JP2019171628A - Conductive laminate - Google Patents

Abstract

To provide a novel conductive laminate comprising a paper sheet and a conductive layer formed on the paper sheet in which the conductive layer has sufficient conductivity.SOLUTION: The conductive laminate 1 comprises a paper sheet 11, a reception layer 12 formed on the paper sheet 11 and a conductive layer 13 formed on the reception layer 12 in which the reception layer 12 includes polyurethane.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a conductive laminate.

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

  In general, a resin sheet is used as the base sheet, but in recent years, a conductive laminate using a paper sheet has been studied. A conductive laminate using a paper sheet has high flexibility, is easy to dispose of, and has a low environmental burden. In addition, a highly versatile method of applying or printing an ink composition capable of forming a conductive layer can be used for forming a circuit (patterned conductive layer), and it can be manufactured at a low cost. Has various advantages. As the ink composition, a composition containing a metal compound such as a metal complex capable of forming 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 in a liquid state, particularly in the case of a solution, when the ink composition is applied or printed, the metal compound in the ink composition is 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 a sufficient amount of metal (conductive layer) cannot be formed on the paper sheet.

  In contrast, JAPAN TAPPI paper pulp test method No. 5-2: By using a paper sheet having an air permeability adjusted to 40000 seconds or more based on 2000, the penetration of the ink composition as a solution into the inside of the paper sheet is suppressed. Has disclosed a method for forming a sufficient amount of metal (see Patent Document 1).

JP 2012-129343 A

  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 having electrical conductivity. Has 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 includes a novel conductive laminate comprising a paper sheet and a conductive layer provided on the paper sheet, the conductive layer having sufficient conductivity. The challenge is to provide a 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,
A conductive laminate is provided in which the receiving layer comprises polyurethane.
In the conductive laminate of the present invention, the polyurethane preferably 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, the conductive layer is preferably formed using a silver ink composition containing an organic silver compound.

  The present invention provides 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 electroconductive laminated body which concerns on one Embodiment of this invention. It is sectional drawing for demonstrating typically the manufacturing method of the electroconductive laminated body which concerns on one Embodiment of this invention.

<< Conductive Laminate >>
An electroconductive laminate according to an 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 a polyurethane. including.

  Since the paper sheet has high liquid permeability, when the ink composition is in a liquid state, when the ink composition is applied or printed, the ink composition penetrates into the paper sheet. When a material for forming a conductive layer (conductive layer forming material) such as a metal compound is included in the ink composition, the conductive layer forming material also penetrates into the paper sheet. When the ink composition is a solution, this tendency is further increased. Then, the amount of the conductive layer forming material remaining on the surface of the paper sheet decreases, 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, regardless of whether 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 problem of penetration.
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 laminate 1 is configured by laminating the paper sheet 11, the receiving layer 12, and the conductive layer 13 in this order in the thickness direction.
In the conductive laminate 1, the receiving layer 12 is laminated on one side (which may be referred to as “first side” in this specification) 11 a of the paper sheet 11, and the paper sheet 11 of the receiving layer 12 is stacked. A conductive layer 13 is laminated on a surface 12a opposite to the side (which may be referred to as a “first surface” in this specification) 12a.
The receiving layer 12 includes polyurethane.

  The shape of the receiving layer 12 (planar shape) when the receiving layer 12 is viewed from above, that is, as viewed from the conductive layer 13 side, is arbitrarily set according to the similar shape (planar shape) of the conductive layer 13. it can. For example, the receiving layer 12 may cover the entire first surface 11a of the paper sheet 11, or may cover only a partial region of the first surface 11a, or only a partial region. In this case, the receiving layer 12 may or may not be patterned.

The shape (planar shape) of the conductive layer 13 when viewed in plan so that the conductive layer 13 is viewed 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 region. In the case where the conductive layer 13 is coated, the conductive layer 13 may or may not be patterned.
For example, the patterned conductive layer 13 is useful as a circuit. When the surface of the conductive layer 13 opposite to the receiving layer 12 side (which may be referred to as “first surface” in this specification) 13a is relatively large, the first surface 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 within the range not impairing the effects of the present invention, a part of the configuration is changed, deleted, or added in the one shown in FIG. 1. It may be a thing.

  For example, the conductive laminate 1 shown in FIG. 1 includes the receiving layer 12 and the conductive layer 13 on the first surface 11a. However, the conductive laminate of the present embodiment is a layer other than these 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 include a coating layer that covers the conductive layer 13 on the first surface 13 a of the conductive layer 13. Examples of the coating layer include, but are not limited to, a laminated structure of the paper sheet 11, the receiving layer 12, and the conductive layer 13, particularly a protective layer for protecting the conductive layer 13.

Further, the conductive laminate 1 may include 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 adhesion layer for adhering two adjacent layers and an adhesive layer for adhering two adjacent layers.

In addition, the conductive laminate 1 is formed on the other surface of the paper sheet 11 (the surface opposite to the receiving layer 12 side, which may be referred to as “second surface” in this specification) 11b. A layer may be provided. Examples of the layer on the second surface 11b include the same layers as any of the layers on the first surface 11a.
For example, when the conductive laminate 1 includes one or both of a receiving layer and a conductive layer on the second surface 11b, the receiving layer and the conductive layer are on the first surface 11a. It may be 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.

  In addition, the conductive laminate 1 illustrated in FIG. 1 may further include another base material separately from the base material 11 on the second surface 11 b of 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 such that the receiving layer is provided in direct contact with the paper sheet, like the conductive laminate 1 shown in FIG. 1, and the conductive layer is directly on the receiving layer. What is provided in contact is preferable.
Next, each configuration of the conductive laminate 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 paper 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, and synthetic paper.

The paper sheet may be composed of one layer (single layer) or may be composed of two or more layers. When the paper sheet consists of a plurality of layers, these layers may be the same as or different from each other, and the combination of these 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. Means that only a part of the layers may be the same ”, and“ a plurality of layers are different from each other ”means that“ at least one of the constituent materials and thickness of each layer is different from each other ”. Means.

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, further preferably 100 to 1000 μm, for example, any of 100 to 500 μm and 100 to 300 μm. There may be. When the thickness of the paper sheet is equal to or more than the lower limit value, the structures of the receiving layer and the conductive layer can be more stably maintained. When the thickness of the paper sheet is not more than the above upper limit value, the handleability of the conductive laminate as the target product becomes better.
When the paper sheet is composed of a plurality of layers, the total thickness of each layer may be set to the thickness of the preferable paper sheet.

JAPAN TAPPI Paper Pulp Test Method No. Although measured according to 5-2: 2000, the Oken air permeability of the paper sheet (in this specification, it may be abbreviated as “Oken air permeability”) is not particularly limited, It is preferably 5000 seconds or longer, and may be, for example, 10,000 seconds or longer, 30000 seconds or longer, and 100,000 seconds or longer. When a paper sheet having the Oken type air permeability equal to or higher than the lower limit is used, the conductivity of the conductive layer becomes higher.
On the other hand, the upper limit value of the Oken air permeability is not particularly limited.

<Receptive layer>
The receiving layer preferably contains polyurethane and is mainly composed of polyurethane.
For example, the receiving layer may contain only polyurethane (consisting of polyurethane), or in addition to polyurethane, a component that does not correspond to any of polyurethane and solvent (in this specification, “others” It may contain the component (1) ”.
Polyurethane is a resin having 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 penetration of this component into the paper sheet. It is guessed.

The polyurethane is not particularly limited as long as it is an oligomer or polymer having a urethane bond (a bond represented by the formula “—NH—C (═O) —O—”).
Examples of the polyurethane include 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”). And a polyurethane that does not fall under either an anionic polyurethane or a cationic polyurethane (in the present specification, it may be referred to as “nonionic polyurethane”). An 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 receptor layer. Good.

  Only one type of polyurethane contained in the receiving layer may be used, or two or more types may be used, and in the case of two or more types, the combination and ratio thereof can be arbitrarily adjusted.

The other component (1) can be arbitrarily selected according to the purpose and is not particularly limited.
As other component (1), a well-known additive etc. are mentioned, for example.
As said additive, the thing similar to the nitrogen-containing compound in the silver ink composition mentioned later is mentioned, for example.

  The other component (1) contained in the receiving layer may be only one type, or two or more types, and in the case of two or more types, the combination and ratio thereof can be arbitrarily adjusted.

The content of polyurethane in 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. Any of the above may be used. The electroconductivity of the said conductive layer becomes higher because content of the said polyurethane is more than the said lower limit.
On the other hand, the polyurethane content of the receiving layer is 100% by mass or less.

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

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, for example, any of 10 g / m ² or more, 15 g / m ² or more, and 20 g / m ² or more. May be. The electroconductivity of the said conductive layer becomes higher because the quantity of the said polyurethane on a paper sheet is more than the said lower limit.

The upper limit value 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 produced 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 one of the above lower limit value and upper limit value. In one embodiment, the amount of the polyurethane on the paper sheet is preferably 6 to 35 g / m ² , more preferably 6.5 to 35 g / m ² , for example, 10 to 35 g / m ² , 15 to 35 g. / ^{m 2,} and may be any of 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 includes a plurality of layers, the plurality of layers may be the same as or different from each other, and the combination of these layers is not particularly limited.

  The receiving layer is formed by adhering a composition for forming a receiving layer containing the polyurethane to the surface on which the receiving layer is to be formed, and with respect to the composition layer (composition layer for receiving layer). It can be formed by performing a drying process.

◎ Receptive layer forming composition Examples of the receiving layer forming composition include, for example, the polyurethane, a solvent, and, if necessary, the other component (1) (component not corresponding to any of polyurethane and solvent). The thing containing is mentioned. Other components (1) are as described above.

The said solvent which the composition for receiving layer formation contains will not be specifically limited if the effect of this invention is not impaired.
Examples of the solvent include water and organic solvents.

  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 Amide (chain amide) such as (DMF) and N, N-dimethylacetamide; Lactam (cyclic amide) such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; Ethyl acetate, n-butyl acetate and the like Esters such as diethyl ether, tetrahydrofuran (THF), 1,2-dimethoxyethane (dimethyl cellosolve), and the like; halogenated hydrocarbons such as dichloromethane and chloroform, and the like.

  The solvent contained in the composition for forming a receiving layer may be only one kind, may be two or more kinds, and in the case of two or more kinds, the combination and ratio thereof can be arbitrarily adjusted. . For example, the two or more types of solvents may be a mixed solvent (water-based mixed solvent) of water and one or two or more types of organic solvents, or a mixed solvent containing only two or more types of organic solvents (non-solvent). An aqueous mixed solvent) may be used.

In the composition for forming a receiving layer, the content ratio of components that do not vaporize at normal temperature is usually the same as the content ratio 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 components other than the solvent ([content of the polyurethane in the composition for forming a receiving layer (% by mass)] / [receiving layer] The total content (% by mass) of components other than the solvent of the composition for forming 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 or more.
In the present specification, “normal temperature” means a temperature that is not cooled or heated, that is, a normal temperature, and examples thereof include a temperature of 15 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 so that, for example, the handleability of the composition is improved.
For example, the content of the solvent in the composition for forming a receiving layer may be preferably 30 to 85% by mass, but this is an example.

Production method of receiving layer forming composition The receiving layer forming composition is 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 the blending of each component, the obtained product may be used as it is as a receiving layer forming composition, or if necessary, a product obtained by subsequent known purification operations may be used as a receiving layer forming composition. .

At the time of blending each component, all the components may be added and then mixed, or some components may be mixed while being added sequentially, or all components may be mixed while being added sequentially. Good.
The mixing method is not particularly limited, a method of mixing by rotating a stirrer or a stirring blade; a method of mixing using a mixer, a three-roller, a kneader, a bead mill or the like; a method of mixing by adding ultrasonic waves, etc. What is necessary is just to select suitably from a well-known method.

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

Method for Using Receptor Layer-Forming Composition The receiving layer-forming composition can be attached to the target product by a known method such as a printing method or a coating method.

  Examples of the printing method include screen printing method, flexographic printing method, offset printing method, dip printing method, ink jet printing method, dispenser printing method, jet dispenser printing method, gravure printing method, gravure offset printing method, The pad printing method etc. are mentioned.

  Examples of the coating method include 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; Examples of the method used include a method using a coating device such as a slot die.

What is necessary is just to perform the drying process of the composition for receptor layer formation (composition layer for receptor layer formation) by a well-known method. For example, the drying treatment may be performed under normal pressure, reduced pressure, or blowing conditions, and may be performed under air or under an inert gas atmosphere.
The temperature at the time of the drying process is not particularly limited, and may be either a heat drying process or a room temperature drying process. 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 the paper sheet is adjusted by adjusting the amount of the composition for the receiving layer to be adhered to the target location or the blending amount of the polyurethane or the like in the composition for the receiving layer. And the thickness of the receiving layer can be adjusted.

<Conductive layer>
The conductive layer includes a liquid composition (in this specification, sometimes referred to as “conductive layer forming composition”) in which a component for forming the conductive layer (conductive layer forming component) is blended. What was formed using was preferable.
The conductive layer is formed by adhering the composition for forming a conductive layer to a surface on which the conductive layer is to be formed, and forming a composition layer on the composition layer (composition layer for forming a conductive layer). It can be formed by appropriately selecting a solidification process such as a heating (firing) process.

  The conductive layer is preferably a metal layer.

The formation amount of the conductive layer 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 according to the purpose, and is not particularly limited, but 4 g / m It is preferably ² or more, more preferably 5 g / m ² or more, still more preferably 6 g / m ² or more, for example, 10 g / m ² or more, 20 g / m ² or more, 30 g / m ^2. As described above, it may be 40 g / m ² or more and 50 g / m ² or more. The electroconductivity of a conductive layer becomes higher because the formation amount of the said conductive layer is more than the said lower limit.
Here, “the amount of conductive layer formed on the receiving layer” is synonymous with the amount of conductive layer formed on the paper sheet (the amount of conductive layer present on the unit area (1 m ² ) of the paper sheet). It is.

The upper limit of the formation amount of the conductive layer 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 from the viewpoint that the flexibility of the conductive laminate is further improved and the conductive laminate can be manufactured at a lower cost.

The formation amount of the conductive layer on the receiving layer can be appropriately adjusted within a range set by arbitrarily combining any one of the above lower limit value and upper limit value. In one Embodiment, the formation amount of the said conductive layer becomes like this. Preferably it is 4-70 g / m < ² >, More preferably, it is 5-70 g / m < ² >, More preferably, it is 6-70 g / m < ² >. 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 may be used.

  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 as or different from each other, and the combination of these layers is not particularly limited.

The thickness of the conductive layer may be appropriately selected according to the purpose and is not particularly limited.
The thickness of the conductive layer is preferably 0.01 to 20 μm. The electroconductivity of a conductive layer becomes higher because the thickness of a conductive layer is more than the said lower limit. When the thickness of the conductive layer is not more than the above upper limit value, the flexibility of the conductive laminate is further improved, and the conductive laminate can be produced 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 the preferable thickness of the conductive layer.

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

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

  The surface resistance value of the conductive layer can be appropriately adjusted within a range set by arbitrarily combining any one 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 25 Ω / □, more preferably 0.05 to 20 Ω / □, such as 0.05 to 10 Ω / □ and 0.05. It may be any of ˜6Ω / □.

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

  The reflectance of light with a wavelength of 550 nm of metallic silver (silver layer) formed using the silver ink composition is set by arbitrarily combining any one of the above lower limit values and any upper limit value. Within the range, it can be adjusted appropriately. For example, the reflectance of the light is preferably 50 to 90%, for example, any of 55 to 90%, 60 to 90%, 65 to 90%, 70 to 90%, and 75 to 90%. May be. However, these are examples of the reflectance of the light.

The composition for forming a conductive layer The conductive layer forming composition 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 and the metal forming material to be blended may be only one kind, two or more kinds, and when two or more kinds, the combination and ratio thereof are It can be adjusted as desired.

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

  The metal forming material to be blended may be any material that has a corresponding metal atom (element) and generates a metal by structural change such as decomposition. Examples of such metal forming materials include metal salts, metal complexes, and compounds having a metal-carbon bond. The metal salt, metal complex, and compound having a metal-carbon bond may be any of a metal compound having an organic group (organic metal compound) and a metal compound having no organic group (inorganic metal compound). . Among these, 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 this 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 such an extent that the metal layer can be regarded as apparently made of only 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 a metal layer is 100 mass%, 99.9 mass%, 99.8 mass%, 99.7 mass%, 99.6 mass%, 99.5 mass%, 99. Although it can be set as any of 4 mass%, 99.3% mass%, 99.2 mass%, and 99.1 mass%, it is not limited to these.

  Hereinafter, a method for forming a metal layer (conductive layer) in the case where a silver ink composition containing a metal silver forming material is used as the metal ink composition will be described. In the same way, the metal layer can be formed.

Preferable metal silver forming materials include, for example, organic silver compounds. The organic silver compound is a compound that has an organic group and a silver atom in one molecule and generates metallic silver by a structural change such as decomposition.
That is, the silver ink composition preferably contains an organic silver compound, for example, an organic silver compound and a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms. It 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 in which silver carboxylate and a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms are blended (in this specification, “silver” Ink composition (I) ”), a silver ink composition containing silver carboxylate and not containing a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms (this specification) In this case, an organic silver complex, a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms, and a nitrogen-containing compound are blended. Examples thereof include a silver ink composition (sometimes referred to as “silver ink composition (III)” in the present specification).
Hereinafter, each silver ink composition will be described in detail.

* Silver ink composition (I)
In the silver ink composition (I), as the organic silver compound, silver carboxylate (a silver salt of carboxylic acid) is blended, and further, a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms is blended. .

[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 the silver carboxylate is not particularly limited.

  In this embodiment, silver carboxylate may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios are adjusted arbitrarily. it can.

The silver carboxylate is represented by the following general formula (1) β-ketocarboxylate silver (hereinafter sometimes abbreviated as “β-ketocarboxylate (1)”) and the following general formula (4). It is preferable that it is 1 type (s) or 2 or more types selected from the group which consists of silver carboxylate (Hereinafter, it may abbreviate as "silver carboxylate (4).").
In the present specification, the simple description of “silver carboxylate” is not limited to “silver β-ketocarboxylate (1)” and “silver carboxylate (4)”, unless otherwise specified. It is intended to 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 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a phenyl group, a hydroxyl group, an amino group, or a general formula “R ¹ -CY” in which one or more hydrogen atoms may be substituted with a substituent. ¹ ₂ − ”,“ CY ¹ ₃ − ”,“ R ¹ —CHY ¹ — ”,“ R ² O— ”,“ R ⁵ R ⁴ N— ”,“ (R ³ O) ₂ CY ¹ — ”or“ R ⁶ —C (═O) —CY ¹ ₂ — ”;
Y ¹ is each independently a fluorine atom, a chlorine atom, a bromine atom or a hydrogen atom; R ¹ is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group; R ² is an aliphatic having 1 to 20 carbon atoms R ³ is an aliphatic hydrocarbon group having 1 to 16 carbon atoms; R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms; R ⁶ is An aliphatic hydrocarbon group having 1 to 19 carbon atoms, a hydroxyl group or a group represented by the formula “AgO—”;
X ¹ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a phenyl group or benzyl group in which one or more hydrogen atoms may be substituted with a substituent, a cyano group, N - phthaloyl-3-aminopropyl group, 2-ethoxyethyl vinyl group, or the general formula ^{"R 7} O -", ^{"R 7} S -", ^"R 7 -C (= O) -" or ^"R 7 -C ( ═O) —O— ”;
R ⁷ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, a thienyl group, or a phenyl group or diphenyl group in which one or more hydrogen atoms may be substituted with a substituent. )

（式中、Ｒ^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. And one or more of the methylene groups may be substituted with a carbonyl group.)

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

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

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

Examples of the alkenyl group in R include a group in which one single bond (C—C) between carbon atoms of the alkyl group in R is substituted with a double bond (C═C).
Examples of the 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 _{(-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, cyclopentenyl group and the like.

Examples of the alkynyl group in R include a group in which one single bond (C—C) between carbon atoms of the alkyl group in R is substituted with a triple bond (C≡C).
Examples of such alkynyl group include ethynyl group (—C≡CH), propargyl group (—CH ₂ —C≡CH), and the like.

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

In the phenyl group in R, one or more hydrogen atoms may be substituted with a substituent. Preferable examples of the substituent include a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, a monovalent group formed by bonding the aliphatic hydrocarbon group to an oxygen atom, fluorine An atom, a chlorine atom, a bromine atom, a hydroxyl group (—OH), a cyano group (—C≡N), a phenoxy group (—O—C ₆ H ₅ ) and the like can be mentioned. 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, the plural substituents may be the same as or different from each other.
As said aliphatic hydrocarbon group which is a substituent, the thing similar to the said aliphatic hydrocarbon group in R except the point which is C1-C16 is mentioned, for example.

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

R ¹ in R is an aliphatic hydrocarbon group having 1 to 19 carbon atoms or a phenyl group (C ₆ H ₅ —). Examples of the aliphatic hydrocarbon group for R ¹ include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 19 carbon atoms.
R ² in R is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, and examples thereof include the same as the aliphatic hydrocarbon group in R.
R ³ in R is an aliphatic hydrocarbon group having 1 to 16 carbon atoms. Examples of the aliphatic hydrocarbon group for R ³ include those similar to the aliphatic hydrocarbon group for R except that the aliphatic hydrocarbon group has 1 to 16 carbon atoms.
R ⁴ and R ⁵ in R are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms. That is, R ⁴ and R ⁵ may be the same or different from each other, and the aliphatic hydrocarbon group in R ⁴ and R ⁵ is, for example, the above in R except that it has 1 to 18 carbon atoms. The thing similar to an aliphatic hydrocarbon group is mentioned.
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 for R ⁶ include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 19.

R is, among these, a linear or branched alkyl group, the general formula ^{"R 6 -C (= O) -CY} 1 2 - " group represented by be a hydroxyl group or a phenyl group preferable. R ⁶ is preferably a linear or branched alkyl group, a hydroxyl group, or a group represented by the formula “AgO—”.

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

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

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

In the general formula (1), two X ^{1 s} may be bonded as one group through a double bond with a carbon atom sandwiched between two carbonyl groups. Examples of such X ¹ include a group represented by the formula “═CH—C ₆ H ₄ —NO ₂ ”.

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

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

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

  The β-ketocarboxylate (1) is decomposed at a low temperature of preferably 60 to 210 ° C., more preferably 60 to 200 ° C. without using a reducing agent known in the art, as described later, Metal silver can be formed. And (beta) -ketocarboxylate (1) decomposes | disassembles at lower temperature and forms metallic silver by using together with a reducing agent.

  In the present invention, the β-ketocarboxylate (1) may be used alone or in combination of two or more, and when two or more are used in combination, their combination and ratio are as follows: Can be adjusted arbitrarily.

(Silver carboxylate (4))
The silver carboxylate (4) is represented by the general formula (4).
In the formula, R ⁸ 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 for R ⁸ include the same aliphatic hydrocarbon groups as those described above for R except that the number of carbon atoms is 1 to 19. However, the aliphatic hydrocarbon group for R ⁸ preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

When the aliphatic hydrocarbon group for R ⁸ has a methylene group (—CH ₂ —), one or more of the methylene groups may be substituted with a carbonyl group. The number and position of the methylene groups that may be substituted with a carbonyl group are not particularly limited, and all 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 alkylene group in which a plurality of groups represented by the formula “—CH ₂ —” are linked. And a group represented by the formula “—CH ₂ —”.

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), isobutyric acid silver _{((CH 3) 2 CH-} C (= O) -OAg), hexane silver 2-ethylhexyl _(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) —CH ₂ —C (═O) —OAg) is preferable. Also, 2 of the silver oxalate (AgO-C (= O) -C (= O) -OAg) and malonic silver _{(AgO-C (= O)} -CH 2 -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) it is also preferred.

  Even when silver carboxylate (4) is used, as with the case of using β-ketocarboxylate (1), the silver ink composition (I) is subjected to solidification treatment such as drying treatment or heating (firing) treatment. In the formed conductor (metal silver), the concentration of the remaining raw materials and impurities can be further reduced. And silver carboxylate (4) is decomposed | disassembled at lower temperature by using together with a reducing agent, and forms metallic silver.

  In this invention, silver carboxylate (4) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios are arbitrary. Can be adjusted.

The silver carboxylate is silver 2-methylacetoacetate, silver acetoacetate, silver 2-ethylacetoacetate, silver propionylacetate, silver isobutyrylacetate, silver pivaloylacetate, silver caproylacetate, silver 2-n-butylacetoacetate, 2-benzylacetoacetate Silver acetate, silver benzoyl acetate, silver pivaloyl acetoacetate, silver isobutyryl acetoacetate, silver acetone dicarboxylate, silver pyruvate, silver acetate, silver butyrate, silver isobutyrate, silver 2-ethylhexanoate, silver neodecanoate, silver It is preferable that it is 1 type, or 2 or more types selected from the group which consists of silver acid silver and silver malonate.
Among these silver carboxylates, silver 2-methylacetoacetate, silver acetoacetate, silver isobutyrylacetate and silver pivaloylacetate are excellent in compatibility with a nitrogen-containing compound (especially an amine compound) described later, and are silver ink compositions. This is 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, and more preferably 8% by mass or more. When the silver content is in such a range, the formed conductive layer (silver layer) has better quality. The upper limit of the silver content is not particularly limited as long as the effects of the present invention are not impaired, but it is preferably 25% by mass in consideration of the handleability of the silver ink composition (I).
In the present specification, “silver derived from carboxylate” is synonymous with silver in silver carboxylate compounded at the time of production of silver ink composition (I), unless otherwise specified. After that, silver constituting the silver carboxylate, silver in the decomposition product generated by decomposition of silver carboxylate after blending, and silver itself (metal silver) generated by decomposition of silver carboxylate after blending The concept includes everything.

[Branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms]
The silver ink composition (I) contains the branched saturated aliphatic carboxylic acid (in this specification, sometimes abbreviated as “branched saturated aliphatic carboxylic acid”). A silver layer having 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 a 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.

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 in one molecule of the branched saturated aliphatic carboxylic acid is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1. .

In the branched 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 the 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 carboxy groups may be bonded to different carbon atoms, or two or three carboxy groups may be the same carbon atom. It may be bonded to.

In the branched 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 terminal carbon atom to which the main chain carboxy group is bonded, or the side to which the main chain carboxy group is bonded. It may be a carbon atom adjacent to the carbon atom at the terminal on the opposite side (second carbon atom from the terminal at the opposite side), or the carbon atom at the terminal to which the above carboxy group is bonded; The carbon atom in the main chain located between the carbon atom adjacent to the terminal carbon atom opposite to the side to which the carboxy group is bonded may be used.
Here, the “main chain” means a chain structure in the branched saturated aliphatic carboxylic acid having the maximum carbon number. When there are a plurality of chain structures having the maximum number of carbon atoms, any chain structure may be handled as the main chain. The carbon number of the main chain is always greater than or equal to 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 this specification, sometimes abbreviated as “monocarboxylic acid (6)”). .
R ³¹ —C (═O) —OH (6)
(In the formula, R ³¹ is a branched alkyl group having 7 to 9 carbon atoms.)

Examples of the branched alkyl group having 7 to 9 carbon atoms (monovalent saturated aliphatic hydrocarbon group) of R ³¹ include 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, etc. A branched alkyl group having 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-trimethyl Rupentyl group, 1,2,2-trimethylpentyl group, 2,2,3-trimethylpentyl group, 2,2,4-trimethylpentyl group, 1,3,3-trimethylpentyl group, 2,3,3-trimethyl A branched alkyl group having 8 carbon atoms such as a pentyl group, 3,3,4-trimethylpentyl group, 1-propylpentyl group, 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- Methylheptyl group, 4,6-dimethylheptyl 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- Limethylhexyl 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- Diethylpentyl group, 1,2-diethylpentyl group, 1,3-diethylpentyl group, 2,2-diethylpentyl group, 2,3-diethylpentyl group, 3,3-diethylpentyl group, 1-ethyl-1- Examples thereof include branched alkyl groups having 9 carbon atoms such as propylbutyl group and 2-ethyl-1-propylbutyl group.

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

The branched saturated aliphatic carboxylic acid has moderate reactivity that suppresses the reduction in gloss and conductivity of metallic silver (silver layer), and is difficult to volatilize from the silver ink composition (I). Thus, the silver ink composition (I) has an appropriate boiling point that is easily vaporized during the solidification treatment, and has particularly suitable characteristics for improving the effects described above.
For example, the boiling point of the branched saturated aliphatic carboxylic acid is preferably 180 to 270 ° C, more preferably 200 to 260 ° C, and particularly preferably 215 to 255 ° C. Since the boiling point of the branched chain saturated aliphatic carboxylic acid is not less than the lower limit, volatilization of the branched chain saturated aliphatic carboxylic acid from the silver ink composition (I) is suppressed, and the branched chain saturated fat is reduced. The effect obtained by using the group carboxylic acid is more remarkably obtained. In addition, since the boiling point of the branched saturated aliphatic carboxylic acid is not more than the above upper limit value, the branched saturated aliphatic carboxylic acid in the metallic silver obtained by the solidification treatment of the silver ink composition (I) Residue is suppressed, and metallic silver having more favorable characteristics such as high glossiness and conductivity is obtained.

Particularly preferred branched saturated aliphatic carboxylic acids (for example, monocarboxylic acid (6)) are neodecanoic acid (C ₉ H 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.
In the present specification, neodecanoic acid means a mixture of isomers of a saturated aliphatic monocarboxylic acid having 10 carbon atoms, and a branched saturated aliphatic monocarboxylic acid having 10 carbon atoms is always contained in the mixture. included. Thus, neodecanoic acid does not mean only one compound.
And the combination and ratio of 2 or more types of C10 saturated aliphatic monocarboxylic acids in neodecanoic acid can be arbitrarily adjusted.

  A branched 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 combination and ratio are arbitrarily adjusted. it can.

As described above, the silver ink composition (I) has higher glossiness and electrical conductivity due to the solidification treatment of the silver ink composition (I) by blending the branched saturated aliphatic carboxylic acid. Metal silver can be formed. The reason is not clear, but is presumed as follows.
That is, in the silver ink composition (I) attached to the surface on which the silver layer is to be formed, silver ions (Ag ⁺ ) are generated from the silver carboxylate. In this case, oxygen is coordinated to silver ions (Ag ⁺ ... O) by the initial solidification treatment of the silver ink composition (I). Next, silver oxide (Ag ₂ O) is generated from silver ions coordinated with oxygen by solidification treatment such as drying treatment or heating (firing) treatment of the silver ink composition (I) for forming metallic silver. Here, in the case of a silver ink composition not containing a branched saturated aliphatic carboxylic acid, the by-produced silver oxide is contained in the metallic silver finally produced by the solidification treatment of the silver ink composition. It is presumed that the metallic silver is reduced in gloss as a result of impurities, and the conductivity is also reduced. On the other hand, in the case of the silver ink composition (I) in which the branched saturated aliphatic carboxylic acid is blended, the branched saturated aliphatic carboxylic acid reacts with silver oxide, so that the number of carbon atoms is 8 to 8. 10 branched-chain saturated aliphatic carboxylic acid silver salts (sometimes abbreviated as “branched saturated aliphatic carboxylic acid silver” in the present specification). This branched chain saturated aliphatic carboxylic acid silver is the above-mentioned carboxylic acid silver (4), and is finally obtained by solidifying the silver ink composition (I) in the same manner as the carboxylic acid silver compounded from the beginning. Metallic silver (silver layer) is produced. As described above, by using the silver ink composition (I) of the present embodiment, the silver oxide produced due to the solidification treatment of the silver ink composition (I) is converted into the action of the branched saturated aliphatic carboxylic acid. Therefore, it is presumed that metallic silver having higher glossiness and conductivity can be formed by being converted into metallic silver itself instead of impurities that are a cause of lowering of metallic gloss and conductivity.

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

Some carboxylic acids other than the branched saturated aliphatic carboxylic acid can form metallic silver having higher gloss and conductivity, like the branched saturated aliphatic carboxylic acid.
Such a carboxylic acid other than the branched saturated aliphatic carboxylic acid (in the present specification, sometimes referred to as “other carboxylic acid”) may be a monovalent carboxylic acid, or a divalent or higher valent 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 reducing group such as a formyl group (—C (═O) —H). The silver ink composition (I) formed by blending with other carboxylic acid not containing such a group is suppressed in production of insoluble matter derived from silver carboxylate during its storage, and has higher handleability.

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

  The boiling point of the other carboxylic acid is preferably 150 to 290 ° C, and may be any of 155 to 280 ° C, 160 to 270 ° C, and 160 to 260 ° C, for example. When the boiling point of the other carboxylic acid is equal to or higher than the lower limit, 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. Is obtained. Further, when the boiling point of the other carboxylic acid is not more than the above upper limit, the remaining 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, Metal silver having more favorable characteristics such as high conductivity can be obtained.

  The said other carboxylic acid may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be adjusted arbitrarily.

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

[Nitrogen-containing compounds]
The silver ink composition (I) is preferably one in which a nitrogen-containing compound is further blended in addition to the silver carboxylate and the branched saturated aliphatic carboxylic acid.
The nitrogen-containing compound is an amine compound having 25 or less carbon atoms (hereinafter sometimes abbreviated as “amine compound”), a quaternary ammonium salt having 25 or less carbon atoms (hereinafter abbreviated as “quaternary ammonium salt”). Ammonia, an ammonium salt obtained by reacting an amine compound having 25 or less carbon atoms with an acid (hereinafter sometimes abbreviated as “ammonium salt derived from an amine compound”), and ammonia reacting with an acid. Or one or more selected from the group consisting of ammonium salts (hereinafter sometimes abbreviated as “ammonium salts derived from ammonia”). That is, the nitrogen-containing compound to be blended may be only one type, or two or more types, and in the case of two or more types, 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 primary amine, secondary amine, and tertiary amine. The quaternary ammonium salt has 4 to 25 carbon atoms. The amine compound and the quaternary ammonium salt may be either chain or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or ammonium salt moiety (for example, the nitrogen atom constituting the amino group (—NH ₂ ) of the primary amine) may be one, or two or more.

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

The alkyl group constituting the monoalkylamine may be linear, branched or cyclic, and examples of such an alkyl group include the same alkyl groups as those described above for 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 examples of preferable monoalkylamine include 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.

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

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

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

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

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

The alkyl group that constitutes the dialkylamine is the same as the alkyl group that constitutes the monoalkylamine, and is a linear or branched alkyl group having 1 to 9 carbon atoms, or 3 to 7 carbon atoms. A cyclic alkyl group is preferred. Two alkyl groups in one molecule of dialkylamine may be the same as or different from each other.
Specific examples of preferable dialkylamines 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. Two aryl groups in one molecule of diarylamine may be the same as or different from each other.

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

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

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

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

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

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

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

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

When the alkyl group constituting the monoalkylamine has a substituent, the alkyl group has an aryl group as a substituent, a linear or branched alkyl group having 1 to 9 carbon atoms, or a substituent As for it, it is preferable that it is a C3-C7 cyclic alkyl group which has a C1-C5 alkyl group. Specific examples of the monoalkylamine having such a substituent include 2-phenylethylamine, benzylamine, 2,3-dimethylcyclohexylamine, and the like.
In the aryl group and 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 a halogen atom include 2-bromobenzylamine. Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

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

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

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

(Ammonium salts derived from amine compounds)
In this 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 may be 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. It is not limited.

(Ammonium salt derived from ammonia)
In the present invention, the ammonium salt derived from ammonia is an ammonium salt formed by reacting ammonia with an acid. Here, examples of the acid include the same ones as in the case of the ammonium salt derived from the amine compound.
Examples of the ammonium salt derived from ammonia include ammonium chloride, but are not limited thereto.

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. In the case where two or more kinds are used in combination, the combination and ratio thereof can be arbitrarily adjusted.
And as said nitrogen-containing compound, you may use individually 1 type selected from the group which consists of said amine compound, quaternary ammonium salt, ammonium salt derived from amine compound, and ammonium salt derived from ammonia, Two or more kinds may be used in combination, and when two or more kinds are used in combination, their combination and ratio 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 amount of the second nitrogen-containing compound to the amount of the first nitrogen-containing compound in the silver ink composition (I) is 0 mol%. It is larger and is preferably less than 18 mol%, more preferably 1 to 17 mol%. When the ratio is in such a range, for example, a thin-line silver layer can be formed more stably.

  When the nitrogen-containing compound is used, the amount of the nitrogen-containing compound in the silver ink composition (I) is preferably 0.3 to 15 moles per mole of the silver carboxylate. It is more preferably 3 to 12 mol, particularly preferably 0.3 to 8 mol, for example, any of 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 within such a range, the silver ink composition (I) is further improved in stability 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 saturated aliphatic carboxylic acid.

  The alcohol is preferably an acetylene alcohol represented by the following general formula (2) (hereinafter sometimes 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 each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.)

(Acetylene alcohol (2))
The acetylene alcohol (2) is represented by the general formula (2).
In the formula, R ′ and R ″ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which one or more hydrogen atoms may be substituted with a substituent.
The alkyl group having 1 to 20 carbon atoms in R ′ and R ″ may be linear, branched or cyclic, and when it is cyclic, it may be monocyclic or polycyclic. Examples of the alkyl group in R ′ and R ″ include the same alkyl groups as in R.

  Examples of the substituent in which the hydrogen atom of the phenyl group in R ′ and R ″ may be substituted include, for example, a saturated or unsaturated monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, the aliphatic A monovalent group formed by bonding an aromatic hydrocarbon group to an oxygen atom, a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, a cyano group, a phenoxy group, 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. In the phenyl group having a substituent, the number and position of the substituents are not particularly limited, and when the number of substituents is plural, the plural substituents may be the same as or different from each other.

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

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

  When acetylene alcohol (2) is used, the compounding amount of acetylene alcohol (2) in the silver ink composition (I) is 0.01 to 0.7 mol per mol of the organic silver compound. Preferably, it is 0.02-0.5 mol, more preferably 0.02-0.3 mol. When the amount of the acetylene alcohol (2) is within such a range, the stability of the silver ink composition (I) is further improved.

  The said alcohol may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be adjusted arbitrarily.

[Other ingredients (2)]
The silver ink composition (I) is a component other than any of the silver carboxylate, branched saturated aliphatic carboxylic acid, nitrogen-containing compound, and alcohol (in the present specification, "Other components (2)") may be blended.
The other component (2) in the silver ink composition (I) can be arbitrarily selected according to the purpose and is not particularly limited. Preferred examples of the other component (2) include solvents other than alcohols, and can be arbitrarily selected according to the type and amount of the compounding components.
In the silver ink composition (I), the other component (2) may be used alone, in combination of two or more, or in combination of two or more. Combinations and ratios can be arbitrarily adjusted.

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

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

  What is necessary is just to select suitably the compounding quantity of the said other component (2) in a silver ink composition (I) according to the kind of said 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 amount of the solvent to the total amount of the components 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, in the silver ink composition (I), the ratio of the blending amount of the other component (2) to the total blending component is 10% by mass. Or less, 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, the silver ink composition (I) sufficiently exhibits its effect even when the other component (2) is not blended. .

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

○ Manufacturing method of silver ink composition (I) The silver ink composition (I) is obtained by blending the silver carboxylate, the branched saturated aliphatic carboxylic acid, and, if necessary, other components. can get. After the blending of each component, the obtained one may be used as it is as the silver ink composition (I), or the one obtained by performing a known refining operation as necessary as the silver ink composition (I). Also good. In this embodiment, in particular, when β-ketocarboxylate (1) is used as the carboxylate, no impurities that reduce glossiness and conductivity are generated at the time of blending the above components, or this The production amount of such impurities can be suppressed to a very small amount. Therefore, even when the silver ink composition (I) that has not been purified is used, metallic silver having sufficient gloss and conductivity can be obtained.

  The blending order of each component is not particularly limited. As an example of a preferable blending method of each component, a method of blending a branched saturated aliphatic carboxylic acid at the end can be mentioned. That is, as an example of a preferable production method of the silver ink composition (I), the production of blending all the components other than the branched saturated aliphatic carboxylic acid and then blending the branched saturated aliphatic carboxylic acid last. A method is mentioned.

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

The temperature at the time of blending is not particularly limited as long as each blending component does not deteriorate, but is preferably −5 to 60 ° C. And the temperature at the time of mixing | blending is good to adjust suitably so that the mixture obtained by mix | blending may become the viscosity which is easy to stir according to the kind and quantity of a mixing | blending component.
Further, the blending time is not particularly limited as long as each blending component does not deteriorate, but it 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, printing that requires thickening of ink such as flexographic printing method, screen printing method, gravure printing method, gravure offset printing method, pad printing method, etc. Suitable for law application.

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

  Carbon dioxide gas may be supplied by various known methods of blowing gas into the liquid, and a suitable supply method may be selected as appropriate. For example, a method in which one end of a pipe is immersed in a supply object, the other end is connected to a carbon dioxide gas supply source, and carbon dioxide gas is supplied to the supply object through the pipe. At this time, the carbon dioxide gas may be supplied directly from the end of the pipe. For example, a plurality of voids that can serve as gas flow paths, such as a porous one, are provided to diffuse the introduced gas. A gas diffusion member that can be discharged as minute bubbles may be connected to the end of the pipe, and the carbon dioxide gas may be supplied through the gas diffusion member. Moreover, you may supply carbon dioxide gas, stirring a supply target object. By doing in this way, carbon dioxide can be supplied efficiently.

  The supply amount of the carbon dioxide gas may be appropriately adjusted according to the amount of the supply object, 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 the 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. In addition, although the viscosity at 20-25 degreeC of silver ink composition (I) was demonstrated here, the temperature at the time of use of silver ink composition (I) is not limited to 20-25 degreeC, Arbitrary Can be selected. In addition, “viscosity” in the present specification means a value measured 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 supply object, and is 1 mL / min or more. More preferably. The upper limit value of the flow rate is not particularly limited, but is preferably 40 mL / min per 1 g of the supply object in consideration of handling properties and the like.
The carbon dioxide gas supply time may be appropriately adjusted in consideration of the required supply amount and flow rate of carbon dioxide gas.

  It is preferable that the temperature of the supply object at the time of carbon dioxide gas supply is 5-70 degreeC, It is more preferable that it is 7-60 degreeC, It is especially preferable that it is 10-50 degreeC. When the temperature is equal to or higher than the lower limit value, carbon dioxide can be supplied more efficiently, and when the temperature is equal to or lower than the upper limit value, the silver ink composition (I) having better quality with fewer 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 a suitable range while considering each value. For example, even if the temperature is set lower, the carbon dioxide gas flow rate is set higher, the carbon dioxide gas supply time is set longer, or both are performed efficiently. Can supply carbon. Moreover, even if the flow rate of carbon dioxide gas is set to a small value, the carbon dioxide gas can be efficiently produced by increasing the temperature, setting the carbon dioxide gas supply time longer, or both. Can supply. That is, a silver ink of good quality can be obtained by flexibly combining the numerical values in the above numerical range exemplified as the flow rate of carbon dioxide gas and the temperature at the time of carbon dioxide gas supply while considering the supply time of carbon dioxide gas. Composition (I) can be obtained efficiently.

The supply of carbon dioxide gas is preferably performed while stirring the supply object. By doing in this way, the supplied carbon dioxide gas diffuses more uniformly in the supply object, and carbon dioxide can be supplied more efficiently.
The stirring method at this time may be the same as in the case of the mixing method at the time of producing the above silver ink composition (I) not using carbon dioxide.

The supply of dry ice (solid carbon dioxide) may be performed by adding dry ice to the supply object. The total amount of dry ice may be added all at once, or may be added stepwise (continuously across a time zone during which no addition is performed).
What is necessary is just to adjust the usage-amount of dry ice in consideration of the supply amount of said carbon dioxide gas.
During and after the addition of dry ice, it is preferable to stir the supply object. For example, it is preferable to stir in the same manner as in the production of the silver ink composition (I) without using carbon dioxide. By doing in this way, carbon dioxide can be supplied efficiently.
The temperature at the time of stirring may be the same as that at the time of supplying carbon dioxide gas. Moreover, what is necessary is just to adjust stirring time suitably according to 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 or 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 addition, in the silver ink composition (I) whose viscosity is higher than usual by supplying carbon dioxide as described above, metallic silver is formed from at least a part of the silver carboxylate, and this metallic silver is precipitated. is there. At this time, when the viscosity of the silver ink composition (I) is high, aggregation of the precipitated metal silver is suppressed, and the dispersibility of the metal silver in the obtained silver ink composition (I) is improved. A 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, no carbon dioxide is supplied to the silver ink composition (I). As compared with the silver layer when using, the gloss is higher, the conductivity is higher (volume resistivity is lower), the surface roughness is lower, and more preferable characteristics are obtained.

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

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

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

The hydrazine as the reducing agent may be a monohydrate (H ₂ N—NH ₂ .H ₂ O).

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

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

Method for producing silver ink composition (II) The silver ink composition (II) is a silver ink except that the branched saturated aliphatic carboxylic acid is not blended and the reducing agent is blended as necessary. 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 above-mentioned silver carboxylate and optional components as necessary. Here, the “optional component” means a reducing agent, a component that does not fall under 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.

* Silver ink composition (III)
In the silver ink composition (III), an organic silver complex is blended as the organic silver compound, and further, a branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms (the branched saturated aliphatic carboxylic acid) and A nitrogen-containing compound is blended.
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 another nitrogen-containing compound, and an excess of the nitrogen-containing compound. In which the reaction solution in which the residual water remains and the branched saturated aliphatic carboxylic acid are included. More specific examples of such silver ink composition (III) include those obtained by further blending a branched saturated aliphatic carboxylic acid with the one described in Japanese Patent No. 5243409.
That is, examples of the silver ink composition (III) include a silver compound represented by the following general formula (91) (in this specification, sometimes abbreviated as “silver compound (91)”), A compound represented by the general formula (92) (in this specification, it may be abbreviated as “nitrogen-containing compound (92)”) and a compound represented by the following general formula (93) (in this specification) An organic silver complex obtained by reacting with one or more nitrogen-containing compounds selected from the group consisting of “nitrogen-containing compound (93)”), and And a liquid composition containing the nitrogen-containing compound and a branched 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 perchlorate group, a tetrafluoroborate group, an acetylacetonate group, a carboxylate group, and derivatives thereof; R ^{101 to} R ¹¹¹ are each independently , A hydrogen atom, an aliphatic or alicyclic alkyl group having 1 to 30 carbon atoms or an aryl group, a functional group-substituted alkyl group or aryl group, and a group selected from a heterocyclic group, However, R ^{101 to} R ¹¹¹ are not all hydrogen atoms.)

  Examples of the organic silver complex include a compound represented by the following general formula (95) -1 (sometimes abbreviated as “organic silver complex (95) -1” in this specification), and the following general formula And a compound represented by formula (95) -2 (in this specification, sometimes 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。）

(Wherein R ^{101 to} R ¹¹¹ are the same as above; m ₁₀₁ and m ₁₀₂ are each independently 0.5 to 1.5.)

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

  A silver compound (91) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be adjusted arbitrarily.

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 content of silver is within 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 effects of the present invention are not impaired, but it 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 during the production of the silver ink composition (III) unless otherwise specified. After the blending, the silver constituting the silver compound (91), the silver in the reaction product produced by the reaction of the silver compound (91) after the blending, and the silver produced by the reaction of the silver compound (91) after the blending It is a concept that includes all of itself (metal silver).

[Nitrogen-containing compound (92)]
The nitrogen-containing compound (92) is an ammonium carbamate compound.
In the nitrogen-containing compound (92), R ^{101 to} R ¹⁰⁵ are each independently a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, 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 Methoxyphenyl group, cyanophenyl group, a tolyl group, or a benzyl group, or a group which is partially substituted in these groups. However, R ^{101 to} R ¹⁰⁵ are not all hydrogen atoms.

Examples of the nitrogen-containing compound (92) include ethylammonium ethylcarbamate, isopropylammonium isopropylcarbamate, n-butylammonium n-butylcarbamate, isobutylammonium isobutylcarbamate, tert-butylammonium tert-butylcarbamate, 2-ethylhexylammonium 2- Ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutyl ammonium dibutyl carbamate, dioctadecyl ammonium dioctadecyl carbamate, methyl decyl ammonium methyl decyl carbamate, hex Methyleneimine ammonium hexamethyleneimine carbamate, morpholino ammonium morpholino carbamate, pyridinium ethylhexylcarbamate, benzylammonium benzylcarbamate, triethoxysilylpropyl ammonium triethoxysilylpropyl carbamate, and the like.
Among these nitrogen-containing compounds (92), 2-ethylhexylammonium 2-ethylhexylcarbamate is excellent in compatibility with the silver compound (91) and is particularly suitable for increasing the concentration of the silver ink composition (III). Furthermore, it is mentioned as being particularly suitable for reducing the surface roughness of metallic silver.

  A nitrogen-containing compound (92) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be adjusted arbitrarily.

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

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

  Examples of the nitrogen-containing compound (93) include ethylammonium ethyl carbonate, isopropylammonium isopropyl carbonate, n-butylammonium n-butylcarbonate, isobutylammonium isobutylcarbonate, tert-butylammonium tert-butylcarbonate, 2-ethylhexylammonium 2- Ethyl hexyl carbonate, 2-methoxyethyl ammonium 2-methoxyethyl carbonate, 2-cyanoethyl ammonium 2-cyanoethyl carbonate, octadecyl ammonium octadecyl carbonate, dibutyl ammonium dibutyl carbonate, dioctadecyl ammonium dioctadecyl carbonate, methyl decyl ammonium methyl decyl carbonate , Hexamethylene iminyl ammonium hexamethylene iminyl carbonate, morpholino ammonium morpholino carbonate, benzyl ammonium benzyl carbonate, triethoxysilylpropyl ammonium triethoxysilylpropyl carbonate.

  A nitrogen-containing compound (93) may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be adjusted arbitrarily.

  The nitrogen-containing compound (93) can be produced by a known method, for example, 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 type or two or more types of nitrogen-containing compounds (92), or only one type or two or more types of nitrogen-containing compounds (93). It may be both one type or two or more types of nitrogen-containing compounds (92) and one type or two or more types of 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 in a nitrogen atmosphere Or in a pressurized state without using a solvent.

[solvent]
The reaction may be performed 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, 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. .
A solvent may be used individually by 1 type, may use 2 or more types together, and when using 2 or more types together, those combinations and ratios can be adjusted arbitrarily.

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

  In the reaction, the total amount of the nitrogen-containing compound (92) and the nitrogen-containing compound (93) is 1 to 4 times the molar amount of the silver atom in the silver compound (91) to be used ( [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) It is preferable.

[Branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms]
The branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms in the silver ink composition (III) is the branched saturated aliphatic carboxylic acid having 8 to 10 carbon atoms in the silver ink composition (I). A chain saturated aliphatic carboxylic acid).
The branched saturated aliphatic carboxylic acid in the silver ink composition (III) is presumed to exhibit 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 mole per mole of the silver atom in the organic silver complex. It is more preferably 0.02 to 0.7 mol, and particularly preferably 0.03 to 0.4 mol. Even if the amount of the branched saturated aliphatic carboxylic acid is in such a range, even when printing is performed while heating the object to be printed, the effect of forming metallic silver with high gloss is obtained. Get higher.
When a precursor compound of the organic silver complex is used during the production of the silver ink composition (III), the branched saturated aliphatic carboxylic acid per mole of silver atoms in the precursor compound is used. A compounding quantity can be made into the above-mentioned numerical range.

  As described above, the silver ink composition (III) is blended with the branched saturated aliphatic carboxylic acid, so that when the silver ink composition (III) is solidified, it has glossiness and conductivity. Can form higher metallic silver. Although the reason is not certain, it is presumed that it is the same as the case of the silver ink composition (I) described above.

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

○ Method of using silver ink composition It is not limited to the case of silver ink composition (I), silver ink composition (II) and silver ink composition (III), and the silver ink composition can be printed or coated. It can be made to adhere to a target object by well-known methods, such as.

Examples of the printing method include screen printing method, flexographic printing method, offset printing method, dip printing method, ink jet printing method, dispenser printing method, jet dispenser printing method, gravure printing method, gravure offset printing method, The pad printing method etc. are mentioned.
Among these, the printing method is preferably an ink jet printing method.

  Examples of the coating method include 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; A method using a coating apparatus such as a slot die; a spray method, and the like.

  When a silver layer is formed by solidifying treatment such as drying treatment or heating (firing) treatment of the silver ink composition after adhesion, the silver ink composition is adhered to the intended 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 formation amount of the silver layer and the thickness of the silver layer can be adjusted.

  What is necessary is just to carry out by a well-known method, when drying a silver ink composition. That is, the drying treatment may be performed, for example, under normal pressure, reduced pressure, or air blowing conditions, and may be performed under air or an inert gas atmosphere. Also, the drying temperature is not particularly limited, and may be either heat drying or room temperature drying. As a preferable drying method when the heat treatment is unnecessary, for example, a method of drying in the atmosphere at 18 to 30 ° C. can be mentioned.

  When the silver ink composition is heated (baked), the conditions may be adjusted as appropriate according to the type of ingredients of the silver ink composition. Usually, it is preferable that heating temperature is 60-370 degreeC, and it is more preferable that it is 70-280 degreeC. Although what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 1 minute-24 hours, and it is more preferable that it is 1 minute-12 hours. Among the organic silver compounds, the silver carboxylate, particularly the β-ketocarboxylate (1) is different from a metal silver forming material such as silver oxide, for example, without using a reducing agent known in the art. Also decomposes at low temperatures. Reflecting such 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 an object having low heat resistance and heated (baked), the heating temperature is preferably less than 130 ° C, more preferably 125 ° C or less, and 120 ° C or less. It is particularly preferred that

  The method for the 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 thermal head, heating by far infrared irradiation, heating by spraying a high-temperature gas, heating by high frequency irradiation, dielectric heating, or the like. Further, the heat treatment may be performed in the atmosphere, in an inert gas atmosphere, or may be performed under humidified conditions. The heat treatment may be performed under normal pressure, reduced pressure, or increased pressure.

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

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

  The heat treatment of the silver ink composition may be performed in two stages. For example, in the first stage heat treatment, there is a method in which the silver ink composition is mainly dried rather than the formation of metallic silver, and in the second stage heat treatment, the formation of metallic silver is performed to the end.

In the first-stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition, but is preferably 60 to 120 ° C, and may be 70 to 110 ° C. . Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 5 second-12 hours, and it is more preferable that it is 30 second-2 hours.
In the second stage heat treatment, the heating temperature may be appropriately adjusted according to the type of compounding component of the silver ink composition so that metallic silver is satisfactorily formed, but it should be 60 to 280 ° C. Preferably, it is 70-260 degreeC. Moreover, what is necessary is just to adjust a heating time according to heating temperature, Usually, it is preferable that it is 1 minute-12 hours, and it is more preferable that it is 1 minute-10 hours.
When the silver ink composition is attached to an object having low heat resistance and is heated (baked), the heating temperature in the first and second stage heat treatment is preferably less than 130 ° C. More preferably, it is not higher than 120 ° C, particularly preferably not higher than 120 ° C.

The heat treatment of the silver ink composition described so far is performed in the gas phase. However, when the heat treatment of the silver ink composition is performed in two steps, the heat treatment in the second step is performed in the gas phase. You may carry out in a liquid phase instead of inside. The silver ink composition that has been completely or partially dried through the first stage heat treatment can be subjected to the second stage heat treatment without impairing its shape by contacting with the heated liquid. And it is preferable to perform the heat processing in the liquid phase of the 2nd step after performing the heat processing of the 1st step of a silver ink composition by immersing a silver ink composition in the heated liquid. The heating temperature and heating time in the heat treatment in the liquid phase are the same as the heating temperature and heating time in the second-stage heat treatment described above.
The heated liquid is preferably hot water (heated water), and the second stage heat treatment is performed by immersing the silver ink composition subjected to the first stage heat treatment in hot water, that is, by hot water bathing. Preferably it is done.
When the second stage heat treatment is performed in the liquid phase, the metallic silver formed by this heat treatment may be further dried.

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

  When heat treatment under humidified conditions is employed, it is particularly preferable that the heat treatment of the silver ink composition is performed by the following two-step method. That is, in the first stage heat treatment, the silver ink composition is mainly dried under the non-humidified condition as described above, rather than the formation of metallic silver, and in the second stage heat treatment, under the humidified condition, As described above, it is particularly preferable to heat-treat the silver ink composition by forming metal silver to the end.

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.
It is preferable that the heating temperature at the time of the heat treatment under the second-stage humidification condition performed after the heat treatment under the first-stage non-humidification condition is 60 to 140 ° C, and 70 to 130 ° C. Is more preferable. The heating time is preferably 1 minute to 2 hours, more preferably 1 minute to 1 hour, and particularly preferably 1 minute to 30 minutes.
When the silver ink composition is attached to an object having low heat resistance and heated (baked), the heat treatment under the first stage non-humidifying condition and the heat treatment under the second stage humidifying condition are performed. The heating temperature is preferably less than 130 ° C, more preferably 125 ° C or less, and particularly preferably 120 ° C or less.

<< Method for Producing Conductive Laminate >>
The conductive laminate of the present embodiment includes, for example, a step of forming a receiving layer on a paper sheet (hereinafter sometimes abbreviated as “receiving layer forming step”) and a conductive layer on the receiving layer. And a process (hereinafter sometimes abbreviated as “conductive layer forming process”).
FIG. 2 is a cross-sectional view for schematically explaining the method for producing the conductive laminate 1 shown in FIG.

<Receptive layer formation process>
In the receiving layer forming step, the receiving layer 12 is formed on the paper sheet 11 as shown in FIG.
The receiving layer 12 forms the composition layer by adhering the composition for forming a receiving layer containing polyurethane to the first surface 11a of the paper sheet 11 which is the surface on which the receiving layer is to be formed. It can form by performing a drying process with respect to (receptive layer forming composition layer).
The method for adhering the composition for forming the receiving layer to the object and the method for the drying treatment are as described above.

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

  Here, the manufacturing method has been described by taking the conductive laminate 1 shown in FIG. 1 as an example, but other conductive laminates of the present embodiment can be manufactured by the same method according to the structure. . For example, the conductive laminate including the other layer can be appropriately added to a suitable location at a suitable timing in the above-described manufacturing method, 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 following examples.

Table 1 shows the paper sheets used in Examples or Comparative Examples, and Table 2 shows compositions for forming the receiving layer.
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 having a polyvinyl alcohol (PVA) -containing layer as a receiving layer on the surface in advance.
The polyurethanes in the composition for forming a receiving layer in Table 2 are all anionic polyurethanes.

[Example 1]
<Manufacture of conductive laminate>
(Manufacture of silver ink composition)
In a beaker, 2-ethylhexylamine (6.53 times mole amount based on 2-methylacetoacetate silver described later) and 3,5-dimethyl-1-hexyn-3-ol (hereinafter abbreviated as “DMHO”) (There is a 0.10-fold molar amount with respect to 2-methylacetoacetate silver described later) and mixed, and while rotating and stirring the mechanical stirrer, the liquid temperature is 40 ° C. or lower. Then, 2-methylacetoacetic acid silver was added to dissolve each compounding component, and stirring was continued for one day at room temperature.
Subsequently, neodecanoic acid (0.13-fold molar amount with respect to silver 2-methylacetoacetate) is dropped into this stirring liquid and stirred so that the liquid temperature becomes 30 ° C. or lower, whereby a composition for forming a conductive layer is formed. As a result, a silver ink composition (I) -1 was obtained.
In addition, “Surfinol 61” manufactured by Nissin Chemical Co., Ltd. was used as DMHO, and “Versatic 10” manufactured by Japan Chemtech Co., Ltd. was used as neodecanoic acid. The same applies to the following examples, comparative examples, and reference examples.

Table 3 shows the types and mixing ratios of the respective components. In Table 3, “nitrogen-containing compound (molar ratio)” means the compounding amount (number of moles) of the nitrogen-containing compound per mol of the organic silver compound ([number of moles of nitrogen-containing compound] / [organic silver compound] Number of moles]). "Alcohol (molar ratio)" also means the blending amount (number of moles) of alcohol per mole of blending organic silver compound ([number of moles of alcohol] / [number of moles of organic silver compound]). Similarly, “branched saturated aliphatic carboxylic acid (molar ratio)” is the blended amount (number of moles) of branched saturated aliphatic carboxylic acid per mole of the organic silver compound ([branched saturated fat] Number of moles of group carboxylic acid] / [number of moles of organic silver compound]). Similarly, the “reducing agent (molar ratio)” is the compounding amount (number of moles) of reducing agent per mole 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 blending amount (number of moles) of solvent per mole of the organic silver compound ([number of moles of solvent] / [number of moles of organic silver compound]). In addition, the description of “-” in the column of the blending component / blending amount of the silver ink composition means that the component is not blended.
In this example, the “organic silver compound” means “silver β-ketocarboxylate (1)”.

(Manufacture of conductive laminate)
On one surface of the paper sheet (P1) -1, the receptor layer-forming composition (PU1) was manually applied with a rod bar and dried at 100 ° C. to form a receptor 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 “Resin amount (g / m ² )” in Table 4.
Then, using a spin coater, the silver ink composition obtained above was applied onto the surface of the receptor layer, and the coated sheet was 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 with a spin coater were 2000 rpm for 5 seconds and then 3000 rpm for 5 seconds. The formation amount of the silver layer was 7.5 g / m ² , and the thickness of the silver layer was 0.15 μm. The formation amount of the silver layer is shown in the column of “conductive layer formation amount (g / m ² )” in Table 4.
Thus, a conductive laminate was obtained.

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

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

[Reference Example 1]
In place of the paper sheet (P1) -1, a film made of polyethylene terephthalate (PET) (Lumirror 188E22, thickness 188 μm, Oken type air permeability of 200000 seconds or more), and a composition for forming a receiving layer A conductive laminate was produced and evaluated in the same manner as in Example 1 except that it was not used. The results are shown in Table 4.
Here, the composition for forming a conductive layer (silver ink composition) is applied directly on the surface of a PET film.

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

[Comparative Example 15]
As shown in Table 3, a silver ink composition was produced in the same manner as in Example 1 except that neodecanoic acid was not used, and silver ink composition (II) -1 was obtained.
And it replaced with silver ink composition (I) -1, and manufactured and evaluated a conductive laminated body by the same method as the case of the comparative example 10 except the point which used this silver ink composition (II) -1. did. The results are shown in Table 5.

[Example 21]
<Manufacture of conductive laminate>
(Manufacture of silver ink composition)
In a beaker, 2-ethylhexylamine (1.45-fold mol amount relative to 2-methylacetoacetate silver described later), n-hexane (1.63-fold mol amount based on 2-methylacetoacetate silver described later), Were added in this order, and silver 2-methylacetoacetate was added to the beaker while rotating and stirring the mechanical stirrer so that the liquid temperature was 50 ° C. or lower.
After completion of the addition of silver 2-methylacetoacetate, formic acid (0.5 molar amount relative to silver 2-methylacetoacetate) was dropped over 10 minutes using a syringe pump in a beaker while maintaining the same state. Then, after completion of the dropwise addition of formic acid, the mixture was further stirred for 1.5 hours.
Subsequently, 3,5-dimethyl-1-hexyn-3-ol (DMHO) (0.10-fold molar amount with respect to silver 2-methylacetoacetate) and 4-ethyl-1-octin-3-ol (hereinafter, “ A mixture of (sometimes abbreviated as “EOO”) (0.004 times mole amount relative to silver 2-methylacetoacetate) is added to a beaker, and after the addition is completed, the mixture is further stirred for 5 minutes. Silver ink composition (II) -2 was obtained as the silver ink composition.
In addition, as EOO, the thing by Tokyo Chemical Industry Co., Ltd. was used.
Table 3 shows the types and mixing ratios of the respective components.

(Manufacture of conductive laminate)
The point that this silver ink composition (II) -2 was used in place of the silver ink composition (I) -1, and the conductive layer formation amount (formation amount of the silver layer) was changed to 7.3 g / m ² and 55. .3 g / m ² and the point that the composition for forming the receiving layer (PU1) was used instead of the composition for forming the receiving layer (PU2). A conductive laminate was produced.

<Evaluation of conductive laminate>
(Measurement of sheet resistance of silver layer)
The conductive laminate obtained above was evaluated in the same manner 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 are provided with a receiving layer containing polyurethane, so that the surface resistance value of the silver layer (conductive layer) is 18 Ω / □ or less (0. 07-18Ω / □), and the conductivity of the silver layer was high.
In the conductive laminates of Examples 1 to 21, the amount of resin (the 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, that is, sufficiently conductive. There is no problem that a conductive layer having a property cannot be formed. Actually, in the conductive laminate of Reference Example 1, the surface resistance value of the silver layer (conductive layer) was a low level of 8.1 Ω / □.
In the conductive laminates of the above-described examples, the surface resistance value of the silver layer (conductive layer) is often lower than that in the case of this reference example 1, and in general, this reference example 1 Was less than or equal to
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 include the receiving layer, and the silver layer did not substantially exhibit conductivity.
For the conductive laminates of Comparative Example 10 and Comparative Example 15, a paper sheet provided with a receiving layer containing polyvinyl alcohol (PVA) was used, but the silver layer showed substantially no conductivity.
Although the conductive laminate of Comparative Example 11 was provided with a receiving layer containing polystyrene, the surface resistance 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 a resin. Although the amount of these resins on the paper sheet was the same as in Comparative Example 11, the silver layer was not substantially conductive.

  The present invention is applicable to all conductive laminates using paper sheets such as circuit boards.

  DESCRIPTION OF SYMBOLS 1 ... Conductive laminated body, 11 ... Paper sheet, 11a ... 1st surface of a paper sheet, 12 ... Receiving layer, 12a ... 1st surface of a receiving layer, 13 ... Conductivity layer

Claims (4)

A paper sheet, a receiving layer provided on the paper sheet, and a conductive layer provided on the receiving layer,
A conductive laminate in which the receiving layer comprises polyurethane.   The conductive laminate according to claim 1, wherein the polyurethane has 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 any one of claims 1 to 3, wherein the conductive layer is formed using a silver ink composition containing an organic silver compound.

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