JP7017451B2 - Conductive laminate - Google Patents

Description

The present invention relates to a conductive laminate.

The conductive laminate provided with the base sheet and the conductive layer provided on the base sheet can be used as a circuit board by, for example, patterning the conductive layer, and has high utility value.

A resin sheet is generally used as the base material sheet, but in recent years, a conductive laminate using a paper sheet has been studied. The conductive laminate using a paper sheet has high flexibility, is easy to dispose of, and has a small environmental load. Not only that, but further, for the formation of the circuit (patterned conductive layer), a highly versatile method of coating or printing an ink composition capable of forming the conductive layer can be adopted, and it can be manufactured at low cost. It has various advantages. As the ink composition, one containing a metal compound such as a metal complex, which can form a metal by performing post-treatment such as drying, can be used.

However, since the paper sheet has high liquid permeability, when the ink composition is liquid, especially when it is a solution, when the ink composition is applied or printed, the metal compound in the ink composition is released. It penetrates into the inside of the paper sheet. As a result, the amount of the metal compound remaining on the surface of the paper sheet is reduced, and there is a problem that a sufficient amount of metal (conductive layer) cannot be formed on the paper sheet.

On the other hand, JAPAN TAPPI pulp and paper test method No. By using a paper sheet whose air permeability is adjusted to 40,000 seconds or more based on the Oken method based on 5-2: 2000, the penetration of the ink composition, which is a solution, into the inside of the paper sheet is suppressed, and the ink composition is suppressed on the paper sheet. A method for forming a sufficient amount of metal is disclosed (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2012-129343

However, the present inventor tried to form metallic silver on a paper sheet by the method disclosed in Patent Document 1, but could not form metallic silver to the extent that it has conductivity. Some have found that a sufficient amount of metal cannot be formed on a paper sheet.

The present invention has been made in view of the above circumstances, and is a novel conductive laminate comprising a paper sheet and a conductive layer provided on the paper sheet, wherein the conductive layer has sufficient conductivity. The challenge is to provide the body.

In order to solve the above problems, the present invention comprises a paper sheet, a receiving layer provided on the paper sheet, and a conductive layer provided on the receiving layer.
Provided is a conductive laminate in which the receiving layer contains polyurethane.
In the conductive laminate of the present invention, it is preferable that the polyurethane has an anionic group.
In the conductive laminate of the present invention, the amount of the polyurethane on the paper sheet is preferably 6 g / m ² or more.
In the conductive laminate of the present invention, it is preferable that the conductive layer is formed by using a silver ink composition containing an organic silver compound.

According to the present invention, there is provided a novel conductive laminate comprising a paper sheet and a conductive layer provided on the paper sheet, wherein the conductive layer has sufficient conductivity.

It is sectional drawing which shows typically the conductive laminated body which concerns on one Embodiment of this invention. It is sectional drawing for schematically explaining the manufacturing method of the conductive laminated body which concerns on one Embodiment of this invention.

<< Conductive laminate >>
The conductive laminate according to the embodiment of the present invention includes a paper sheet, a receiving layer provided on the paper sheet, and a conductive layer provided on the receiving layer, and the receiving layer is polyurethane. including.

Since the paper sheet has high liquid permeability, when the ink composition is liquid, when the ink composition is applied or printed, the ink composition penetrates into the inside of the paper sheet. When a material for forming a conductive layer (conductive layer forming material) such as a metal compound is contained in the ink composition, the conductive layer forming material also penetrates into the inside of the paper sheet. And when the ink composition is a solution, this tendency becomes even stronger. Then, the amount of the conductive layer forming material remaining on the surface of the paper sheet becomes small, and a sufficient amount of the conductive layer (metal layer) cannot be formed on the paper sheet.

On the other hand, in the conductive laminate of the present embodiment, the conductive layer is provided on the paper sheet via the receiving layer containing polyurethane, so that the paper sheet is used, but the paper sheet is used. The conductive layer has sufficient conductivity. This is because a specific range of resin called polyurethane solves the above-mentioned penetration problem.
Hereinafter, first, the overall configuration of the conductive laminate of the present embodiment will be described.

FIG. 1 is a cross-sectional view schematically showing a conductive laminate according to an embodiment of the present invention.
The conductive laminate 1 shown here includes a paper sheet 11, a receiving layer 12 provided on the paper sheet 11, and a conductive layer 13 provided on the receiving layer 12. In other words, the conductive laminated body 1 is composed of a paper sheet 11, a receiving layer 12, and a conductive layer 13 laminated in this order in the thickness direction thereof.
In the conductive laminate 1, the receiving layer 12 is laminated on one surface (sometimes referred to as “first surface” in the present specification) 11a of the paper sheet 11, and the paper sheet 11 of the receiving layer 12 is laminated. The conductive layer 13 is laminated on a surface (sometimes referred to as a "first surface" in the present specification) 12a opposite to the side.
The receiving layer 12 contains polyurethane.

The shape (planar shape) of the receiving layer 12 when the receiving layer 12 is viewed in a plan view from above the conductive layer 13, that is, from the conductive layer 13 side, is arbitrarily set according to the similar shape (planar shape) of the conductive layer 13. can. For example, the receiving layer 12 may cover the entire surface of the first surface 11a of the paper sheet 11, or may cover only a part of the first surface 11a, or only a part of the area. The receiving layer 12 may or may not be patterned.

The shape (planar shape) of the conductive layer 13 when the conductive layer 13 is viewed in a plan view from above, that is, from the side opposite to the receiving layer 12 side can be arbitrarily set according to the use of the conductive layer 13. .. For example, the conductive layer 13 may cover the entire surface of the first surface 12a of the receiving layer 12, or may cover only a part of the first surface 12a, or only a part of the area. The conductive layer 13 may or may not be patterned.
For example, the patterned conductive layer 13 is useful as a circuit. Further, when the area of the surface (sometimes referred to as “first surface” in the present specification) 13a of the conductive layer 13 opposite to the receiving layer 12 side is relatively large, the first surface is described. 13a is useful as a mirror surface.

The conductive laminate of the present embodiment is not limited to the one shown in FIG. 1, and a part of the configuration is changed, deleted or added in the one shown in FIG. 1 within the range not impairing the effect of the present invention. It may be a thing.

For example, the conductive laminate 1 shown in FIG. 1 includes a receiving layer 12 and a conductive layer 13 on its first surface 11a, but the conductive laminate 1 of the present embodiment has other layers. May be provided. The other layers are not particularly limited, and the type, thickness, arrangement position, and the like can be arbitrarily selected according to the purpose.

For example, the conductive laminate 1 may be provided with a coating layer that covers the conductive layer 13 on the first surface 13a of the conductive layer 13. Examples of the coating layer include, but are not limited to, a laminated structure of a paper sheet 11, a receiving layer 12, and a conductive layer 13, particularly a protective layer for protecting the conductive layer 13.

Further, the conductive laminate 1 may be provided with an intermediate layer as the other layer between the paper sheet 11 and the receiving layer 12, or between the receiving layer 12 and the conductive layer 13.
Examples of the intermediate layer include, but are not limited to, an adhesive layer for adhering two adjacent layers and an adhesive layer for adhering two adjacent layers.

Further, the conductive laminate 1 has some surface on the other surface (the surface opposite to the receiving layer 12 side, which may be referred to as a "second surface" in the present specification) 11b of the paper sheet 11. It may have a layer. Examples of the layer on the second surface 11b include those similar to any layer on the first surface 11a.
For example, when the conductive laminate 1 includes one or both of the receiving layer and the conductive layer on the second surface 11b, the receiving layer and the conductive layer are on the first surface 11a. It may have the same form as the receiving layer 12 and the conductive layer 13, and may be the same as or different from the receiving layer 12 and the conductive layer 13 on the first surface 11a.

Further, the conductive laminate 1 shown in FIG. 1 may further have another base material on the second surface 11b of the base material 11 in addition to the base material 11. The other base material may have the same form as the base material 11, and may be the same as or different from the base material 11.

However, the conductive laminate of the present embodiment is preferably provided with the receiving layer in direct contact with the paper sheet as in the conductive laminate 1 shown in FIG. 1, and the conductive layer is directly attached to the receiving layer. Those provided in contact with each other are preferable.
Next, each configuration of the conductive laminated body of this embodiment will be described.

<Paper sheet>
The paper sheet is not particularly limited as long as it is made of paper and has a sheet shape, and may be a known one classified as paper.
Examples of the paper sheet include Kent paper, coated paper, paperboard, high-quality paper, art paper, cast-coated paper, resin-coated paper, synthetic paper and the like.

The paper sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the paper sheet is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.
In the present specification, not only in the case of a paper sheet, "a plurality of layers may be the same or different from each other" means "all layers may be the same or all layers are different". It may be, and only some of the layers may be the same. ”Furthermore,“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and the thickness of each layer is different from each other ”. Means.

The thickness of the paper sheet may be appropriately selected according to the purpose and is not particularly limited.
The thickness of the paper sheet is preferably 10 to 5000 μm, more preferably 50 to 3000 μm, still more preferably 100 to 1000 μm, and for example, 100 to 500 μm or 100 to 300 μm. There may be. When the thickness of the paper sheet is at least the lower limit value, the structures of the receiving layer and the conductive layer can be maintained more stably. When the thickness of the paper sheet is not more than the upper limit value, the handleability of the target conductive laminate is improved.
When the paper sheet is composed of a plurality of layers, the total thickness of each layer may be set to be the above-mentioned preferable thickness of the paper sheet.

JAPAN TAPPI Paper and pulp test method No. The Oken-type air permeability of the paper sheet measured in accordance with 5-2: 2000 (in this specification, it may be abbreviated as "Oken-type air permeability") is not particularly limited, but is not limited. It is preferably 5000 seconds or longer, and may be, for example, 10000 seconds or longer, 30000 seconds or longer, or 100,000 seconds or longer. When a paper sheet having the Oken-type air permeability of the lower limit value or more is used, the conductivity of the conductive layer becomes higher.
On the other hand, the upper limit of the Oken-type air permeability is not particularly limited.

<Receptive layer>
The receiving layer contains polyurethane, and it is preferable that the receiving layer contains polyurethane as a main constituent material.
For example, the receiving layer may be one containing only polyurethane (consisting of polyurethane), or other than polyurethane, a component that does not correspond to any of polyurethane and a solvent (in the present specification, "other components". It may contain (sometimes referred to as “component (1)”).
Polyurethane is a resin that has a particularly high affinity with a component for forming a conductive layer (conductive layer forming component) among many resins, and has a particularly high effect of suppressing the penetration of this component into the inside of a paper sheet. It is presumed.

The polyurethane is not particularly limited as long as it is an oligomer or polymer having a urethane bond (bond represented by the formula "-NH-C (= O) -O-").
The polyurethanes are, for example, a polyurethane having an anionic group (sometimes referred to as "anionic polyurethane" in the present specification) and a polyurethane having a cationic group (in the present specification, "cationic polyurethane"". (May be referred to as) and polyurethane that does not fall under either anionic polyurethane or cationic polyurethane (in this specification, it may be referred to as “nonionic polyurethane”). , Anionic polyurethane is preferred.

When the polyurethane has a functional group (hydrophilic group) such as the anionic group or the cationic group, the functional group may or may not form a salt in the receiving layer. good.

The polyurethane contained in the receiving layer may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be adjusted arbitrarily.

The other component (1) can be arbitrarily selected depending on the intended purpose, and is not particularly limited.
Examples of the other component (1) include known additives and the like.
Examples of the additive include those similar to the nitrogen-containing compound in the silver ink composition described later.

The other component (1) contained in the receiving layer may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily adjusted.

The polyurethane content of the receiving layer is preferably 50% by mass or more, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, 97% by mass or more, and 99% by mass. It may be any of the above. When the content of the polyurethane is at least the lower limit value, the conductivity of the conductive layer becomes higher.
On the other hand, the content of polyurethane in the receiving layer is 100% by mass or less.

The polyurethane content of the receiving layer can be appropriately adjusted within a range set by any combination of the lower limit value and the upper limit value of any of the above. In one embodiment, the polyurethane content of the receiving layer is preferably 50-100% by mass, for example 60-100% by mass, 70-100% by mass, 80-100% by mass, 90-100% by mass. It may be any of 97 to 100% by mass and 99 to 100% by mass. However, these are examples of the polyurethane content.

The amount of the polyurethane on the paper sheet (the amount of the polyurethane in the receiving layer present on the unit area (1 m ² ) of the paper sheet) is not particularly limited as long as the effect of the present invention is not impaired. It is preferably 6 g / m ² or more, more preferably 6.5 g / m ² or more, and is, for example, 10 g / m ² or more, 15 g / m ² or more, and 20 g / m ² or more. You may. When the amount of the polyurethane on the paper sheet is at least the lower limit value, the conductivity of the conductive layer becomes higher.

The upper limit of the amount of the polyurethane on the paper sheet is not particularly limited.
For example, the amount of the polyurethane on the paper sheet is preferably 35 g / m ² or less in that the flexibility of the conductive laminate is further improved and the conductive laminate can be manufactured at a lower cost.

The amount of the polyurethane on the paper sheet can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. In one embodiment, the amount of the polyurethane on the paper sheet is preferably 6-35 g / m ² , more preferably 6.5-35 g / m ² , for example 10-35 g / m ² , 15-35 g. It may be either / m ² and 20 to 35 g / m ² .

The receiving layer may be composed of one layer (single layer) or may be composed of two or more layers. When the receiving layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

In the receiving layer, the polyurethane-containing composition for forming a receiving layer is adhered to the surface to be formed of the receiving layer to form a composition layer, and the composition layer (composition layer for forming a receiving layer) is formed. , Can be formed by performing a drying treatment.

◎ Composition for forming a receiving layer The composition for forming a receiving layer includes, for example, the polyurethane, a solvent, and, if necessary, the other component (1) (a component that does not correspond to any of polyurethane and a solvent). Can be mentioned. The other component (1) is as described above.

The solvent contained in the composition for forming a receiving layer is not particularly limited as long as it does not impair the effects of the present invention.
Examples of the solvent include water, organic solvents and the like.

Examples of the organic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone; nitriles such as acetonitrile; N, N-dimethylformamide. Amides such as (DMF), N, N-dimethylacetamide (chain amides); lactams (cyclic amides) such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone; ethyl acetate, n-butyl acetate and the like. Esters; ethers such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane (dimethylserosolve); halogenated hydrocarbons such as dichloromethane and chloroform.

The solvent contained in the composition for forming a receptive layer may be only one kind, two or more kinds, and when two or more kinds, the combination and the ratio thereof can be arbitrarily adjusted. .. For example, the two or more kinds of solvents may be a mixed solvent of water and one kind or two or more kinds of organic solvents (aqueous mixed solvent), or a mixed solvent of only two or more kinds of organic solvents (non-mixed solvent). It may be an aqueous mixed solvent).

In the composition for forming a receiving layer, the ratio of the contents of the components that do not vaporize at room temperature is usually the same as the ratio of the contents of the components of the receiving layer.
For example, in the composition for forming a receiving layer, the ratio of the content of the polyurethane to the total content of the components other than the solvent ([content of the polyurethane in the composition for forming the receiving layer (% by mass)] / [receptive layer]. The total content (% by mass) of the components other than the solvent in the forming composition is preferably 50% by mass or more, and for example, 60% by mass or more, 70% by mass or more, and 80% by mass or more. , 90% by mass or more, 97% by mass or more, and 99% by mass or more.
In addition, in this specification, "normal temperature" means a temperature which is not particularly cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 to 25 ° C.

The content of the solvent in the composition for forming the receiving layer is not particularly limited, and can be appropriately adjusted, for example, so that the handling of the composition is good.
For example, the solvent content of the composition for forming a receptive layer may be preferably 30 to 85% by mass, which is an example.

-Method for producing a composition for forming a receptive layer The composition for forming a receptive layer can be obtained by blending the polyurethane, a solvent, and, if necessary, the other component (1).
The blending order of each component is not particularly limited.
After blending each component, the obtained composition may be used as it is as a composition for forming a receiving layer, or, if necessary, a composition obtained by continuously performing a known purification operation may be used as a composition for forming a receiving layer. ..

When blending each component, all the components may be added and then mixed, some components may be added sequentially and mixed, or all the components may be sequentially added and mixed. good.
The mixing method is not particularly limited, and a method of rotating and mixing a stirrer, a stirring blade, or the like; a method of mixing using a mixer, a three-roll, a kneader, a bead mill, or the like; a method of adding ultrasonic waves and the like, etc. It may be appropriately selected from known methods.

The temperature at the time of compounding is not particularly limited as long as each compounding component is not deteriorated, but is preferably 5 to 60 ° C.
The blending time is also not particularly limited as long as each blending component is not deteriorated, but is preferably 10 minutes to 2 hours.

◎ Method of using the composition for forming a receiving layer The composition for forming a receiving layer can be attached to a target product by a known method such as a printing method or a coating method.

Examples of the printing method include a screen printing method, a flexo printing method, an offset printing method, a dip printing method, an inkjet printing method, a dispenser printing method, a jet dispenser printing method, a gravure printing method, and a gravure offset printing method. The pad printing method and the like can be mentioned.

As the coating method, for example, a method using various coaters such as a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, and a gravure coater; Method to be used; Examples thereof include a method using a coating device such as a slot die.

The drying treatment of the composition for forming the receiving layer (composition layer for forming the receiving layer) may be carried out by a known method. For example, the drying treatment may be performed under normal pressure, reduced pressure, or blowing conditions, and may be performed under the atmosphere of the atmosphere or the atmosphere of the inert gas.
The temperature at the time of the drying treatment is not particularly limited, and may be either a heat drying treatment or a room temperature drying treatment. In the case of heat-drying treatment, the heating temperature is preferably 60 to 230 ° C, more preferably 80 to 220 ° C, and particularly preferably 100 to 210 ° C. The heating time is preferably 1 to 120 minutes, more preferably 2 to 60 minutes, and particularly preferably 5 to 30 minutes.

At the time of forming the receiving layer, for example, the polyurethane on a paper sheet can be adjusted by adjusting the amount of the composition for the receiving layer to be attached to the target portion or the blending amount of the polyurethane or the like in the composition for the receiving layer. The amount of water and the thickness of the receiving layer can be adjusted.

<Conductive layer>
The conductive layer is a liquid composition (in the present specification, may be referred to as a "composition for forming a conductive layer") in which a component for forming the conductive layer (conducting layer forming component) is blended. The one formed by using is preferable.
In the conductive layer, the composition for forming the conductive layer is adhered to the surface to be formed of the conductive layer to form a composition layer, and the composition layer (composition layer for forming the conductive layer) is subjected to a drying treatment or a drying treatment. It can be formed by appropriately selecting and performing a solidification treatment such as a heating (firing) treatment.

The conductive layer is preferably a metal layer.

The amount of the conductive layer formed on the receiving layer (the amount of the conductive layer existing on the unit area (1 m ² ) of the receiving layer) can be arbitrarily selected depending on the intended purpose, and is not particularly limited, but is 4 g / m. ² or more is preferable, 5 g / m ² or more is more preferable, 6 g / m ² or more is further preferable, and for example, 10 g / m ² or more, 20 g / m ² or more, 30 g / m ² or more. As mentioned above, it may be either 40 g / m ² or more and 50 g / m ² or more. When the amount of the conductive layer formed is equal to or greater than the lower limit, the conductivity of the conductive layer becomes higher.
Here, "the amount of the conductive layer formed on the receiving layer" is synonymous with the amount of the conductive layer formed on the paper sheet (the amount of the conductive layer existing on the unit area (1 m ² ) of the paper sheet). Is.

The upper limit of the amount of the conductive layer formed on the receiving layer is not particularly limited.
For example, the amount of the conductive layer formed is preferably 70 g / m ² or less in that the flexibility of the conductive laminate is further improved and the conductive laminate can be manufactured at a lower cost.

The amount of the conductive layer formed on the receiving layer can be appropriately adjusted within a range set by arbitrarily combining any of the above-mentioned lower limit values and upper limit values. In one embodiment, the amount of the conductive layer formed is preferably 4 to 70 g / m ² , more preferably 5 to 70 g / m ² , still more preferably 6 to 70 g / m ² , and for example, 10 to 70 g / m 2. It may be any of m ² , 20 to 70 g / m ² , 30 to 70 g / m ² , 40 to 70 g / m ² , and 50 to 70 g / m ² .

The conductive layer may be composed of one layer (single layer) or may be composed of two or more layers. When the conductive layer is composed of a plurality of layers, the plurality of layers may be the same or different from each other, and the combination of the plurality of layers is not particularly limited.

The thickness of the conductive layer may be appropriately selected depending on the intended purpose, and is not particularly limited.
The thickness of the conductive layer is preferably 0.01 to 20 μm. When the thickness of the conductive layer is at least the above lower limit value, the conductivity of the conductive layer becomes higher. When the thickness of the conductive layer is not more than the upper limit, the flexibility of the conductive laminate is further improved, and the conductive laminate can be manufactured at a lower cost.
When the conductive layer is composed of a plurality of layers, the total thickness of each layer may be set to be the above-mentioned preferable thickness of the conductive layer.

The surface resistance value (sheet resistance value) of the conductive layer is, for example, preferably 25 Ω / □ or less, more preferably 20 Ω / □ or less, and for example, 10 Ω / □ or less, or 6 Ω / □ or less. May be good.
In the present specification, the “surface resistance value” means a measured value by the four-ended needle method, as will be described later in Examples, unless otherwise specified.

The lower limit of the surface resistance value of the conductive layer is not particularly limited, and may be, for example, 0Ω / □.
In terms of facilitating the formation of the conductive layer, it is preferably 0.05 Ω / □ or more, and may be, for example, 1 Ω / □ or more, 3 Ω / □ or more, and 5 Ω / □ or more.

The surface resistance value of the conductive layer can be appropriately adjusted within a range set by arbitrarily combining any of the above lower limit values and any upper limit value. In one embodiment, the surface resistance value of the conductive layer is preferably 0.05 to 25Ω / □, more preferably 0.05 to 20Ω / □, for example, 0.05 to 10Ω / □, and 0.05. It may be any of ~ 6Ω / □.

As will be described later, the conductive layer has a higher glossiness depending on the type of the composition for forming the conductive layer.
For example, a silver layer formed by using a silver ink composition containing a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms, as described later, has a light reflectance, for example, a wavelength of 400 to 400. Excellent reflectance of 700 nm light.
For example, in such a case, the reflectance of the metallic silver (silver layer) at a wavelength of 550 nm is preferably 50% or more, for example, 55% or more, 60% or more, 65% or more, 70% or more, and 75. It may be any of% or more. However, these are examples of the reflectance of metallic silver light having a wavelength of 550 nm.
Further, the upper limit of the reflectance of light having a wavelength of 550 nm of the above-mentioned metallic silver (silver layer) is not particularly limited and may be, for example, 90%, which is an example of the upper limit.

The reflectance of light having a wavelength of 550 nm of the metallic silver (silver layer) formed by using the silver ink composition is set by arbitrarily combining any of the above lower limit values and any of the upper limit values. It can be adjusted as appropriate within the range. For example, the reflectance of the light is preferably 50 to 90%, for example, 55 to 90%, 60 to 90%, 65 to 90%, 70 to 90%, and 75 to 90%. You may. However, these are examples of the reflectance of the light.

◎ Composition for forming a conductive layer The composition for forming a conductive layer is preferably a metal ink composition for forming the metal layer.
Examples of the metal ink composition include a composition in which one or both of a metal and a metal forming material are blended.
The metal to be blended and the metal-forming material may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof are intended for the purpose. It can be adjusted arbitrarily according to the situation.

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

The material for forming the metal to be blended may be any material as long as it has a corresponding metal atom (element) and produces a metal by a structural change such as decomposition. Examples of the material for forming such a metal include metal salts, metal complexes, compounds having a metal-carbon bond, and the like. The metal salt, the metal complex, and the compound having a metal-carbon bond may be either a metal compound having an organic group (organic metal compound) or a metal compound having no organic group (inorganic metal compound). .. Among them, the metal forming material is preferably a metal salt or a metal complex, more preferably a silver salt, a copper salt, a silver complex or a copper complex, and particularly preferably a silver salt or a silver complex.

The metal ink composition preferably contains at least the metal forming material, more preferably does not contain a resin component such as a binder, and particularly preferably the metal forming material is uniformly dispersed. ..

By using a metal forming material, a metal is generated from this material, and a metal layer (the conductive layer) containing the metal as a main component is formed. In the metal layer in this case, preferably, by not using the resin component, the ratio of the metal can be sufficiently increased to the extent that the metal layer can be regarded as apparently composed only of the metal. In this case, for example, the ratio of the metal in the metal layer is preferably 97% by mass or more, more preferably 98% by mass or more, and particularly preferably 99% by mass or more. The upper limit of the ratio of the metal in the metal layer is, for example, 100% by mass, 99.9% by mass, 99.8% by mass, 99.7% by mass, 99.6% by mass, 99.5% by mass, 99. It can be, but is not limited to, 4% by mass, 99.3% by mass, 99.2% by mass and 99.1% by mass.

Hereinafter, a method for forming a metal layer (conductive layer) when a silver ink composition containing a metal silver forming material is used as the metal ink composition will be described, but when the metal type is other than silver. Can also form a metal layer in the same way.

Preferred metal silver forming materials include, for example, organic silver compounds. The organic silver compound has an organic group and a silver atom in one molecule, and is a compound that produces metallic silver by structural changes such as decomposition.
That is, the silver ink composition is preferably a compound containing an organic silver compound, for example, a compound containing an organic silver compound and a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms. May be. The organic silver compound is preferably silver carboxylate or an organic silver complex.

As the preferable silver ink composition, for example, a silver ink composition comprising silver carboxylate and a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms (in the present specification, "silver"). Ink composition (I) ”), a silver ink composition containing silver carboxylate and not containing a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms (the present specification). In the above, it may be referred to as "silver ink composition (II)"), an organic silver complex, a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms, and a nitrogen-containing compound. Examples thereof include a silver ink composition (in the present specification, it may be referred to as “silver ink composition (III)”).
Hereinafter, each silver ink composition will be described in detail.

〇 Silver ink composition (I)
The silver ink composition (I) contains silver carboxylate (silver salt of carboxylic acid) as the organic silver compound, and further contains a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms. ..

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

In the present embodiment, one type of silver carboxylate may be used alone, or two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof may be arbitrarily adjusted. can.

The silver carboxylate is represented by the following general formula (1), β-ketocarboxylate silver (hereinafter, may be abbreviated as “β-ketocarboxylate silver (1)”) and the following general formula (4). It is preferably one or more selected from the group consisting of silver carboxylate (hereinafter, may be abbreviated as "silver carboxylate (4)").
In this specification, the description of "silver carboxylate" is not limited to "β-ketosilver carboxylate (1)" and "silver carboxylate (4)" unless otherwise specified. Inclusive, it shall mean "silver carboxylate having a group represented by the formula" -COOAg "".

（式中、Ｒは１個以上の水素原子が置換基で置換されていてもよい炭素数１～２０の脂肪族炭化水素基若しくはフェニル基、水酸基、アミノ基、又は一般式「Ｒ^１－ＣＹ^１ _２－」、「ＣＹ^１ _３－」、「Ｒ^１－ＣＨＹ^１－」、「Ｒ^２Ｏ－」、「Ｒ^５Ｒ^４Ｎ－」、「（Ｒ^３Ｏ）_２ＣＹ^１－」若しくは「Ｒ^６－Ｃ（＝Ｏ）－ＣＹ^１ _２－」で表される基であり；
Ｙ^１はそれぞれ独立にフッ素原子、塩素原子、臭素原子又は水素原子であり；Ｒ^１は炭素数１～１９の脂肪族炭化水素基又はフェニル基であり；Ｒ^２は炭素数１～２０の脂肪族炭化水素基であり；Ｒ^３は炭素数１～１６の脂肪族炭化水素基であり；Ｒ^４及びＲ^５はそれぞれ独立に炭素数１～１８の脂肪族炭化水素基であり；Ｒ^６は炭素数１～１９の脂肪族炭化水素基、水酸基又は式「ＡｇＯ－」で表される基であり；
Ｘ^１はそれぞれ独立に水素原子、炭素数１～２０の脂肪族炭化水素基、ハロゲン原子、１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはベンジル基、シアノ基、Ｎ－フタロイル－３－アミノプロピル基、２－エトキシビニル基、又は一般式「Ｒ^７Ｏ－」、「Ｒ^７Ｓ－」、「Ｒ^７－Ｃ（＝Ｏ）－」若しくは「Ｒ^７－Ｃ（＝Ｏ）－Ｏ－」で表される基であり；
Ｒ^７は、炭素数１～１０の脂肪族炭化水素基、チエニル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基若しくはジフェニル基である。）

(In the formula, R is an aliphatic hydrocarbon group or phenyl group having 1 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent, a hydroxyl group, an amino group, or the general formula "R1 ^- CY". ¹ _2- "," CY ¹ _3- "," R ¹ -CHY ^1- "," R ² O- "," R ⁵ R ⁴ N- "," (R ³ O) ₂ CY ^1- "or" R ⁶ -C (= O) -CY ¹ _2- "is a group represented by;
Y ¹ is an independently fluorine atom, chlorine atom, bromine atom or hydrogen atom; R ¹ is an aliphatic hydrocarbon group or phenyl group having 1 to 19 carbon atoms; R ² is a fat having 1 to 20 carbon atoms. Group hydrocarbon groups; R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are independently aliphatic hydrocarbon groups having 1 to 18 carbon atoms; R ⁶ is an aliphatic hydrocarbon group. An aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula "AgO-";
X ¹ is an independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, and a phenyl group or a benzyl group, a cyano group, or N in which one or more hydrogen atoms may be substituted with a substituent. -Phenyl-3-aminopropyl group, 2-ethoxyvinyl group, or general formula "R ⁷ O-", "R ⁷ S-", "R ⁷ -C (= O)-" or "R ⁷ -C ( = O) -O- "is a group represented by;
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or a diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )

（式中、Ｒ^８は炭素数１～１９の脂肪族炭化水素基、カルボキシ基又は式「－Ｃ（＝Ｏ）－ＯＡｇ」で表される基であり、前記脂肪族炭化水素基がメチレン基を有する場合、１個以上の前記メチレン基はカルボニル基で置換されていてもよい。）

(In the formula, R ⁸ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group or a group represented by the formula "-C (= O) -OAg", and the aliphatic hydrocarbon group is a methylene group. When, one or more of the methylene groups may be substituted with a carbonyl group.)

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

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

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

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

Examples of the alkynyl group in R include a group in which one single bond (CC) between carbon atoms of the alkyl group in R is replaced with a triple bond (C≡C).
Examples of such an alkynyl group include an ethynyl group (-C≡CH), a propargyl group ( _-CH2 -C≡CH) and the like.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms in R may have one or more hydrogen atoms substituted with a substituent. Preferred substituents include, for example, a fluorine atom, a chlorine atom, a bromine atom and the like. Further, in the aliphatic hydrocarbon group, the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other. That is, all the substituents may be the same, all the substituents may be different, or only some of the substituents may be different.

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

Y ¹ in R is a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom, respectively. Further, in the general formulas "R ¹ -CY 1 _2- ", "CY ¹ _3- " and "R ⁶ -C (= O) -CY ¹ _2- ", even if ^a plurality of Y ^1s are the same as each other. It may be different.

R ¹ in R is an aliphatic hydrocarbon group or a phenyl group (C ₆ H _5- ) having 1 to 19 carbon atoms. Examples of the aliphatic hydrocarbon group in R ¹ include the same as the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 19.
R ² in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the same group as the aliphatic hydrocarbon group in R.
R3 in R is an aliphatic hydrocarbon group having ¹ to 16 carbon atoms. Examples of the aliphatic hydrocarbon group in R ³ include the same as the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 16.
R ⁴ and R ⁵ in R are aliphatic hydrocarbon groups having 1 to 18 carbon atoms independently. That is, R ⁴ and R ⁵ may be the same as or different from each other, and the aliphatic hydrocarbon group in R ⁴ and R ⁵ may be, for example, the above-mentioned in R except that the number of carbon atoms is 1 to 18. Examples are similar to the aliphatic hydrocarbon group.
R ⁶ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group, or a group represented by the formula "AgO-". Examples of the aliphatic hydrocarbon group in R ⁶ include the same as the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 19.

Among the above, R may be a linear or branched alkyl group, a group represented by the general formula "R6 ^- C ( ₌ O) ^-CY 12-", a hydroxyl group or a phenyl group. preferable. And R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group or a group represented by the formula "AgO-".

In the general formula (1), X ¹ is an independently hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. A benzyl group (C ₆ H ₅ -CH _2- ), a cyano group, an N-phthaloyl-3-aminopropyl group, a 2-ethoxyvinyl group (C ₂ H ₅ -O-CH = CH-), or the general formula "R". It is a group represented by " ⁷ O-", "R ⁷ S-", "R ⁷ -C (= O)-" or "R ⁷ -C (= O) -O-".
Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in X ¹ include the same group as the aliphatic hydrocarbon group in R.

Examples of the halogen atom in X ¹ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The phenyl group and the benzyl group in X1 may have ^one or more hydrogen atoms substituted with a substituent. Preferred substituents include, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a nitro group (-NO ₂ ) and the like. In the phenyl group and the benzyl group having a substituent, the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.

R ⁷ in X ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group _{( C4H3S-} ), or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent. It is a diphenyl group (biphenyl group, C ₆ H ₅ -C ₆ H _4- ). Examples of the aliphatic hydrocarbon group in R ⁷ include the same group as the aliphatic hydrocarbon group in R except that the number of carbon atoms is 1 to 10. Further, examples of the substituent contained in the phenyl group and the diphenyl group in ^R7 include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom) and the like. In the phenyl group and the diphenyl group having a substituent, the number and position of the substituent are not particularly limited. When the number of substituents is plural, these plurality of substituents may be the same or different from each other.
When R ⁷ is a thienyl group or ^a diphenyl group, the bonding position with the adjacent group or atom (oxygen atom, sulfur atom, carbonyl group, carbonyloxy group) in X1 is not particularly limited. For example, the thienyl group may be either a 2-thienyl group or a 3-thienyl group.

In the general formula (1), the two X ^1s may be bonded to a carbon atom sandwiched between two carbonyl groups as one group via a double bond. Examples of such X ¹ include a group represented by the formula "= CH-C ₆ H ₄ -NO ₂ ".

Among the above, X ¹ is preferably a hydrogen atom, a linear or branched alkyl group, a benzyl group, or a group represented by the general formula " ^R7 -C (= O)-". , It is preferable that at least one X ¹ is a hydrogen atom.

The β-ketocarboxylate silver (1) is 2-methylacetate silver (CH ₃ -C (= O) -CH (CH ₃ ) -C (= O) -OAg) and silver acetoacetate (CH ₃ -C (=). O) -CH ₂ -C (= O) -OAg), 2-ethylacetate silver (CH ₃ -C (= O) -CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver propionyl acetate (CH ₃ CH ₂ -C (= O) -CH ₂ -C (= O) -OAg), silver isobutylyl acetate ((CH ₃ ) ₂ CH-C (= O) -CH ₂ -C (= O)- OAg), silver pivaloyl acetate ((CH ₃ ) ₃ C-C (= O) -CH ₂ -C (= O) -OAg), silver caproyl acetate (CH ₃ (CH ₂ ) ₃ CH ₂ -C (= O) ) -CH ₂ -C (= O) -OAg), 2-n-silver acetate acetate (CH ₃ -C (= O) -CH (CH ₂ CH ₂ CH ₂ CH ₃ ) -C (= O) -OAg ), 2-benzylacetate silver acetate (CH ₃ -C (= O) -CH (CH ₂ C ₆ H ₅ ) -C (= O) -OAg), silver benzoyl acetate (C ₆ H ₅ -C (= O)) ) -CH ₂ -C (= O) -OAg), silver pivaloylacetate acetate ((CH ₃ ) ₃ C-C (= O) -CH ₂ -C (= O) -CH ₂ -C (= O) -OAg ), Silver Isobutyrylacetate Acetate ((CH ₃ ) ₂ CH-C (= O) -CH ₂ -C (= O) -CH ₂ -C (= O) -OAg), 2-Acetylpivaloyl Acetate Silver ((CH ₃ ) ₃ C-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg), 2-acetylisobutyryl silver acetate ((CH ₃ )) ₂ CH-C (= O) -CH (-C (= O) -CH ₃ ) -C (= O) -OAg) or silver acetate dicarboxylate (AgO-C (= O) -CH ₂ -C ( = O) -CH ₂ -C (= O) -OAg) is preferable.

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

As will be described later, the silver β-ketocarboxylate (1) is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent known in the art. Metallic silver can be formed. Then, the silver β-ketocarboxylate (1) is decomposed at a lower temperature to form metallic silver when used in combination with a reducing agent.

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

(Silver carboxylate (4))
The silver carboxylate (4) is represented by the general formula (4).
^In the formula, R8 is an aliphatic hydrocarbon group having 1 to 19 carbon atoms, a carboxy group (-COOH) or a group represented by the formula "-C (= O) -OAg".
Examples of the aliphatic hydrocarbon group in R ⁸ include those similar to the aliphatic hydrocarbon group in R, except that the number of carbon atoms is 1 to 19. However, the aliphatic hydrocarbon group ⁱⁿ R8 preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

When the aliphatic hydrocarbon group ⁱⁿ R8 has a methylene group ( _-CH2- ), one or more of the methylene groups may be substituted with a carbonyl group. The number and position of the methylene groups which may be substituted with a carbonyl group are not particularly limited, and all the methylene groups may be substituted with a carbonyl group. Here, the "methylene group" is not only a single group represented by the formula "-CH _2- " but also one of the alkylene groups in which a plurality of groups represented by the formula "-CH _2- " are connected. It shall also include the group represented by the formula "-CH _2- " of.

The silver carboxylate (4) is silver pyruvate (CH ₃ -C (= O) -C (= O) -OAg), silver acetate (CH ₃ -C (= O) -OAg), silver butyrate (CH ₃ ). -(CH ₂ ) ₂ -C (= O) -OAg), silver isobutyrate ((CH ₃ ) ₂ CH-C (= O) -OAg), silver 2-ethylhexanoate (CH _3- (CH ₂ )) ) ₃ -CH (CH ₂ CH ₃ ) -C (= O) -OAg), silver neodecanoate, silver oxalate (AgO-C (= O) -C (= O) -OAg), or silver malonate () AgO-C (= O) _-CH2 -C (= O) -OAg) is preferable. In addition, 2 of the above-mentioned silver oxalate (AgO-C (= O) -C (= O) -OAg) and silver malonic acid (AgO-C (= O) _-CH2 -C (= O) -OAg). Of the groups represented by the formula "-COOAg", one is a group represented by the formula "-COOH" (HO-C (= O) -C (= O) -OAg, HO. -C (= O) -CH ₂ -C (= O) -OAg) is also preferable.

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

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

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

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

[Branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms]
The silver ink composition (I) contains the branched-chain saturated aliphatic carboxylic acid (in this specification, it may be abbreviated as "branched-chain saturated aliphatic carboxylic acid"). A silver layer with higher gloss and conductivity can be formed.

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

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

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

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

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

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

The number of branched chains in one molecule of the branched saturated aliphatic carboxylic acid is preferably 1 to 3, not limited to the monocarboxylic acid (6).
The number of carbon atoms in one branched chain of the branched-chain saturated aliphatic carboxylic acid is preferably 1 to 3, not limited to the monocarboxylic acid (6).
Not limited to the monocarboxylic acid (6), the branched-chain saturated aliphatic carboxylic acid satisfies both of these conditions, that is, the number of branched chains in one molecule is 1 to 3 and one. It is more preferable that the branched chain of the above has 1 to 3 carbon atoms.

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

Particularly preferred branched chain saturated aliphatic carboxylic acids (eg, monocarboxylic acid (6)) are neodecanoic acid (C _{9H 19 COOH} ), 2-propylvaleric acid (2-propylpentanoic acid, (CH ₃ )). CH ₂ CH ₂ CH (CH ₃ CH ₂ CH ₂ ) COOH), 3,5,5-trimethylhexanoic acid ((CH ₃ ) ₃ CCH ₂ CH (CH ₃ ) CH ₂ COOH) and the like can be mentioned.
In the present specification, neodecanoic acid means a mixture of isomers of a saturated aliphatic monocarboxylic acid having 10 carbon atoms, and the mixed has a branched chain saturated aliphatic monocarboxylic acid having 10 carbon atoms. included. As described above, neodecanoic acid does not mean only one compound.
The combination and ratio of two or more kinds of saturated aliphatic monocarboxylic acids having 10 carbon atoms in neodecanoic acid can be arbitrarily adjusted.

The branched-chain saturated aliphatic carboxylic acid may be used alone or in combination of two or more, and when two or more are used in combination, their combinations and ratios are arbitrarily adjusted. can.

As described above, the silver ink composition (I) contains the branched saturated aliphatic carboxylic acid, so that the silver ink composition (I) has higher gloss and conductivity due to the solidification treatment. Metallic silver can be formed. The reason is not clear, but it is presumed as follows.
That is, in the silver ink composition (I) adhering to the surface to be formed of the silver layer, silver ions (Ag ⁺ ) are generated from the silver carboxylate. In this case, oxygen is coordinated to the silver ions by the initial solidification treatment of the silver ink composition (I) (Ag ⁺ ... O). Next, silver oxide (Ag ₂ O) is generated from the oxygen-coordinated silver ions by a solidification treatment such as a drying treatment or a heating (baking) treatment of the silver ink composition (I) for forming metallic silver. Here, in the case of a silver ink composition that does not contain a branched saturated aliphatic carboxylic acid, silver oxide produced as a by-product is contained in the metallic silver finally produced by the solidification treatment of the silver ink composition. It is presumed that it is mixed as an impurity, the glossiness of metallic silver is lowered, and the conductivity is also lowered. On the other hand, in the case of the silver ink composition (I) containing the branched saturated aliphatic carboxylic acid, the branched saturated aliphatic carboxylic acid reacts with silver oxide to have 8 to 8 carbon atoms. A silver salt of 10 branched chain saturated aliphatic carboxylic acids (may be abbreviated as "branched chain saturated aliphatic carboxylic acid silver" in the present specification) is produced. This branched chain saturated aliphatic carboxylate silver is the above-mentioned silver carboxylate (4), and is finally solidified by the solidification treatment of the silver ink composition (I), similarly to the silver carboxylate compounded from the beginning. Produces metallic silver (silver layer). As described above, by using the silver ink composition (I) of the present embodiment, the silver oxide generated due to the solidification treatment of the silver ink composition (I) is the action of the branched chain saturated aliphatic carboxylic acid. Therefore, it is presumed that the metallic silver having higher gloss and conductivity can be formed by converting the metallic silver into the metallic silver itself instead of the impurities that cause the decrease in the gloss and conductivity of the metallic silver.

In the silver ink composition (I), the blending amount of the branched chain saturated aliphatic carboxylic acid is preferably 0.01 to 1 mol per 1 mol of the silver atom in the organic silver compound, and is 0. It is more preferably 0.02 to 0.7 mol, and particularly preferably 0.03 to 0.4 mol. When the blending amount of the branched chain saturated aliphatic carboxylic acid is in such a range, the effect of forming metallic silver having high glossiness and conductivity is further enhanced.

Similar to the branched saturated aliphatic carboxylic acid, there are some carboxylic acids other than the branched saturated aliphatic carboxylic acid that enable the formation of metallic silver having higher gloss and conductivity.
The carboxylic acid other than such a branched chain saturated aliphatic carboxylic acid (sometimes referred to as “other carboxylic acid” in the present specification) may be a monovalent carboxylic acid or a divalent or higher carboxylic acid. It may be a polyvalent carboxylic acid, an aliphatic carboxylic acid, or an aromatic carboxylic acid.

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

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

The boiling point of the other carboxylic acid is preferably 150 to 290 ° C, and may be, for example, 155 to 280 ° C, 160 to 270 ° C and 160 to 260 ° C. When the boiling point of the other carboxylic acid is at least the above lower limit, the volatilization of the other carboxylic acid from the silver ink composition (I) is suppressed, and the effect of using the other carboxylic acid is more remarkable. Obtained in. Further, when the boiling point of the other carboxylic acid is not more than the upper limit value, the residual of the other carboxylic acid in the metallic silver obtained by the solidification treatment of the silver ink composition (I) is suppressed, and the glossiness is improved. Metallic silver having more preferable characteristics such as high conductivity can be obtained.

The other carboxylic acids may be used alone or in combination of two or more, and when two or more of them are used in combination, their combinations and ratios can be arbitrarily adjusted.

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

[Nitrogen-containing compound]
The silver ink composition (I) is preferably a compound containing a nitrogen-containing compound in addition to the silver carboxylate and the branched-chain saturated aliphatic carboxylic acid.
The nitrogen-containing compound is an amine compound having 25 or less carbon atoms (hereinafter, may be abbreviated as "amine compound") and a quaternary ammonium salt having 25 or less carbon atoms (hereinafter, abbreviated as "quaternary ammonium salt"). (May be), ammonia, an ammonium salt formed by reacting an amine compound with 25 or less carbon atoms with an acid (hereinafter, may be abbreviated as "ammine salt derived from an amine compound"), and ammonia reacting with an acid. One or more selected from the group consisting of ammonium salts (hereinafter, may be abbreviated as "ammonium-derived ammonium salts"). That is, the nitrogen-containing compound to be blended may be only one kind, may be two or more kinds, and when there are two or more kinds, the combination and ratio thereof can be arbitrarily adjusted.

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

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

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

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

The heteroaryl group constituting the mono (heteroaryl) amine has a hetero atom as an atom constituting the aromatic ring skeleton, and the hetero atom includes, for example, a nitrogen atom, a sulfur atom, an oxygen atom, and the like. Examples include a boron atom. Further, the number of the heteroatoms constituting the aromatic ring skeleton is not particularly limited, and may be one or two or more. When there are two or more, these heteroatoms may be the same or different from each other. That is, these heteroatoms may all be the same, may be all different, or may be partially different.
The heteroaryl group may be either monocyclic or polycyclic, and the number of ring members (the number of atoms constituting the ring skeleton) is not particularly limited, but is preferably 3 to 12 membered rings.

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

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

Examples of the secondary amine include dialkylamines, diarylamines, di (heteroaryl) amines, etc., in which one or more hydrogen atoms may be substituted with a substituent.

The alkyl group constituting the dialkylamine is the same as the alkyl group constituting the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms or a carbon number of 3 to 7 carbon atoms. It is preferably a cyclic alkyl group. Further, the two alkyl groups in one molecule of dialkylamine may be the same or different from each other.
Specific examples of the preferred dialkylamine include N-methyl-n-hexylamine, diisobutylamine, and di (2-ethylhexyl) amine.

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

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

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

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

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

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

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

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

Examples of the substituent in the amine compound and the quaternary ammonium salt include an alkyl group, an aryl group, a halogen atom, a cyano group, a nitro group, a hydroxyl group, a trifluoromethyl group (-CF ₃ ) and the like. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

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

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

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

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

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

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

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

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

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

[alcohol]
The silver ink composition (I) is preferably one in which an alcohol is further blended in addition to the silver carboxylate and the branched-chain saturated aliphatic carboxylic acid.

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

（式中、Ｒ’及びＲ’’は、それぞれ独立に水素原子、炭素数１～２０のアルキル基、又は１個以上の水素原子が置換基で置換されていてもよいフェニル基である。）

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

(Acetylene alcohol (2))
The acetylene alcohol (2) is represented by the general formula (2).
In the formula, R'and R'' are hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, or phenyl groups in which one or more hydrogen atoms may be substituted with substituents, respectively.
The alkyl group having 1 to 20 carbon atoms in R'and R'' may be linear, branched or cyclic, and when cyclic, it may be monocyclic or polycyclic. Examples of the alkyl group in R'and R'' include the same as the alkyl group in R.

Examples of the substituent in which the hydrogen atom of the phenyl group in R'and R'' may be substituted include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the fat. Examples thereof include a monovalent group formed by bonding a group hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group and the like. These substituents are the same as the substituents in which the hydrogen atom of the phenyl group in R may be substituted. The number and position of the substituents in the phenyl group having a substituent are not particularly limited, and when the number of the substituents is a plurality, the plurality of substituents may be the same or different from each other.

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

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

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

The alcohol may be used alone or in combination of two or more, and when two or more are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

[Other ingredients (2)]
The silver ink composition (I) does not correspond to any of the silver carboxylate, the branched-chain saturated aliphatic carboxylic acid, the nitrogen-containing compound, and the alcohol, and other components (in the present specification, It may be a mixture of (sometimes referred to as "other component (2)").
The other component (2) in the silver ink composition (I) can be arbitrarily selected depending on the intended purpose, and is not particularly limited. Preferred examples of the other component (2) include a solvent other than alcohol, which can be arbitrarily selected depending on the type and amount of the compounding component.
In the silver ink composition (I), the other component (2) may be used alone or in combination of two or more, and when two or more are used in combination, they may be used alone. The combinations and ratios can be adjusted arbitrarily.

(solvent)
The solvent is not particularly limited as long as it is other than alcohol (which does not have a hydroxyl group).
However, the solvent is preferably liquid at room temperature.

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

The blending amount of the other component (2) in the silver ink composition (I) may be appropriately selected according to the type of the other component (2).

For example, when the other component (2) is a solvent other than alcohol, the blending amount of the solvent may be selected according to the purpose such as the viscosity of the silver ink composition (I). However, usually, in the silver ink composition (I), the ratio of the blending amount of the solvent to the total blending component is preferably 35% by mass or less, more preferably 30% by mass or less, and 25% by mass. % Or less is particularly preferable.

For example, when the other component (2) is a component other than the solvent, the ratio of the blending amount of the other component (2) to the total blending component in the silver ink composition (I) is 10% by mass. It is preferably less than or equal to, and more preferably 5% by mass or less.
The ratio of the blending amount of the other component (2) to the total blending component is 0 mass, that is, even if the other component (2) is not blended, the silver ink composition (I) sufficiently exhibits its effect. ..

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

〇Silver ink composition (II)
The silver ink composition (II) contains silver carboxylate (silver salt of carboxylic acid) as the organic silver compound, and does not contain a branched chain saturated aliphatic carboxylic acid having 8 to 10 carbon atoms. It is a thing.

The silver ink composition (II) may be the same as the silver ink composition (I) except that the branched chain saturated aliphatic carboxylic acid is not blended.
That is, examples of the compounding component of the silver ink composition (II) include the silver carboxylate, a nitrogen-containing compound, an alcohol, and another component (2).
The blending amount of the silver carboxylate, the nitrogen-containing compound, the alcohol, and the other component (2) in the silver ink composition (II) may be the same as in the case of the silver ink composition (I).
The silver ink composition (II) may be further supplied with carbon dioxide. The method of supplying carbon dioxide in this case is the same as that of the silver ink composition (I) described above, except that the branched-chain saturated aliphatic carboxylic acid is not a compounding component.

[Reducing agent]
The silver ink composition (II) may be further blended with a reducing agent in addition to the silver carboxylate.
The reducing agent includes oxalic acid (HOOC-COOH), hydrazine (H2N _{- NH2} ) and a compound represented by the following general formula (5) (hereinafter, may be abbreviated as "compound (5)"). One or more selected from the group consisting of.
HC (= O) -R ²¹ ... (5)
(In the formula, R ²¹ is an alkyl group having 20 or less carbon atoms, an alkoxy group or an N, N-dialkylamino group, a hydroxyl group or an amino group.)
That is, the reducing agent to be blended may be only one kind, may be two or more kinds, and when two or more kinds are used in combination, the combination and the ratio can be arbitrarily adjusted.

The hydrazine as the reducing agent may be a monohydrate (H2N _{- NH2} · _H2O ).

Preferred reducing agents include, for example, formic acid (HC (= O) -OH); methyl formate (HC (= O) -OCH ₃ ), ethyl formate (HC (= O)-. Formic acid esters such as OCH ₂ CH ₃ ), butyl formate (HC (= O) -O (CH ₂ ) ₃ CH ₃ ); Propanal (HC (= O) -CH ₂ CH ₃ ), butanal ( Aldehydes such as HC (= O)-(CH ₂ ) ₂ CH ₃ ), hexanal (HC (= O)-(CH ₂ ) ₄ CH ₃ ); formamide (HC (= O) -NH ₂ ), N, N-dimethylformamides (HC (= O) -N (CH ₃ ) ₂ ) and other formamides (expressed by the formula "HC (= O) -N (-)-" Compounds having a group); Formic acid and the like can be mentioned.

When a reducing agent is used, in the silver ink composition (II), the blending amount of the reducing agent is preferably 0.04 to 3.5 mol per 1 mol of the silver carboxylate blending amount, preferably 0.06 to 3.0 mol. More preferably, it is 2.5 mol. When the blending amount of the reducing agent is in such a range, the silver ink composition (II) can more easily and more stably form metallic silver.

○ Method for producing silver ink composition (II) Silver ink composition (II) is silver ink except that the branched chain saturated aliphatic carboxylic acid is not blended and the reducing agent is blended as needed. It can be produced by the same method as in the case of the composition (I).
That is, the silver ink composition (II) can be obtained by blending the silver carboxylate and, if necessary, an arbitrary component. Here, the "arbitrary component" means a reducing agent and a component that does not correspond to any of the silver carboxylate and the reducing agent. For example, in the production of the silver ink composition (II), the blending order of each component is not particularly limited.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the nitrogen-containing compound (93) include ethylammonium ethyl carbonate, isopropylammonium isopropylcarbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, tert-butylammonium tert-butylcarbonium, and 2-ethylhexylammonium 2-. Ethylhexyl carbonate, 2-methoxyethylammonium 2-methoxyethyl carbonate, 2-cyanoethylammonium 2-cyanoethyl carbonate, octadecylammonium octadecylcarbonate, dibutylammonium dibutylcarbonate, dioctadecylammonium dioctadecylcarbonate, methyldecylammonium methyldecylcarbonate, hexamethylene i Examples thereof include minylammonium hexamethyleneiminyl carbonate, morpholinoammonium morpholinocarbonate, benzylammonium benzyl carbonate, triethoxysilylpropylammonium triethoxysilylpropylcarbonate and the like.

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

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

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

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

[solvent]
The reaction may be carried out using a solvent. Examples of the solvent at this time include water; alcohols such as methanol, ethanol, 2-propanol and butanol; glycols such as ethylene glycol and glycerin; acetates such as ethyl acetate, butyl acetate and carbitol acetate; diethyl ether, tetrahydrofuran, etc. Ethers such as dioxane; ketones such as methyl ethyl ketone and acetone; aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride can be mentioned. ..
As the solvent, one type may be used alone, two or more types may be used in combination, and when two or more types are used in combination, the combination and ratio thereof can be arbitrarily adjusted.

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

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

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

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

As described above, the silver ink composition (III) contains the branched saturated aliphatic carboxylic acid, so that when the silver ink composition (III) is solidified, it has gloss and conductivity. Can form higher metallic silver. The reason is not clear, but it is presumed to be the same as in the case of the silver ink composition (I) described above.

The silver ink composition used in this embodiment is as described above.
Next, a method of using the silver ink composition will be described.

○ How to use the silver ink composition The silver ink composition is not limited to the silver ink composition (I), the silver ink composition (II) and the silver ink composition (III), and the silver ink composition can be used by a printing method or a coating method. It can be attached to an object by a known method such as.

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

As the coating method, for example, a method using various coaters such as a spin coater, an air knife coater, a curtain coater, a die coater, a blade coater, a roll coater, a gate roll coater, a bar coater, a rod coater, and a gravure coater; Method to be used; Method using a coating device such as a slot die; Spray method and the like can be mentioned.

When the silver ink composition is adhered to a target location and a silver layer is formed by solidification treatment such as drying treatment or heating (baking) treatment of the silver ink composition after the adhesion, the silver ink composition is adhered to the target location. By adjusting the amount of the silver ink composition to be adhered or the blending amount of the organic silver compound in the silver ink composition, the amount of the silver layer formed and the thickness of the silver layer can be adjusted.

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

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

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

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

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

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

The heat treatment of the silver ink composition may be performed in two steps. For example, in the first-step heat treatment, the silver ink composition is mainly dried instead of forming metallic silver, and in the second-step heat treatment, the metallic silver is formed to the end.

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

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

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

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

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

<< Manufacturing method of conductive laminate >>
The conductive laminate of the present embodiment has, for example, a step of forming a receiving layer on a paper sheet (hereinafter, may be abbreviated as "receptive layer forming step") and a step of forming a conductive layer on the receiving layer. It can be manufactured by a manufacturing method having a step (hereinafter, may be abbreviated as "conductive layer forming step").
FIG. 2 is a cross-sectional view for schematically explaining a method for manufacturing the conductive laminate 1 shown in FIG.

<Receptive layer formation step>
In the receiving layer forming step, as shown in FIG. 2B, the receiving layer 12 is formed on the paper sheet 11.
The receiving layer 12 forms the composition layer by adhering the polyurethane-containing composition for forming the receiving layer to the first surface 11a of the paper sheet 11, which is the surface to be formed of the receiving layer, and forms the composition layer. It can be formed by subjecting (the composition layer for forming a receiving layer) to a drying treatment.
The method for adhering the composition for forming a receiving layer to the target substance and the method for the drying treatment are as described above.

<Conductive layer forming process>
In the conductive layer forming step, as shown in FIG. 2C, the conductive layer 13 is formed on the receiving layer 12.
The conductive layer 13 forms the composition layer by adhering the composition for forming the conductive layer to the first surface 12a of the receiving layer 12, which is the surface to be formed of the conductive layer, and forms the composition layer (conducting layer formation). The composition layer) can be formed by appropriately selecting and performing a solidification treatment such as a drying treatment or a heating (baking) treatment.
The method of adhering the composition for forming a conductive layer to the target material and the method of the solidification treatment are as described above.

Here, the method of manufacturing the conductive laminate 1 shown in FIG. 1 has been described as an example, but other conductive laminates of the present embodiment can also be manufactured by the same method depending on the structure. .. For example, in the conductive laminate provided with the other layer, in the above-mentioned manufacturing method, the step of forming the other layer is appropriately added to a suitable place at a suitable timing. , Can be manufactured.

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

The paper sheets used in Examples or Comparative Examples are shown in Table 1, and the composition for forming a receptive layer is shown in Table 2.
As the paper sheets in Table 1, those having a size of 50 mm × 50 mm were used. The paper sheet (P7) -1 is a commercially available glossy paper for a laser printer, which is provided with a polyvinyl alcohol (PVA) -containing layer on the surface in advance as a receiving layer.
The polyurethanes in the composition for forming the receiving layer in Table 2 are all anionic polyurethanes.

[Example 1]
<Manufacturing of conductive laminate>
(Manufacturing of silver ink composition)
2-Ethylhexylamine (6.53 times the amount of silver 2-methylacetate acetate described later) and 3,5-dimethyl-1-hexin-3-ol (hereinafter, abbreviated as "DMHO") in a beaker. (There is) (0.10 times the amount of silver 2-methylacetate acetate described later), and mix, and while rotating the mechanical stirrer and stirring, the liquid temperature is 40 ° C or less. 2-Methylacetate silver was added so as to dissolve each compounding component, and stirring was continued for 1 day at room temperature.
Next, the composition for forming a conductive layer is formed by dropping neodecanoic acid (0.13 times the molar amount with respect to silver 2-methylacetate acetate) and stirring the stirring liquid so that the liquid temperature becomes 30 ° C. or lower. The silver ink composition (I) -1 was obtained.
As DMHO, "Surfinol 61" manufactured by Nisshin Kagaku Co., Ltd. was used, and as neodecanoic acid, "Versatic 10" manufactured by Japan Chemtech Co., Ltd. was used. This also applies to the following Examples, Comparative Examples, and Reference Examples.

Table 3 shows the types and mixing ratios of each compounding ingredient. In Table 3, "nitrogen-containing compound (molar ratio)" refers to the amount of the nitrogen-containing compound (number of moles) per mol of the amount of the organic silver compound ([number of moles of the nitrogen-containing compound] / [organic silver compound]. Number of moles]). Similarly, "alcohol (molar ratio)" means the amount of alcohol compounded (number of moles) ([number of moles of alcohol] / [number of moles of organic silver compound]) per mole of compounding amount of organic silver compound. Similarly, "branched chain saturated aliphatic carboxylic acid (molar ratio)" also contains the amount of branched chain saturated aliphatic carboxylic acid (number of moles) per mol of the amount of the organic silver compound ([branched chain saturated fat]. Number of moles of group carboxylic acid] / [Number of moles of organic silver compound]). Similarly, for the "reducing agent (molar ratio)", the blending amount (number of moles) of the reducing agent per mole of the blending amount of the organic silver compound ([number of moles of reducing agent] / [number of moles of organic silver compound]) means. Similarly, "solvent (molar ratio)" means the amount of substance (number of moles) ([number of moles of solvent] / [number of moles of organic silver compound]) per mol of amount of organic silver compound. Further, the description of "-" in the column of the compounding component / blending amount of the silver ink composition means that the component is not compounded.
In this example, the "organic silver compound" is "silver β-ketocarboxylate (1)".

(Manufacturing of conductive laminate)
The composition for forming a receptive layer (PU1) was manually applied on one surface of the paper sheet (P1) -1 with a rod bar and dried at 100 ° C. to form a receptive layer. The amount of polyurethane on the paper sheet was 25 g / m ² . The amount of this polyurethane (the amount of resin in the receiving layer on the paper sheet) is shown in the column of "Amount of resin (g / m ² )" in Table 4.
Then, using a spin coater, the silver ink composition obtained above is coated on the surface of the receiving layer, and the coated sheet is immediately placed in an oven and heated at 130 ° C. for 5 minutes. By doing so, a silver layer was formed. The rotation conditions during coating by the spin coater were 2000 rpm for 5 seconds and then 3000 rpm for 5 seconds. The amount of the silver layer formed was 7.5 g / m ² , and the thickness of the silver layer was 0.15 μm. The amount of silver layer formed is shown in the column of "Amount of conductive layer formed (g / m ² )" in Table 4.
From the above, a conductive laminated body was obtained.

<Evaluation of conductive laminate>
(Measurement of surface resistance of silver layer)
Using a resistivity meter (Mitsubishi Chemical Analytech Co., Ltd. "Loresta MCP-T610, PSP type probe"), measure the surface resistance value of the silver layer in the conductive laminate obtained above by the 4-end needle method. did. The results are shown in the column of "Surface resistance value of conductive layer (Ω / □)" in Table 4.
The description of "OL" in the column of "surface resistance value of conductive layer (Ω / □)" means that the surface resistance value is too large to measure (non-conducting).

<Manufacturing and evaluation of conductive laminate>
[Examples 2 to 19, Comparative Examples 1 to 14]
Implementation except that one or more of the type of paper sheet, the type of the composition for forming the receiving layer, the amount of resin in the receiving layer on the paper sheet, and the amount of forming the conductive layer were changed as shown in Table 4. A conductive laminate was manufactured and evaluated in the same manner as in Example 1. The results are shown in Table 4.
In addition, in Table 4, the description of "-" in the column of "composition for forming a receiving layer" means that the composition for forming a receiving layer is not used. When the composition for forming the receiving layer is not used, the composition for forming the conductive layer (silver ink composition) is applied directly on the surface of the paper sheet.

[Reference Example 1]
Instead of the paper sheet (P1) -1, a polyethylene terephthalate (PET) film (Lumirror 188E22, thickness 188 μm, Oken-type air permeability of 200,000 seconds or more) was used, and a composition for forming a receiving layer was used. A conductive laminate was produced and evaluated by the same method as in Example 1 except that it was not used. The results are shown in Table 4.
Here, the composition for forming the conductive layer (silver ink composition) is directly applied onto the surface of the PET film.

[Example 20]
As shown in Table 3, a silver ink composition was produced by the same method as in Example 1 except that neodecanoic acid was not used, and a silver ink composition (II) -1 was obtained.
Then, instead of the silver ink composition (I) -1, the point where the silver ink composition (II) -1 was used, the conductive layer forming amount (silver layer forming amount) was replaced with 7.3 g / m ² . The same method as in Example 10 except that the composition was 7.5 g / m ² and the composition for forming the receiving layer (PU1) was used instead of the composition for forming the receiving layer (PU2). The conductive laminate was manufactured and evaluated in the above. The results are shown in Table 5.

[Comparative Example 15]
As shown in Table 3, a silver ink composition was produced by the same method as in Example 1 except that neodecanoic acid was not used, and a silver ink composition (II) -1 was obtained.
Then, a conductive laminate is produced and evaluated by the same method as in Comparative Example 10 except that the silver ink composition (II) -1 is used instead of the silver ink composition (I) -1. did. The results are shown in Table 5.

[Example 21]
<Manufacturing of conductive laminate>
(Manufacturing of silver ink composition)
In a beaker, 2-ethylhexylamine (1.45 times the molar amount of 2-methylacetate silver acetate described later) and n-hexane (1.63 times the molar amount of 2-methylacetate silver acetate described later), Was added in this order, and silver 2-methylacetate was added to the beaker so that the liquid temperature was 50 ° C. or lower while rotating and stirring the mechanical stirrer.
After the addition of 2-methylacetate silver is completed, formic acid (0.5 times the amount of 2-methylacetate silver) is added dropwise in a beaker over 10 minutes while maintaining the same state. After the addition of formic acid was completed, the mixture was further stirred as it was for 1.5 hours.
Then, 3,5-dimethyl-1-hexin-3-ol (DMHO) (0.10 times molar amount with respect to silver 2-methylacetate acetate) and 4-ethyl-1-octyne-3-ol (hereinafter, ". A mixture of (sometimes abbreviated as "EOO") (0.004 times the molar amount of 2-methylacetate silver) is added to the beaker, and after the addition is completed, the mixture is further stirred for 5 minutes in that state. A silver ink composition (II) -2 was obtained as a silver ink composition.
As the EOO, one manufactured by Tokyo Chemical Industry Co., Ltd. was used.
Table 3 shows the types and mixing ratios of each compounding ingredient.

(Manufacturing of conductive laminate)
The point that this silver ink composition (II) -2 was used instead of the silver ink composition (I) -1, and the conductive layer formation amount (silver layer formation amount) was 55 instead of 7.3 g / m ² . The same method as in Example 10 except that the composition was set to 3 g / m ² and the composition for forming the receiving layer (PU1) was used instead of the composition for forming the receiving layer (PU2). A conductive laminate was manufactured.

<Evaluation of conductive laminate>
(Measurement of sheet resistance of silver layer)
The conductive laminate obtained above was evaluated by the same method as in Example 10. The results are shown in Table 5.

As is clear from the above results, the conductive laminates of Examples 1 to 21 have a receiving layer containing polyurethane, so that the surface resistance value of the silver layer (conductive layer) is 18Ω / □ or less (0. It was 07 to 18Ω / □), and the conductivity of the silver layer was high.
In the conductive laminates of Examples 1 to 21, the amount of resin (amount of polyurethane) on the paper sheet is 7 g / m ² or more (7 to 30 g / m ² ), and the amount of silver layer formed (conducting layer formation). The amount) was 6.5 g / m ² or more (6.5 to 55.3 g / m ² ).

The conductive laminate of Reference Example 1 has a resin film (resin sheet) instead of a paper sheet, does not have a receiving layer, and has a paper sheet, which is a problem, that is, sufficiently conductive. It does not have the problem that a conductive layer having properties cannot be formed. In fact, in the conductive laminate of Reference Example 1, the surface resistance value of the silver layer (conductive layer) was as low as 8.1 Ω / □.
In the conductive laminates of each of the above examples, the surface resistance value of the silver layer (conductive layer) is often lower than that of Reference Example 1, and it is generally found that the surface resistance value is lower than that of Reference Example 1. It was equal to or less than the case of.
That is, the conductive laminates of these examples were extremely excellent in the conductivity of the silver layer.

On the other hand, the conductive laminates of Comparative Examples 1 to 9 did not have a receiving layer, and the silver layer did not substantially show conductivity.
The conductive laminates of Comparative Examples 10 and 15 used a paper sheet provided with a receiving layer containing polyvinyl alcohol (PVA), but the silver layer did not substantially exhibit conductivity.
Although the conductive laminate of Comparative Example 11 had a receiving layer containing polystyrene, the surface resistance value of the silver layer (conductive layer) was 33Ω / □, and the conductivity of the silver layer was low.
The conductive laminates of Comparative Examples 12 to 14 each include a receiving layer containing a modified epoxy resin (Example 12), polyester (Example 13), and styrene maleic acid resin (Example 14) as resins. Although the amount of these resins on the paper sheet was the same as in the case of Comparative Example 11, the silver layer showed substantially no conductivity.

The present invention can be used for all conductive laminated bodies using paper sheets such as circuit boards.

1 ... Conductive laminate, 11 ... Paper sheet, 11a ... First surface of paper sheet, 12 ... Receptive layer, 12a ... First surface of receptive layer, 13 ... Conductive layer

Claims (3)

A paper sheet, a receiving layer provided on the paper sheet, and a conductive layer provided on the receiving layer are provided.
A conductive laminate in which the receiving layer contains polyurethane having an anionic group . The conductive laminate according to claim 1 , wherein the amount of the polyurethane on the paper sheet is 6 g / m ² or more. The conductive laminate according to claim 1 or 2 , wherein the conductive layer is formed by using a silver ink composition containing an organic silver compound.

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