanyl groups. Among these, pyridazyl, pyrazyl, pyrimidyl, and triazyl groups are preferred.

[0047] Examples of aliphatic groups include alkylene groups having 1 to 6 carbon atoms, such as methylene, ethylene, methylmethylene, n-propylene, i-propylene, butylene, propylene, and hexylene. Examples of heteroatoms include nitrogen, oxygen, and sulfur atoms.

[0048] The hydrophilic group in general formula (6) and the hydrophilic group in general formula (7) are preferably independently groups represented by the following general formula (8).

[0049] TIFF2023010589000015.tif26170

[0050] In general formula (8), R x and R y Each of these independently represents an alkyl group, and R z R represents an alkylene group. In general formula (8), R x and R yThe alkyl group represented by may be linear, branched, or cyclic, and preferably has 1 to 12 carbon atoms. The cyclic alkyl group may be monocyclic or compound, and preferably has 3 to 10 carbon atoms constituting the ring. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, neopentyl, hexyl, cyclopentyl, and cyclohexyl groups.

[0051] In general formula (8), R z The alkylene group represented by may be linear or cyclic, and an alkylene group having 1 to 6 carbon atoms is preferred. Examples of linear alkylene groups include methylene, ethylene, n-propylene, i-propylene, butylene, propylene, and hexylene groups. Examples of cyclic alkylene groups include 1,2-cyclobutylene, 1,2-cyclopentylene, 1,2-cyclohexylene, 1,2-cyclooctylene, and 1,2-cyclodecylene groups.

[0052] In each general formula, hydrophilic functional groups such as hydroxyl groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, phosphonic acid groups, tertiary alkylamino groups, and heteroaromatic groups may form salts. Examples of cations that form salts include alkali metal ions, ammonium ions, and organic ammonium ions. Examples of alkali metal ions include lithium, sodium, and potassium ions. Examples of organic ammonium ions include alkylamines and alkanolamines. Examples of anions that form salts include hydroxide ions and halide ions. Examples of halide ions include iodine, bromine, and chlorine ions.

[0053] If the conductive composition further contains an aqueous medium, hydrophilic groups can be selected according to the pH of the aqueous medium. For example, if the pH of the aqueous medium is acidic (pH < 7), tertiary alkylamino groups and heteroaromatic groups are more likely to form salts. On the other hand, if the pH of the aqueous medium is alkaline (pH > 7), hydroxyl groups, carboxylic acid groups, sulfonic acid groups, phosphate groups, and phosphonic acid groups are more likely to form salts.

[0054] Examples of compounds represented by each general formula are shown in Tables 1-1, 1-2, 2-1 to 2-4, and 3 to 7, with acidic groups in the acidic form and basic groups in the basic form. Of course, in the present invention, compounds represented by each general formula are not limited to the compound examples shown below, as long as they are included in the structure and definition of each general formula. In Tables 1-1, 1-2, 2-1 to 2-4, and 3 to 7, the abbreviations are Me: methyl group, Et: ethyl group, Ph: phenyl group, tBu: t-butyl group, and 2Py: 2-pyridyl group.

[0055] TIFF2023010589000016.tif255155

[0056] TIFF2023010589000017.tif255165

[0057] TIFF2023010589000018.tif253170

[0058] TIFF2023010589000019.tif255152

[0059] TIFF2023010589000020.tif239170

[0060] TIFF2023010589000021.tif255153

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[0065] TIFF2023010589000026.tif213170

[0066] All compounds represented by general formulas (1) to (7) can be used as coating agents to stably disperse metal particles in a liquid medium. Among these, compounds represented by general formulas (1), (2), (6), and (7) are preferred because they offer excellent dispersion stability of metal particles and stability of the coating agent, with compounds represented by general formulas (1) and (2) being even more preferred. On the other hand, among the coating agents, compounds represented by general formulas (3) to (5) tend to result in a slightly smaller zeta potential (absolute value) of the coated particles, and their dispersion stability tends to be relatively low. Furthermore, because compounds represented by general formulas (3) to (5) tend to have relatively low stability as coating agents, compounds represented by general formulas (1), (2), (6), and (7) are more preferred.

[0067] (liquid medium) The conductive composition may further contain a liquid medium. Both non-aqueous and aqueous media can be used as the liquid medium. Examples of non-aqueous media include liquid media composed of organic solvents such as heptane and petroleum ether. Non-aqueous media do not contain water. Aqueous media contain water and may further contain various organic solvents. It is preferable that the conductive composition further contains an aqueous medium.

[0068] Aqueous media are water, or mixed media mainly composed of water combined with protic or aprotic organic solvents. It is preferable to use organic solvents that are miscible with water in any proportion (water-miscible organic solvents) or that dissolve in water in any proportion (water-soluble organic solvents). In particular, it is preferable to use a homogeneous mixed media containing 50% or more water as the aqueous medium. As water, it is preferable to use deionized water (ion-exchanged water) or ultrapure water.

[0069] Protic organic solvents are organic solvents that have hydrogen atoms bonded to oxygen or nitrogen atoms (acidic hydrogen atoms). Aprotic organic solvents are organic solvents that do not have acidic hydrogen atoms. Examples of organic solvents include alcohols, (poly)alkylene glycols, glycol ethers, glycol ether esters, carboxylic acid amides, ketones, keto alcohols, cyclic ethers, nitrogen-containing solvents, and sulfur-containing solvents.

[0070] Examples of aqueous media include water, water / alcohol mixed solvents, water / (poly)alkylene glycol mixed solvents, and water / nitrogen-containing solvent mixed solvents. The water content (mass%) in the conductive composition is preferably 10.0% by mass or more and 90.0% by mass or less, and more preferably 50.0% by mass or more and 90.0% by mass or less, based on the total mass of the conductive composition.

[0071] The content (by mass) of water-soluble organic solvent in the conductive composition is preferably 5.0% by mass or more and 90.0% by mass or less, and more preferably 10.0% by mass or more and 50.0% by mass or less, based on the total mass of the conductive composition.

[0072] (Other additives) The conductive composition may further contain, as needed, water-soluble organic compounds such as polyhydric alcohols like trimethylolpropane and trimethylolethane; urea derivatives such as urea and ethylene urea; and, as needed, various additives such as surfactants, pH adjusters, rust inhibitors, preservatives, fungicides, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, and resins.

[0073] As the surfactant, anionic, cationic, and nonionic surfactants can be used. The surfactant content (mass%) in the conductive composition is preferably 0.1% by mass or more and 5.0% by mass or less, and more preferably 0.1% by mass or more and 2.0% by mass or less, based on the total mass of the conductive composition.

[0074] As surfactants, it is preferable to use nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene alkylphenyl ethers, polyoxyethylene-polyoxypropylene block copolymers, and acetylene glycol compounds.

[0075] <Method for producing conductive compositions> Next, a method for producing the conductive composition described above will be explained. The method for producing the conductive composition of the present invention comprises a first step of reducing a metal salt in an aqueous medium to form metal particles, and a second step of bringing the formed metal particles into contact with a treatment agent.

[0076] (1st step) In the first step, a metal salt is reduced in an aqueous medium to form metal particles. As the aqueous medium, the aforementioned aqueous medium that can be contained in the conductive composition can be used. Examples of metal salts include metal salts composed of metal ions and inorganic anion species, metal salts composed of metal ions and organic anion species, and metal salts composed of metal ions and inorganic organic anion species. As the metal ions, metal ions such as nickel, palladium, platinum, copper, silver, and gold that can form metal particles can be used. Examples of inorganic anion species include anions of oxides, halogens, carbonic acid, and nitric acid. Examples of organic anion species include carboxylic acid anions such as formic acid and acetic acid.

[0077] Specific examples of metal salts include nickel compounds such as nickel(II) chloride and nickel(II) nitrate; palladium compounds such as palladium(II) chloride, palladium(II) acetate, and palladium(II) oxide; platinum compounds such as platinum(II) chloride and platinum(IV) oxide; copper compounds such as copper(I) chloride, copper(II) chloride, copper(I) oxide, and copper(II) oxide; silver compounds such as silver(I) chloride, silver nitrate, silver oxide, and silver acetate; and gold compounds such as gold(III) oxide, gold(I) chloride, tetragold octachloride, gold(III) chloride, gold(III) bromide, gold(III) fluoride, gold(V) fluoride, gold(I) hydroxide, and gold(III) hydroxide.

[0078] In recent years, it has been pointed out that precious metals and rare metals used in electronic devices and other products may be depleted within a few decades if their use continues at the current rate. These materials are called critical materials, and efforts are being made in various countries to recover and recycle these resources from used precious metal products and discarded electronic devices in order to prevent resource depletion. Among these, the recycling of precious metals such as platinum, gold, and silver is more advanced than that of other resources, and recycling technologies are being established. One method of recycling gold involves removing other metals from recovered waste products, dissolving and leaching the gold with aqua regia or organic solvents, recrystallizing the gold with a reducing agent to increase its purity, and then further melting it to remove organic matter and form a solid. When recovering precious metals are reused as products, purity assurance is required. For example, in the case of gold, a high purity of 99.99% must be guaranteed.

[0079] From this perspective, it is also preferable to use recovered metal salts recovered from metal waste liquid as the metal salt. For example, when producing a conductive composition containing gold particles as metal particles, chlorauric(III) acid made from recovered gold can be used. Chlorauric(III) acid can be prepared by drying the gold-o aqueous solution produced during the gold regeneration method described above.

[0080] When manufacturing a conductive composition containing gold particles as metal particles, regenerated chlorauric(III) acid can be used as one of the starting materials. Because gold has high reducing properties, gold particles are preferentially formed even if other metal impurities are present in the regenerated chlorauric(III) acid. Therefore, a high purity guarantee is not required for the regenerated chlorauric(III) acid. The purity of the chlorauric(III) acid is preferably 90% or higher, and more preferably 95% or higher. In the gold regeneration process, processes related to purity assurance can be omitted, thereby reducing raw material costs.

[0081] Furthermore, when manufacturing a conductive composition containing silver particles as metal particles, a high purity guarantee is not required for silver(I) nitrate, which can be used as one of the starting materials. The purity of silver(I) nitrate is preferably 90% or higher, and more preferably 95% or higher. In the silver recycling process, processes related to purity assurance can be omitted, thereby reducing raw material costs.

[0082] Silver(I) nitrate can be recovered from waste according to known methods. For example, if nitric acid is added to a silver-containing waste liquid to make it acidic, and a dichromate salt is added to the filtrate obtained by separating the precipitate, a precipitate of silver dichromate will be formed. After dissolving the silver dichromate precipitate in hot dilute nitric acid, silver(I) nitrate can be recovered by treating it with an NO3 type anion exchange resin.

[0083] To reduce metal salts, it is preferable to use a reducing agent. Examples of reducing agents include alcohols having primary hydroxyl groups such as methanol, ethanol, 1-propanol, and ethylene glycol; alcohols having secondary hydroxyl groups such as 2-propanol and 2-butanol; alcohols having both primary and secondary hydroxyl groups such as glycerin; thiols; aldehydes such as formaldehyde and acetaldehyde; sugars such as glucose, fructose, glyceraldehyde, lactose, arabinose, and maltose; organic acids and their salts such as citric acid, tannic acid, and ascorbic acid; boron hydrides and their salts; hydrazines such as hydrazine, alkylhydrazine, and hydrazine sulfate. Examples of anions that form salts of organic acids and boron hydrides include alkali metal ions such as lithium, sodium, and potassium; alkaline earth metal ions such as calcium and magnesium; ammonium ions; and organic ammonium ions.

[0084] As a reducing agent, it is preferable to use organic acids or their salts. Organic acids and their salts reduce the metal salt and, at the same time, adhere to the surface of the formed metal particles, generating a repulsive force that prevents aggregation or coalescence of the metal particles. Ascorbic acid and its salts, citric acid and its salts are preferred organic acids and their salts. Among these, ascorbic acid salts and citrate salts are even more preferred.

[0085] Furthermore, compounds such as polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, gelatin, starch, dextrin, carboxymethylcellulose, methylcellulose, and ethylcellulose can be used as reducing agents. These compounds, like the organic acids and their salts mentioned above, reduce metal salts and also adhere to the surface of the formed metal particles, generating a repulsive force that prevents aggregation or coalescence of the metal particles.

[0086] The amount of reducing agent used should be appropriately set according to the type of metal, the concentration of the metal salt, the size (particle diameter) of the metal particles to be formed, and the temperature and stirring force when adding the reducing agent. In the first step, it is preferable to reduce the metal salt while stirring vigorously. Furthermore, in the first step, it is preferable to reduce the metal salt under heating conditions, and it is even more preferable to reduce the metal salt while refluxing the aqueous medium. For example, when water is used as the aqueous medium, it is preferable to set the temperature to 115°C or higher and 200°C or lower. The temperature can be adjusted by the temperature of the oil bath used to heat the reaction vessel.

[0087] Even after being reduced by a reducing agent, metal particles that are not coated with a treatment agent exhibit a zeta potential value corresponding to the type of reducing agent. For example, in the example described later, citric acid is used as a reducing agent to form gold particles. The zeta potential of gold particles coated with citric acid is approximately -40mV. However, since reducing agents such as citric acid have weak adhesion to metal particles, a conductive composition in which metal particles are continuously and stably dispersed is not formed.

[0088] (2nd process) In the second step, the metal particles formed in the first step are brought into contact with the treatment agent. Specifically, the metal particles and the treatment agent can be mixed in an aqueous medium. This allows the desired conductive composition to be obtained. If the amount of treatment agent should be just enough to uniformly cover the surface of all the metal particles (and not excessive), the approximate amount can be determined by following the method below.

[0089] If the particle size of the metal particles is determined, the surface area per metal particle can be calculated. Therefore, if the area occupied per molecule of the treatment agent can be estimated, the number of molecules required to cover the surface of one metal particle can be calculated. The occupied area can also be estimated by calculating the cross-sectional area assuming an atomic diameter of 1.5 Å and multiplying it by the number of atoms in the treatment agent.

[0090] Alternatively, the saturation adsorption amount that coats the metal particles can be estimated and used as a guideline for the amount to be added. Specifically, the amount of adsorption is plotted against the amount of treatment agent added. If the resulting plot (adsorption isotherm) follows a Langmuir-type adsorption isotherm, there is a region where the amount of adsorption does not increase even if the amount of additive is increased, and saturation occurs. In this region, the amount of adsorption can be considered the saturation adsorption amount. In the second step, it is preferable to bring the metal particles into contact with the treatment agent while heating to a temperature of 20°C to 50°C. Residue of the reducing agent used in the first step may adhere to the surface of the metal particles as an impurity. By heating to a temperature of 20°C to 50°C, it is thought that the impurities are removed while being replaced by a treatment agent with stronger interactions.

[0091] <Method for recording conductive images> Next, a method for recording conductive images will be described. The method for recording conductive images of the present invention includes a step of applying the above-mentioned conductive composition to a substrate. By applying the conductive composition to the substrate, a desired conductive image can be obtained. Examples of methods for applying the conductive composition to the substrate include inkjet printing, flexographic printing, and spin coating. Among these, it is preferable to apply the conductive composition to the substrate by inkjet printing. Inkjet printing is a method of applying the conductive composition to a substrate such as a recording medium by ejecting it from an inkjet-type ejection head. Methods for ejecting the conductive composition from the ejection head include methods that impart mechanical energy to the conductive composition and methods that impart thermal energy to the conductive composition. Aside from using the above-mentioned conductive composition, any known method can be used for applying the conductive composition to the substrate by inkjet printing.

[0092] When a conductive composition is dispensed from an inkjet ejection head onto a substrate to record (form) a conductive image, it is preferable to use a conductive composition whose surface tension and viscosity are appropriately controlled. Specifically, the content (mass%) of metal particles in the conductive composition is preferably 5.0% by mass or more and 20.0% by mass or less, based on the total mass of the composition. If the content of metal particles in the conductive composition is less than 5.0% by mass, the amount of conductive composition required to form a film-like conductive image may become too large. On the other hand, if the content of metal particles in the conductive composition exceeds 20.0% by mass, the ejection port of the ejection head may become easily clogged.

[0093] The surface tension of the conductive composition at 25°C is preferably 10 mN / m to 60 mN / m, more preferably 20 mN / m to 60 mN / m, and particularly preferably 30 mN / m to 50 mN / m. The viscosity of the conductive composition at 25°C is preferably 1.0 mPa·s to 10 mPa·s, and more preferably 1.0 mPa·s to 5 mPa·s. The pH of the conductive composition at 25°C is preferably 5.0 to 9.0.

[0094] The method for recording conductive images may further include a step of drying the conductive composition applied to the substrate. Using the above-mentioned conductive composition, a conductive image with excellent conductivity can be formed simply by drying at a low temperature such as room temperature (25°C), without having to dry it at a high temperature of, for example, 100°C or higher. The conductive composition applied to the substrate may be dried by blowing air or heating, but it is also acceptable to dry it without using these methods, i.e., by natural drying. The temperature for drying the conductive composition applied to the substrate is preferably 20°C to 120°C, and more preferably 20°C to 50°C. If the drying temperature is below 20°C, the drying time may be longer. Shortening the drying time tends to increase the conductivity of the recorded conductive image. If the heat resistance temperature of the substrate is high, it is also possible to raise the drying temperature to the heat resistance temperature. In the recording method of the present invention, after applying the conductive composition to the substrate, it is not necessary to perform steps of heating or sintering, or curing by irradiation with active energy rays, etc.

[0095] <Conductive image> The conductive image of the present invention is a conductive image comprising a substrate and a conductive layer formed on the substrate, wherein the conductive layer contains metal particles whose particle surface is coated with the above-mentioned treatment agent. Preferably, the conductive image of the present invention is a conductive image recorded on a substrate and is an image formed by the above-mentioned conductive composition.

[0096] (base material) The substrate can be any material that can form a conductive image by drying the applied conductive composition. Since the conductive composition exhibits conductivity even when dried at low temperatures, a substrate with a low heat resistance temperature can also be used. Preferably, the substrate is glass, paper, resin material, ceramics, or silicon.

[0097] Examples of resin materials include synthetic resins such as polyethylene terephthalate, polyimide, and polyethylene glycol; and biocompatible synthetic or natural resins such as polyhydroxybutyric acid, polycyanoacrylate, polyanhydride, polyketone, poly(orthoester), poly-ε-caprolactone, polyacetal, poly(α-hydroxyester), polycarbonate, poly(iminocarbonate), polyphosphazene, poly(β-hydroxyester), polypeptide, gelatin, cellulose, chitosan, collagen, and fibroin. The resin material is preferably in sheet form.

[0098] As the resin material, it is preferable to use a biocompatible material. As a biocompatible material, a sheet-like material formed from resins such as polyhydroxybutyric acid, polycyanoacrylate, polyanhydride, polyketone, poly(orthoester), poly-ε-caprolactone, polyacetal, poly(α-hydroxyester), polycarbonate, poly(iminocarbonate), polyphosphazene, poly(β-hydroxyester), polypeptide, gelatin, cellulose, chitosan, collagen, and fibroin is preferred. Among these, a biocompatible material formed from at least one natural polymer selected from the group consisting of gelatin, cellulose, chitosan, collagen, and fibroin is preferred. [Examples]

[0099] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited in any way by the following examples unless it exceeds the gist of the invention. Unless otherwise specified, amounts of components indicated in "parts" and "%" are based on mass.

[0100] <Synthesis of treatment agents> Of the treatment agents, those not commercially available as reagents were synthesized according to known methods described in the following literature. Treatment agents other than those for which synthesis examples are provided were synthesized in the same manner, except for the change to a starting material having the corresponding structure. The structures of the synthesized compounds were identified by analysis using liquid chromatography / mass spectrometry (LC / MS) (trade name "LC / MSD TOF," manufactured by Agilent Technologies). Electrospray ionization (ESI) was used as the ionization method. • Journal of the American Chemical Society, 2007, Vol. 129, No. 34, pp. 10320-10321. Tetrahedron Letters, 2007, Vol. 48, No. 48, pp. 8409-8412 • Nature Chemistry, 2017, Vol. 9, No. 3, pp. 234-243

[0101] (Example compound 1-1) 0.94 g of 1,1-dimethylhydrazine, 220 mg of Pd2(dba)3·CHCl3 (manufactured by Fujifilm Wako Pure Chemical Industries), 140 mg of P(t-Bu)3·HBF4 (manufactured by Tokyo Chemical Industries), and 8.1 g of cesium carbonate were added to 100 mL of toluene to obtain a suspension. Under an argon atmosphere, 2.4 g of ethyl 4-bromobenzoate was added to the suspension and heated under reflux at 100 °C for 12 hours. After cooling to room temperature, water was added and the mixture was extracted with toluene. The toluene layer was concentrated using a rotary evaporator, and the resulting components were purified by column chromatography to obtain 0.9 g of ethyl (2,2-dimethylhydrazinyl)benzoate. An aqueous sodium hydroxide solution was added and the mixture was stirred at 25 °C for 3 hours. Hydrochloric acid was added, and the resulting solid was filtered to obtain 0.8 g of exemplary compound 1-1 (m / z = 180.1, yield 37%).

[0102] (Example compound 2-1) 1.5 g of 4-hydrazinobenzoic acid was dissolved in 20 mL of ethanol, to which 0.6 g of acetaldehyde was added and the mixture was stirred at 70°C for 5 hours. After cooling to 25°C, the liquid was removed using a rotary evaporator to obtain 1.4 g of example compound 2-1 (m / z = 178.1, yield 80%).

[0103] (Example compound 3-1) 0.5 mmol of 4-nitrobenzoic acid, 5 mmol of 4-aminobenzoic acid, 5 mmol of potassium hydroxide, 6 mL of methanol, and 7 mL of water were placed in a pressure-resistant glass bottle and sealed with an aluminum clin cap. The mixture was heated and stirred in an oil bath at 100°C for 24 hours, then cooled to 25°C. The solvent was removed using an evaporator, and the mixture was extracted with cold methanol and filtered to obtain a solid. The obtained solid was dissolved in dichloromethane, and 20 mL of concentrated hydrochloric acid and 20 mL of acetic anhydride were added and stirred at 25°C for 24 hours. 100 mL of water and 50 mL of dichloromethane were added, and the organic layer was extracted to obtain an extract. The obtained extract was purified by silica gel column chromatography to obtain exemplary compound 3-1 (m / z = 270.1, yield 37%).

[0104] (Example compound 4-1) 0.18 mol of 4-aminobenzoic acid, 5 g of concentrated hydrochloric acid, and 150 mL of methanol were placed in a 300 mL round-bottom flask and cooled to 0°C while stirring in an ice bath. 0.2 mol of sodium nitrite dissolved in 25 mL of purified water was slowly added dropwise while keeping the temperature in the container below 5°C, and the mixture was stirred to obtain a beige suspension containing the diazonium salt. 0.2 mol of 4-aminobenzoic acid, 0.6 mol of sodium acetate, and 300 mL of methanol were placed in a 1 L round-bottom flask and cooled to 0°C while stirring in an ice bath to prepare a suspension. The previously prepared suspension containing the diazonium salt was slowly added to the prepared suspension and stirred at 25°C for 15 hours. The reaction product was filtered by suction, the solids were washed with 500 g of water and 100 g of methanol, and then vacuum-dried to obtain exemplary compound 4-1 (m / z = 285.1, yield 56%).

[0105] (Example Compounds 4-11) 0.18 mol of 4-aminobenzoic acid, 5 g of concentrated hydrochloric acid, and 150 mL of methanol were placed in a 300 mL round-bottom flask and cooled to 0°C while stirring in an ice bath. 0.2 mol of sodium nitrite dissolved in 25 mL of purified water was slowly added dropwise while stirring, keeping the temperature in the container below 5°C, to obtain a beige suspension containing the diazonium salt. 0.2 mol of 4-aminopyridine, 0.6 mol of sodium acetate, and 300 mL of methanol were placed in a 1 L round-bottom flask and cooled to 0°C while stirring in an ice bath to prepare a suspension. The previously prepared suspension containing the diazonium salt was slowly added to the prepared suspension and stirred at 25°C for 15 hours. The reaction product was filtered by suction, the solids were washed with 500 g of water and 100 g of methanol, and then vacuum-dried to obtain exemplary compound 4-11 (m / z = 94.1, yield 38%).

[0106] (Example compound 5-27) Under an argon atmosphere, 0.8 g of N,N-dimethylethylenediamine was added to 1.0 g of 4-cyanobenzoyl chloride in 20 mL of chloroform and reacted with stirring at 25°C for 5 hours. The mixture was concentrated using a rotary evaporator, and the resulting components were purified by column chromatography to obtain 1.3 g of exemplary compound 5-27 (m / z = 217.1, yield 99%).

[0107] (Example compounds 7-12) In a 300 mL round-bottom flask equipped with a nitrogen line, 50 mL of anhydrous tetrahydrofuran, 9.3 mmol of dimethylaminoethanethiol, and 10 mmol of sodium hydride were placed and stirred while maintaining the temperature at 0°C in an ice bath. A solution of 8.4 mmol of 2-bromophenanthroline dissolved in 10 mL of anhydrous tetrahydrofuran was added dropwise, and the temperature was slowly raised to 25°C and stirred for 72 hours. The solvent was removed using an evaporator, extracted with cold methanol, and filtered to obtain a solid. The obtained solid was dissolved in dichloromethane and purified by silica gel column chromatography to obtain exemplary compounds 7-12 (m / z = 283.1, yield 24%).

[0108] (Example compounds 7-15) In a 300 mL round-bottom flask equipped with a nitrogen line, 50 mL of anhydrous tetrahydrofuran, 9.3 mmol of dimethylaminoethanethiol, and 10 mmol of sodium hydride were added and stirred while maintaining the temperature at 0°C in an ice bath. A solution of 4.2 mmol of 2,9-dibromophenanthroline dissolved in 100 mL of anhydrous tetrahydrofuran was added dropwise, and the temperature was slowly raised to 25°C and stirred for 72 hours. The solvent was removed using an evaporator, extracted with cold methanol, and filtered to obtain a solid. The obtained solid was dissolved in dichloromethane and purified by silica gel column chromatography to obtain exemplary compounds 7-15 (m / z = 386.2, yield 15%).

[0109] <Preparation of recovered metal salts> A recovered metal salt was prepared using gold recovered from a substrate as the raw material. The gold-plated substrate was cut and crushed into pieces approximately 5 mm x 5 mm in size to facilitate chemical treatment. The obtained crushed pieces were immersed in 10% dilute nitric acid for 2 hours to dissolve the copper and nickel and lift the gold-plated foil from the substrate. The gold-plated foil was then separated by passing dilute nitric acid through a filter lined with filter paper. The dilute nitric acid had a bluish-green color due to the dissolved copper and nickel. Dilute nitric acid was added to the gold-plated foil on the filter paper to wash away any remaining copper and nickel from the surface of the gold-plated foil. The obtained gold-plated foil, along with the filter paper, was transferred to another container, and a solution of 35% hydrochloric acid and 60% nitric acid mixed in a 3:1 (volume ratio) was added dropwise to dissolve the gold. Once the gold was dissolved, the filter paper was removed, and the resulting gold-o Using an acid-resistant rotary evaporator, the filtrate was heated and distilled under reduced pressure to remove nitric acid, hydrochloric acid, and water in that order, yielding chloraurugric(III) tetrahydrate.

[0110] <Manufacturing of conductive composition (dispersion)> A conductive composition (dispersion) was prepared by the method described below. The average particle size (volume-based cumulative 50% particle size, D50) of the metal particles in the prepared conductive composition was measured using a small-angle X-ray scattering instrument (product name "Nano-Viewer", manufactured by Rigaku). The measurement conditions were wavelength (λ): 0.154 nm and incident angle: 1.7°. The zeta potential of the metal particles in the conductive composition was measured using a zeta potential meter (product name "Zetasizer Nano", manufactured by Malvern). For this measurement, the prepared conductive composition was subjected to centrifugation to remove the supernatant and obtain a wet cake, which was then diluted with ultrapure water to a concentration suitable for measurement. The zeta potentials of gold particles and silver particles produced by reducing gold(III) chloride tetrahydrate and silver(I) nitrate (both manufactured by Kishida Chemical Co., Ltd.) with trisodium citrate dihydrate were 1 mV and 0 mV, respectively.

[0111] (Conductive composition using gold particles) The amounts of chlorauric(III) tetrahydrate and 1,300 mL of ultrapure water shown in Tables 8-14 were heated under reflux, and the amounts of trisodium citrate dihydrate shown in Tables 8-14 were added. The mixture was stirred for 2 hours while maintaining the internal temperature at 100°C. In the tables, chlorauric(III) tetrahydrate is denoted as "chlorauric(III) acid," and trisodium citrate dihydrate is denoted as "citric acid." After cooling to 25°C, the pH of the liquid was adjusted to 5 using 0.1 mol / L hydrochloric acid as needed, and 3 mmol of the type of treatment agent shown in Tables 8-14 was added. The mixture was stirred for 15 hours to obtain each conductive composition. In Tables 8-14, "Au (recovered)" in the metal particle column refers to the chlorauric(III) tetrahydrate obtained in the "Preparation of recovered metal salts" described above.

[0112] (Conductive composition using silver particles) The amounts of silver(I) nitrate (manufactured by Kishida Chemical Co., Ltd.) and trisodium citrate dihydrate shown in Tables 8-14 were dissolved in 1,000 mL of ultrapure water and stirred for 30 minutes while cooling with ice to obtain an aqueous solution. To the obtained aqueous solution, a solution of 33 mg of sodium borohydride dissolved in 1 g of deionized water was added, and the mixture was stirred for another 30 minutes while cooling with ice to obtain a brown, transparent dispersion. After cooling the obtained dispersion to 25°C, the pH of the liquid was adjusted to 3 using 0.1 mol / L hydrochloric acid as needed, and 3 mmol of the type of treatment agent shown in Tables 8-14 was added while stirring. The mixture was then stirred at 25°C for another 30 minutes to obtain each conductive composition.

[0113] (Conductive composition D1) Conductive composition D1 was prepared by the method shown below (comparative example). Conductive composition D1 was obtained in the same manner as the preparation of the conductive composition [dispersion] using gold particles described above, except that 4,5-bis[(2-N,N-dimethylaminoethyl)thio]phthalonitrile (phthalocyanine derivative) was used as the treatment agent. The average particle size of the metal particles in the obtained conductive composition D1 was 20 nm, and the zeta potential of the metal particles was 39 mV. 4,5-bis[(2-N,N-dimethylaminoethyl)thio]phthalonitrile was synthesized using 4,5-dichlorophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) as a raw material, according to a known method described in the following literature. Details of conductive composition D1 are shown in Table 15. • Journal of Medicinal Chemistry, 2015, Vol. 58, No. 4, pp. 1736-1749

[0114] (Conductive composition D2) Conductive composition D2 was prepared by the following method (comparative example). 1 g of chlorauro(III) tetrahydrate (manufactured by Kishida Chemical) and 1,300 mL of ultrapure water were heated under reflux, and 1.75 g of trisodium citrate dihydrate was added and stirred for 2 hours. The mixture was cooled to 25°C to obtain conductive composition D2. The average particle size of the metal particles in the obtained conductive composition D2 was 20 nm, and the zeta potential of the metal particles was -38 mV. Details of conductive composition D2 are shown in Table 15.

[0115] (Conductive composition D3) Conductive composition D3 was prepared by the method shown below (comparative example). Conductive composition D3 with the following composition was obtained according to the preparation method of "dispersion paste 4" described in "Example 4" of Patent Document 4. The zeta potential of the metal particles in the obtained conductive composition D3 was 28 mV. Details of conductive composition D3 are shown in Table 15. ·Copper fine particles: 20 parts • Copolymerized polyester: 0.875 parts n-butylcarbitol acetate: 1.625 parts · 4-(diethylamino)benzaldehyde-1,1-diphenylhydrazone: 1 part • Ethyl carbitol acetate: 4 parts

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[0124] <Manufacturing of conductive compositions (inks)> Using the conductive compositions (dispersions) prepared above, aqueous inks (conductive compositions) containing an aqueous medium and a surfactant were manufactured by the method described below. The average particle size of the metal particles in the obtained inks was within ±1 nm of the average particle size of the metal particles in the conductive compositions (dispersions) used as raw materials. This indicates that the metal particles are stably dispersed in the conductive compositions (dispersions) and the ink.

[0125] Each conductive composition (dispersion) was centrifuged using a centrifuge (product name "CR22N," manufactured by Eppendorf Hi-Mac Technologies) at 8,000 rpm for 30 minutes, and the supernatant was removed to obtain a concentrate. Each ink was obtained by mixing 10.0 parts of this concentrate (the amount at which the metal particle content in the ink is 10.0%) with the following components. As the surfactant, an acetylene glycol-based surfactant (product name "Orfin PD-005," manufactured by Nisshin Chemical Industry Co., Ltd.) was used. In Tables 16-23, water-soluble organic solvents are represented as follows: EG: ethylene glycol, BDO: 1,3-butanediol. • Concentrates of conductive compositions (types shown on the left side of Tables 16-23): 10.0 parts • Water-soluble organic solvents (types shown on the left side of Tables 16-23): 20.0 parts • Surfactant: 0.1 part ·Ultra pure water: 69.9 parts

[0126] <Manufacturing of conductive images> Ink (conductive composition) was filled into an ink cartridge and set in an inkjet recording device equipped with a recording head of the ejection type shown in the center of Tables 16-23. In this embodiment, the recording duty cycle of a solid image recorded by applying 8 ink droplets of 2.5 pL each to a unit area of ​​1 / 600 inch x 1 / 600 inch is defined as "100%". Using this inkjet recording device, a 2 mm x 3 cm solid image with a recording duty cycle of 100% was recorded on the substrate shown in the center of Tables 16-23 under conditions of 25°C and 50% relative humidity to obtain a recorded material. The obtained recorded material was dried under the drying temperature and drying time conditions shown in the center of Tables 16-23 to obtain each conductive image.

[0127] The ejection methods described in Tables 16-23, and the details of the inkjet recording devices used for ejection in these methods, are shown below. • Thermal: An inkjet recording device that ejects ink from the recording head using the action of thermal energy (product name "PIXUS iP7230", manufactured by Canon). • Piezo: An inkjet recording device that ejects ink from the recording head using the action of mechanical energy (product name "LaboJet-500", manufactured by MicroJet).

[0128] Details of the substrates listed in Tables 16-23 are shown below. • PET: Product name "Panacrea ACX", manufactured by Panac. • Glossy paper: Product name "Glossy Paper Standard SD-201", manufactured by Canon. • Glass: Product name "Cover Glass NEO", manufactured by Matsunami Glass Industry Co., Ltd. • Gelatin sheet: A 0.1% gelatin solution manufactured by Fujifilm Wako Pure Chemical Industries is applied to the above PET using a bar coater and dried. • Fibroin sheet: A 5% aqueous fibroin solution manufactured by MilliporeSigma is applied to the above PET using a bar coater and then dried.

[0129] <Evaluation of conductivity> The film thickness of conductive images obtained using a stylus-type film thickness gauge (manufactured by Tencor) was measured. The cross-sectional area of ​​the conductive image was calculated from the measured film thickness, and the volume resistivity was measured and calculated using the four-point stylus method. The measured and calculated volume resistivity is shown on the right side of Tables 16-23. In addition, the conductivity of the conductive images was evaluated according to the evaluation criteria shown below. In the evaluation criteria shown below, "A" was defined as an acceptable range and "B" as an unacceptable range. The results are shown on the right side of Tables 16-23. A: Volume resistivity is 1 × 10⁻⁶ -4 It was less than Ω·cm. B: Volume resistivity is 1 × 10⁻⁶ -4 The conductivity was either above Ω·cm or did not show any conductivity.

[0130] TIFF2023010589000035.tif238170

[0131] TIFF2023010589000036.tif246170

[0132] TIFF2023010589000037.tif211170

[0133] TIFF2023010589000038.tif217170

[0134] TIFF2023010589000039.tif233170

[0135] TIFF2023010589000040.tif223170

[0136] TIFF2023010589000041.tif154170

[0137] TIFF2023010589000042.tif62170

[0138] This embodiment includes the following configurations and methods. (Composition 1) A conductive composition containing metal particles and a treatment agent for coating the metal particles, A conductive composition characterized in that the treatment agent is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following general formula (5), a compound represented by the following general formula (6), and a compound represented by the following general formula (7).

[0139] TIFF2023010589000043.tif28170 (In the above general formula (1), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is the hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0140] TIFF2023010589000044.tif28170 (In the above general formula (2), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is the hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0141] TIFF2023010589000045.tif22170 (In the above general formula (3), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0142] TIFF2023010589000046.tif23170 (In the above general formula (4), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0143] TIFF2023010589000047.tif16170 (In the above general formula (5), R1 represents a hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0144] TIFF2023010589000048.tif37170 (In the above general formula (6), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond.)

[0145] TIFF2023010589000049.tif43170(In the general formula (7), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group that may contain a heteroatom, an amide bond, or an ester bond to which the hydrophilic functional group is bonded.)

[0146] (Configuration 2) The conductive composition according to Configuration 1, wherein the hydrophilic group in the general formula (1), the hydrophilic group in the general formula (2), the hydrophilic group in the general formula (3), the hydrophilic group in the general formula (4), and the hydrophilic group in the general formula (5) are each independently (ii) a phenyl group to which the hydrophilic functional group is bonded; or (iii) a phenyl group to which the hydrophilic functional group is bonded via an aliphatic group that may contain a heteroatom, an amide bond, or an ester bond.) (Configuration 3) The conductive composition according to Configuration 2, wherein the hydrophilic group is a phenyl group to which at least one of a carboxylic acid group and a sulfonic acid group is bonded.) (Configuration 4) The conductive composition according to Configuration 3, wherein the total number of carboxylic acid groups and sulfonic acid groups bonded to the phenyl group is 2 or 3.) (Configuration 5) The conductive composition according to Configuration 1, wherein the hydrophilic group in the general formula (1) and the hydrophilic group in the general formula (2) are each independently any heteroaromatic group selected from the group consisting of a pyridazinyl group, a pyrazyl group, a pyrimidyl group, and a triazyl group.) (Configuration 6) The conductive composition according to Configuration 1, wherein the hydrophilic group in the general formula (6) and the hydrophilic group in the general formula (7) are each independently a group represented by the following general formula (8).)

[0147] TIFF2023010589000050.tif26170(In the general formula (8), R x and R yEach of these independently represents an alkyl group, and R z (This represents an alkylene group.)

[0148] (Configuration 7) The conductive composition according to any one of Configurations 1 to 6, wherein the metal particles are formed of at least one metal selected from the group consisting of silver and gold. (Configuration 8) The conductive composition according to any one of Configurations 1 to 7, wherein the cumulative 50% particle diameter of the metal particles on a volume basis is 5 nm or more and 100 nm or less. (Composition 9) A conductive composition according to any one of Compositions 1 to 8, further comprising an aqueous medium.

[0149] (Method 1) A method for producing a conductive composition according to any one of items 1 to 9, A first step involves reducing a metal salt in an aqueous medium to form the metal particles, A method for producing a conductive composition, comprising a second step of bringing the formed metal particles into contact with the treatment agent. (Method 2) A method for producing a conductive composition according to Method 1, wherein the metal salt is a recovered metal salt recovered from metal waste liquid.

[0150] (Method 3) A method for recording a conductive image, characterized by comprising the step of applying the conductive composition described in any one of the items 1 to 9 to a substrate. (Method 4) A method for recording a conductive image according to Method 3, wherein the conductive composition is applied to the substrate by an inkjet method. (Method 5) A method for recording a conductive image according to Method 3 or 4, further comprising the step of drying the conductive composition applied to the substrate at a temperature of 20°C to 50°C.

[0151] (Configuration 10) A conductive image having a substrate and a conductive layer formed on the substrate, The conductive layer contains metal particles and a treatment agent for coating the metal particles. A conductive image characterized in that the processing agent is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following general formula (5), a compound represented by the following general formula (6), and a compound represented by the following general formula (7).

[0152] TIFF2023010589000051.tif28170 (In the above general formula (1), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is the hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0153] TIFF2023010589000052.tif28170 (In the above general formula (2), R1 to R4 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R4 is the hydrophilic group, and the remaining ones cannot all be hydrogen atoms at the same time. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0154] TIFF2023010589000053.tif22170 (In the above general formula (3), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0155] TIFF2023010589000054.tif23170 (In the above general formula (4), R1 and R2 each independently represent an aromatic group or a hydrophilic group, and at least one of R1 and R2 is the hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0156] TIFF2023010589000055.tif16170 (In the above general formula (5), R1 represents a hydrophilic group. The hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.)

[0157] TIFF2023010589000056.tif37170 (In the above general formula (6), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond.)

[0158] TIFF2023010589000057.tif43170 (In the above general formula (7), R1 to R8 each independently represent a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group, and at least one of R1 to R8 is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond.)

[0159] (Configuration 11) A conductive image recorded on a substrate, A conductive image characterized by being formed from a conductive composition according to any one of the items 1 to 9. (Configuration 12) A conductive image according to Configuration 11, wherein the substrate is glass, paper, or a resin material. (Configuration 13) A conductive image according to Configuration 12, wherein the resin material is a biocompatible material. (Configuration 14) The conductive image according to Configuration 13, wherein the biocompatible material is at least one selected from the group consisting of gelatin, cellulose, chitosan, collagen, and fibroin.

Claims

1. A conductive composition containing metal particles and a treatment agent for coating the metal particles, The conductive composition, wherein the treating agent is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following general formula (5), a compound represented by the following general formula (6), and a compound represented by the following general formula (7). (In the general formula (1), R １ ~R ４ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ４ At least one of the above is the hydrophilic group, and the remaining groups are not all hydrogen atoms at the same time. The hydrophilic groups are (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (2), R １ ~R ４ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ４ At least one of the above is the hydrophilic group, and the remaining groups are not all hydrogen atoms at the same time. The hydrophilic groups are (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (3), R １ and R ２ each independently represents an aromatic group or a hydrophilic group, R １ and R ２ The hydrophilic group is at least one of (i) a heteroaromatic group, (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded, or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (4), R １ and R ２ each independently represents an aromatic group or a hydrophilic group, R １ and R ２ The hydrophilic group is at least one of (i) a heteroaromatic group, (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded, or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (5), R １ represents a hydrophilic group, and the hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (6), R １ ~R ８ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ８ At least one of the above is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (7), R １ ~R ８ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ８ At least one of the above is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond.

2. 2. The conductive composition according to claim 1, wherein the hydrophilic group in the general formula (1), the hydrophilic group in the general formula (2), the hydrophilic group in the general formula (3), the hydrophilic group in the general formula (4), and the hydrophilic group in the general formula (5) are each independently (ii) a phenyl group to which the hydrophilic functional group is bonded; or (iii) a phenyl group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond.

3. 3. The conductive composition according to claim 2, wherein the hydrophilic group is a phenyl group to which at least one of a carboxylic acid group and a sulfonic acid group is bonded.

4. 4. The conductive composition according to claim 3, wherein the total number of carboxylic acid groups and sulfonic acid groups bonded to the phenyl group is 2 or 3.

5. 2. The conductive composition according to claim 1, wherein the hydrophilic group in the general formula (1) and the hydrophilic group in the general formula (2) are each independently (i) any heteroaromatic group selected from the group consisting of a pyridazyl group, a pyrazyl group, a pyrimidyl group, and a triazyl group.

6. The conductive composition according to claim 1, wherein the hydrophilic group in the general formula (6) and the hydrophilic group in the general formula (7) are each independently a group represented by the following general formula (8): (In the general formula (8), R ｘ and R ｙ each independently represents an alkyl group, R ｚ represents an alkylene group)

7. 7. The conductive composition according to claim 1, wherein the metal particles are formed of at least one metal selected from the group consisting of silver and gold.

8. 7. The conductive composition according to claim 1, wherein the metal particles have a volume-based cumulative 50% particle diameter of 5 nm or more and 100 nm or less.

9. The conductive composition according to claim 1 , further comprising an aqueous medium.

10. A method for producing the conductive composition according to any one of claims 1 to 6, comprising: a first step of reducing a metal salt in an aqueous medium to form the metal particles; a second step of contacting the formed metal particles with the treating agent.

11. The method for producing a conductive composition according to claim 10, wherein the metal salt is a recovered metal salt recovered from a metal waste liquid.

12. A method for recording a conductive image, comprising the step of applying the conductive composition according to claim 1 to a substrate.

13. The method for recording a conductive image according to claim 12, wherein the conductive composition is applied to the substrate by an ink jet method.

14. The method for recording a conductive image according to claim 12, further comprising a step of drying the conductive composition applied to the substrate at a temperature of 20°C or higher and 50°C or lower.

15. A conductive image having a substrate and a conductive layer formed on the substrate, the conductive layer contains metal particles and a treatment agent for coating the metal particles, A conductive image, characterized in that the treating agent is at least one selected from the group consisting of a compound represented by the following general formula (1), a compound represented by the following general formula (2), a compound represented by the following general formula (3), a compound represented by the following general formula (4), a compound represented by the following general formula (5), a compound represented by the following general formula (6), and a compound represented by the following general formula (7). (In the general formula (1), R １ ~R ４ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ４ At least one of the above is the hydrophilic group, and the remaining groups are not all hydrogen atoms at the same time. The hydrophilic groups are (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (2), R １ ~R ４ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ４ At least one of the above is the hydrophilic group, and the remaining groups are not all hydrogen atoms at the same time. The hydrophilic groups are (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (3), R １ and R ２ each independently represents an aromatic group or a hydrophilic group, R １ and R ２ The hydrophilic group is at least one of (i) a heteroaromatic group, (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded, or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (4), R １ and R ２ each independently represents an aromatic group or a hydrophilic group, R １ and R ２ The hydrophilic group is at least one of (i) a heteroaromatic group, (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded, or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (5), R １ represents a hydrophilic group, and the hydrophilic group is (i) a heteroaromatic group; (ii) an aromatic group to which at least one hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group is bonded; or (iii) an aromatic group to which the hydrophilic functional group is bonded via an aliphatic group which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (6), R １ ~R ８ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ８ At least one of the above is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond. (In the general formula (7), R １ ~R ８ each independently represents a hydrogen atom, an aliphatic group, an aromatic group, an acid ester group, or a hydrophilic group; R １ ~R ８ At least one of the above is the hydrophilic group. The hydrophilic group is (i) any hydrophilic functional group selected from the group consisting of a hydroxy group, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phosphonic acid group, a tertiary alkylamino group, and a heteroaromatic group; or (ii) an aliphatic group to which the hydrophilic functional group is bonded, which may contain a heteroatom, an amide bond, or an ester bond.

16. A conductive image recorded on a substrate, comprising: A conductive image formed from the conductive composition according to any one of claims 1 to 6.

17. The conductive image according to claim 16, wherein the substrate is glass, paper, or a resin material.

18. 18. The conductive image according to claim 17, wherein the resin material is a biocompatible material.

19. 19. The conductive image according to claim 18, wherein the biocompatible material is at least one selected from the group consisting of gelatin, cellulose, chitosan, collagen, and fibroin.

Images